LABORATORY SOILS TESTINGThe falling-head test is generally used for less pervicus-* soils (fine...

REPRINT WITH CORRECTED COPY INCORPORATED

ENGINEER MANUAL EM 1110-2-1.90630 November 1970

ENGINEERING AND DESIGN

LABORATORY SOILS TESTING

'' •'' -'-U-.WV-'-- •••• ••71"'

HEADQUARTERS, DEPARTMENT OF THE ARMYOFFICE OF THE CHIEF OF ENGINEERS

EM 1110-2-190630 Nov 70

APPENDIX VII:

PE-RMEABIUTY'TESTS

1. DARCY'S LAW FOR FLOW OF WATER THROUGH SOIL. The flow ofwater through a soil medium is assumed to follow Darcy's law:

q = k i A

where q = rate of discharge through a soil of cross-sectional area Ak = coefficient of permeabilityi = hydraulic gradient: the loss of hydraulic head per unit

distance of flow

The application of Darcy's law to a specimen of soil in the laboratory isillustrated in Figure 1. The coefficient of permeability, k (often termed

• WATER SUPPLY

OVERFLOWTO MAINTAINCONSTANT HEAD

WHERE q = RATE Of DISCHARGEs QUANTITY Of FLOW. Q.

PER UNIT Or TIME, t

k * COEFFICIENT OFPERMEABILITY

i « HYDRAULIC GRADIENT

A * CROSS-SECTIONAL AREAOF SPECIMEN

GRADUATE

Figure 1. Flow of water through soil

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1r

EM 1110-2-1906Appendix VII30 Nov 70

"permeability"), is defined as the rate of discharge of water at a tern- ^

perature of 20 C under conditions of laminar flow '.hrough a unit cross-sectional area of a soil medium under a unit hydraulic gradient. Thecoefficient of permeability has the dimensions of a velocity and is usually"!expressed in centimeters per second. The permeability of a soil depends!primarily on the size and shape of the soil grains, the void ratio of thesoil, the shape and arrangement of the voids, and the degree of saturation?

Permeability computed on the basis of Darcy's law is limited to the .4conditions of laminar flow and complete saturation of the voids. In turbu^Jlent flow, the flow is no longer proportional to the first power of thehydraulic gradient. Unde'r conditions of incomplete saturation, the flow isin a transient state and is time-dependent. The laboratory procedurespresented herein for determining the coefficient of permeability are based-;on the Darcy conditions of flow. Unless otherwise required, the coefficientof permeability shall be determined for a condition of complete saturationof the specimen. Departure from the Darcy flow conditions to simulatenatural conditions is sometimes necessary; however, the effects of turbu-lent flow and incomplete saturation on the permeability should be recognize^and taken into consideration.2. TYPES OF TESTS AND EQUIPMENT, a. Types of Tests. (1) Constant)head test. The simplest of all methods for determining the coefficient ofpermeability is the constant-head type of test illustrated in Figure 1. Thistest is performed by measuring the quantity of water, Q, flowing throughthe soil specimen, the length of the soil specimen, L, the head of water,h, and the elapsed time, t. The head of water is kept constant throughout ":

the test. For fine-grained soils, Q is small and may be difficult tc mea-sure accurately. Therefore, the constant-head test is used principally for \coarse-grained soils (clean sands and gravels) with k values greater than "•about 10 X 10"4 cm per sec. „*

(2) Falling-head test. The principle of the falling-head test ,f,it illustrated in Figure 2. This test is conducted in the same manner as

VII-2

EM 1110-Z-1906Appendix VII

30 Nov 70

STANDPlPC -

OVERFLOW

jf r*s^~

(a) (b)

USING SETUP SHOWN IN (1). THE COEFFICIENT OF PERMEABILITY ISDETERMINED AS FOLLOWS:

USING SETUP SHOWN m (bi.OCTCAMINCO AS FOULOWS:

K{ * HEIGHT OF CAPILLARY RISC

O s INSIDE AREA OF STANOPIPE

A • CROSS-SECTIONAL AREA OF SPECIMEN

L & LENGTH OF SPECIMEN

h * HEIGHT OF WATER IN STANOPIPE ABOVE* DISCHARGE LEVEL MINUS KC AT TIME, t^

h. s HEIGHT OF WATER IN STANOPIPE ABOVEDISCHARGE LEVEL MINUS h^ AT TIME. t(

t x ELAPSED TIME, t, . t.

Figure Z. Principle of falling-head test

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EM 1110-2-1906Appendix Vlf30 Nov 70

If

ant-head test, except that the head of water is not maintainedconstant but is permitted to fall within the upper part of the specimencontainer or in a standpipe directly connected to the specimen. The qitity of water flowing through the specimen is determined indirectly bycomputation. The falling-head test is generally used for less pervicus-*soils (fine sands to fat clays) with k values less than 10 X 10"4 cmper sec.

b_. Equipment. The apparatus used for permeability testing ma'vary considerably in detail depending primarily on the condition andcharacter of the sample to be tested. Whether the sample is fine-graine'S'or coarse-grained, undisturbed, remolded, or compacted, saturated or ijnonsaturated will, influence the type of apparatus to be employed. Thebasic types of apparatus, grouped according to the type of specimen con-!tainer (permeameter), are as follows:

(1) Permeameter cylinders(2) Sampling tubes(3) Pressure cylinders j(4) Consolidometers j

The permeability of remolded cohesionless soils is determined in 'permeameter cylinders, while the permeability of undisturbed cohesion-less soils in a vertical direction can be determined using the sampling ij

-r*tube as a permeameter. The permeability of remolded cohesionless soils:is generally used to approximate the permeability of undisturbed cohesion-less soils in a horizontal direction. Pressure cylinders and consolidome-ters are used for fine-grained soils in the remolded, undisturbed, orcompacted state. Fine-grained soils can be tested with the specimen ;

oriented to obtain the permeability in either the vertical or horizontal di-rection. The above-listed devices are described in detail under theindividual test procedures. Permeability tests-utilizing the different typesjof apparatus, together with recommendations regarding their use, arediscussed in the following paragraphs.

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30 Nov 70

3. CONSTANT-HEAD PERMEABILITY TEST WITH PERMEAMETERCYLINDER. ±. Use. The constant-head permeability test with thepermeameter cylinder shall in general be used for determining the per-

meability of remolded samples of coarse-grained soils such as cleansands and gravels having a permeability greater than about 10 X 10" cmper sec.

b. Apparatus. The apparatus and accessory equipment shouldconsist of the following:

(1) A permeameter cylinder similar to that shown schemati-cally in Figure 3a. The permeameter cylinder should be constructed of atransparent plastic material. The inside diameter of the cylinder shouldbe not less than about 10 times the diameter of the largest soil particles,except when the specimenis encased ina rubber membrane as in the perme-ability test with pressure chamber, in which case the diameter of the cylin-der should be at least six times the diameter of the largest soil particles.

) COMSTAMT~MCAO A*»A«AT Ch) FAILINC-HCAD APPARATUS

Figure '3. Schematic diagram of constant-head and falling-headpermeability apparatus

VII-5


:'

Piezometer taps along the side of the permeameter within limits to be?cupied by the sample are advantageous in that the head loss within the'?sample is always measured across a fixed distance and rapid <tion of hydraulic gradient can be made.

(2) Perforated metal or plastic disks and circular wirescreens, 35 to 100 mesh, cut for a close fit inside The permeameter. if

(3) Class tubing, rubber or plastic tubing, stoppers, screwsclamps, etc., necessary to make connections as shown in Figure 3a.

(4) Filter materials such as Ottawa sand, coarse sand, andjgravel of various gradations.

(5) A device for maintaining a constant-head water supply.'̂(6) Deaired distilledf water. Tapwater contains dissolved?

air and gases which separate from solution in the initial layers of a test^Sspecimen of soil in the form of small bubbles. These bubbles reduce the'fpermeability of the soil by decreasing the void space available for theflow of water. The most common method for removing dissolved airfrom water is by boiling the water and then cooling it at reduced pres-sures. This method is applicable only with small quantities of water.Freshly distilled water also has a very negligible amount of air. Large -Squantities of deaired distilled water may be prepared and retained forsubsequent use by spraying distilled water in a fine stream into a con-tainer from which the air has been evacuated (see Tig. 4). Permeability Stests on saturated specimens should show no significant decrease in ;|

^permeability with time if properly deaired distilled water is used. How-.?ever, if such a decrease in permeability occurs during a test, then a pre-Jfilter, consisting of a layer of the same material as the test specimen, 'should be used between the deaired distilled water reservoir and the test •specimen to remove the air remaining in solution.t

T Demineralized water or tapwater when it is known to be relatively free ;of minerals may be used in place of distilled water.

t G. E. Bertram, An Experimental Investigation of Protective Filters,Soil Mechanics Series No. 7, Harvard University (Cambridge, Mass., •January 1940, reprinted May 1959). ;

vii- 6

I FU::?

EM 1110-2-1906Appendix Vff"

30 Nov 70

Figure 4. Schematic diagram of apparatus for preparingdeaired distilled water

(7) Manometer board with tubing leading from the piezom-eter taps. If piezometer taps are not provided, equipment to measurethe distance between the constant-head source and tailwater is required.

(8) Timing device, a watch or clock with second hand.(9) Graduated cylinder, 100-ml capacity.

(10) Centigrade thermometer, range 0 to 50 C, accurateto 0.1 C.

(11) Balance, sensitive to 0.1 g.(12) Oven (see Appendix I, WATER CONTENT - GENERAL).

VII-7


*-{111

- ; l

ilSli

(13) Scale, graduate-d in centimeters.£. Placement and Saturation of Specimen. Placement and satura?

lion of the specimen shall be done in the following steps:

(1) Record all identifying information for the specimen, suchias project, boring number, sample number, or other pertinent data, on a)data sheet (Plate VII-1 is a suggested form).

(2) Oven-dry the specimen. Allow it to cool and weigh to the)nearest 0.1 g. Record the oven-dry weight of material on the data sheet -1opposite W . The amount of material should be sufficient to provide a .specimen in the permeameter having a minimum length of about one to rw?times the diameter ol the specimen.

(3) Place a wire screen, with openings small enough to retain';the specimen, over a perforated disk near the bottom of the permeameterabove the inlet. The screen openings should be approximately equal to the.10 percent size of the specimen.

(4) Allow deaired distilled water to enter the water inlet of thepermeameter to a height of about 1/2 in. above the bottom of the screen, :taking care that no air bubbles are trapped under the screen.

(5) Mix the material thoroughly and place in the permeameterto avoid segregation. The material should be dropped just at the watersurface, keeping the water surface about 1/2 in. above the top of the soilduring placement. A funnel or a special spoon as shown in Figure 5 isconvenient for this purpose.

(6) The placement procedure outlined above will result in as

saturated specimen of uniform density although in a relatively loose condi- -•tion. To oroduce a higher density in the specimen, the sides of the perme-.-;ameter containing the soil sample are tapped uniformly along its circum-ference and length with a rubber mallet to produce an increase in density;however, extreme caution should be exercised so that fines are not put intosuspension and segregated within the sample. As an alternative to this pro-

cedure, the specimen may be placed in the in the dry using a funnel or

VII-8


30 Nov 70

spoon which permits the material

^to fall a constant height. The de-£ sired density may be achieved byV vibrating the specimen to obtain a

['specimen of predetermined height.Compacting the specimen in layersis not recommended as a film ofdust may be formed at the surfaceof the compacted layer which mightaffect the permeability results.

S- After placement, apply a vacuum* to the top of the specimen and per-

mit water to enter the evacuatedspecimen through the base of theperrneameter.

(7) After the speci-men has been placed, weigh theexcess material, if any, and thecontainer. The specimen weight isthe difference between the originalweight of sample and the weight ofthe excess'material. Care mustbe taken so that no material is lostd'-ring placement of the specimen.If there is evidence that material hasbeen lost, oven-dry the specimenand weigh after the test as a check.

(8) Level the top of the specimen, cover with a wire screensimilar to that used at the base, and fill the remainder of the permeameterwith a filter material.

(9) Measure the length of the specimen and inside diameter ofthe permeameter to the nearest 0.1 cm and record on the data sheet asinitial height and diameter of specimen.

(10) Test the specimen at the estimated natural void ratio or

Figure 5. Spoon for placingcohesionless soils

VII-9

i!;

13

Uij».

EM 1110-2-1906Appendix VII30 Nov 70-

ac a series of different void ratios, produced by increasing the amouivibration aft jr each permeability determination. Measure and recorlength (height) of specimen in the permeameter prior to each determination. Permeability determinations at three different void ratios areusually sufficient to establish the relation of void ratio to permeability.

d_. Procedure, The procedure shall consis't of the following stej^-j(1) Measure the distance, L., between the centers of the

piezometer taps to the nearest 0.01 cm and record on the data sheet.(2) Adjust the height of the constant-head tank to obtain the-

desired hydraulic gradient. The hydraulic gradient should be selected sothat the flow through the sp.ecjmen_is_laminar. The range of laminarconditions can be determined by plotting discharge versus hydraulic gra-.dient. A straight-line relation indicates laminar flow, while deviationsfrom the straight-line at high gradients indicate turbulent flow. Laminar -flaw_fo_r fine sands is limited to hydraulic_gradients less than approxi-mately 0.3j It is usually not practicable to achieve laminar flow forcoarser soils, and the tests generally should be run at the hydraulicgradient anticipated in the field.

(3) Open valve A (see Fig. 3a) and record the initial piezom- .«eter readings after the flow has become stable. Exercise care in building jup heads in the permeameter so that the specimen is not disturbed. 1

(4) After allowing a few minutes for equilibrium conditions >to be reached, measure by means of a graduate the quantity of discharge ;corresponding to a given time interval. Measure the piezometric heads •and the water temperature in the permeameter.

(5) Record the quantity of flow, piezometer readings, watertemperature, and the time interval during which the quantity of flow wasmeasured on the data sheet, Plate VII-1..

(6) Repeat steps (4) and (5) several times over a period ofabout 1 hr, and compute the coefficient of permeability corresponding toeach set of measured data. If there is no substantial change in the

VII-10

EM 1110-2-1906Appendix VII

30 Nov 70

permeability, then the computed permeability is probably reliable. If thereC is a slight decrease in the permeabili ty, then the permeability computed

from the initial measurements, rather than the average, should be reported,50 long as a plot of permeability versus time shows that the initial measure-ments are consistent with the subsequent measurements; a difference in

permeability may result from a change in density caused by inadvertentjarring of the specimen in the permeameter. If there is any substantial de-crease of the permeability with time, a prefilter should be used between thewater reservoir and the permeameter (see paragraph 3J>{6)). The criterion .for judging whether a change in the computed permeability is "substantial"depends on the desired accuracy of the coefficient of permeability.

(7)' 11 desired, reduce the void ratio as previously describedand repeat the constant-head test.

i e_. Computations. The computations consist ofthe following steps:(1) Compute the test void ratios in accordance with Appendix

U., UNIT WEIGHTS, VOID RATIO. POROSITY. AND DEGREE OF SATURA-TION. The specific gravity shall be estimated or determined in accord-ance with Appendix IV. SPECIFIC GRAVITY.

(Z) Compute the coefficient of permeability, k, by'means ofthe following equation: Q X L, X R

where20 " h X A X t

k - = coefficient of permeability, cm per sec at 20 CQ = quantity of flow, ccL = length of specimen over which head loss is measured, cm.

If piezometer taps are used, L = L . = distance betweenpiezometer taps, cm

R_ = temperature correction factor for viscosity of water ob-T tained from Table VU-1h = loss of head in length, L, or difference in piezometer

readings = h. . h,, cmA s cross-sectional area of specimen, sq cmt = elapsed time, sec

VII-11

SHC 1110-2-1906Appendix VII30.Nov 70

Correction Factor, Rj ,

Teoper&tuiDegree • C

0.01.0

• 2.03-0*.o

. • 5-06.07.08.09.0

10.011.012.013-01*.015-016.017.018.019.0

' 20.021.022.023-02*-025.026.027-028.029-0

. 30.031.032.033-03*.035.036.037-038.039.0*0.0*1.01.2.0*3.0

**.o*5.0*6.0*7.0*8.0*9.0

•«'— °a

1^7231.66*1.6111.5601-511l.*65l.*211.3791.3391.3011.2651.2301.1971.1651.135-1.1061.0771.0511.0251.0000.9760.9530.9310.9100.8890.8690.8500.8320.81*0.7970.7800.76*0.7*90.7330.7190.7050.6910.6780.6650.6530.6*10.6290.6180.6070.5960.5850.5750.5650.556

for

Table VTI-1

Viscbilty of Utter at Various Teaperaturea

Tenths of1

1.7771.7171.6591.6061.5551.507l.*6l•l.*171.3751.3361.2981.2621.2271.19*1.1621.1321.1031.0751.0*81.0220.9980.97*0.9510.929

o 9080.8870.8670.8*80.8300.8120.7950.7780.7630.7*70.7320.7180.70*0.6900.6770.66*0.6520.6390.6260.6160.6060.5950.58*0.57*0.56*0.555

2 31.771 OS?l..7'J.1.65*1.6011.5501..502l.*57l.*131.3711.3321..291*1.2581.2231.1901.1591.1291.1OO1.0721.1.0.0.0.0.0.0.0.o.o.0.0.0.o.o.0.o.0.0.0.0.0.

0*50209%9729*99279068858668*78288107937777617*6731716702689675663650

0.6380.o.0.o.0.0.0.0.

62761560*59^58357356*55*

1.705i.6*a1.5961.5*5l.*98l.*521.*O91.3671.3281.2901-2551.2201.1871.1561.1261.0971.0691.0*31.0170.9930.9690.9*70.9250.90*0.8830.86*0.8*50.8260.8090.7920.7750.7590.7**0.7290.7150.7010.6870.67*0.6610.6*90.6370.6260.61*O.6O30.5930.5820.5720.5630.553

kH7591.6991.6*31-5901.5*0l.*931.U.8l.liO*

'1.3631.32*1.2871.2511.2171.18*1.1531.1231.09*1.0671.0*01.0150.9900.9670.9**0.9230.9010.8810.8620.8*30.8250.8070.7900.77*0-7580.7*30.7280.7130.6990.6860.6730.6600.6*80.6360.62*0.6130.6020.5920.5810.5710.5620-552

Denrtei

1.753

l!6381.5851.535I.*fi8l.**3l.*001.3591.320

1.2*81.2131.1811.1501.1201.0911.06*1.0381.0120.9880.9650.9*20.9200.8990.8790.8600.8*10.8230.8050.7BS0.7720-7560.7*10.7260.7120.6980.6850.6720.6590.6*70.6350.6230.6120.6010-5910.5&00.5700.5610.551

i6

l!o881.6321.5SO1-531I.it8bl.*391.3961-3551.J171.2791.2*41.2101.1781.1*71.1171.0891.0611.0351.0100.9860.9620.9*O0.9180.8970.8770.8580.8390.8210.80*0.7870-7700-7550.7390.7250-TU0.6970.6830.6700.6580.6*60.63*0.6220.6110.6000-5900.5790.5690.5600-550

n*T1.6821.6271.5751-526l.*79l-*351-3921-3511-313

1.2*11.2071.1751.1**1.11*1.0861-0591.0331.0070.9830.9600.9380.9160.8950.8750.8560.8370.8190.8020.7850.7690.7530.7380.7230-7090.6950.6820.6690.6560.6U.0.6320.6210.6100.5990.5880.5780.5680.5590.5*9

" 81-7351.6761.6221.5701.521l.*75l.*301.3881.3*71.309

1.2371.2031.1711.1*11.1111.0831.0561.0301.0050.9810.9580.9360.91*0.8930.8736.85*0.8360.8160.8000-7830.7670.7520.7360.7220.7080.69*0.6810.6680.6550.6*30.6310.6200.6090.5980.5870.57T0.5670.5580.5*8

1-7291.6701.6161.565-1.516/I.*?©1

l.*261.3831.3*31-305

1.23*1.2001.1681.1381.1081.0801-0531.0271.0020-9790.9550-9330.9120.8910.8710.8520.83*0.8160.7980.7820-7660.7500.7350.7200.7060.6930.6790.6660.65*0.6*20.6300.6190.6080.5970.5860.5760.5660.5570.5*8

Conputed tnm Table 170 - Solthsonlan Phyaical Tables - 8th EditionCorrection factor, R_ , i* found by dividing the viscosity of vater at the test

temperature by the vl*co«ity of vater at 20 C.

V1I-12


30 Nov 70

_f. Presentation of Results. The coeff ic ient of permeability shallbe reported in units with coeff ic ients of 1.0, 1 X 10"4, and 1 X 10"' cm per

sec. The void ratio of the specimen shall be reported with all values of kThe coefficient of permeability, k, is logarithmically dependent upon thevoid ratio of the soil. Where k is determined at several void ratios, thetest results shall be presented on a semilogarithmic chart as shown infigure 6 in which k is plotted on the abscissa (logarithmic scale) and thevoid ratio is plotted on the ordirtate (arithmetic scale).

Figure 6. Relation between permeability and void ratiofor cohesionless soils

4. FALLING-HEAD PERMEABILITY TEST WITH PERMEAMETERCYLINDER. a_. Use. The falling-head test with the permeameter

t .0 -f /e'"5'

attf',m

EM 1110-Z-1906Appendix VII30 Nov 70

cylinder should in general be used for determining the permeability of

remolded samples of cohesionless soils having a permeability less thanabout 10 x tO"4 cm per sec.

b. Apparatus. The apparatus and accessory equipment should'consist of the following:

(1) A permeameter cylinder similar to that shown schemat*ically in Figure 3b, or modified versions thereof. The permeametercylinder should be constructed of a transparent plastic material. The iside diameter of the cylinder should be not less than about 10 times thediameter of the largest soil particles. The use of two piezometer taps,shown by Figure 3b, connected to a standpipe and discharge level tubeeliminates the necessity for taking into account the height of capillary ris?which would be necessary in the case of a single standpipe of small size.The height of capillary rise for a given tube and condition can be mea-sured simply by standing the tube upright in a beaker full of water. The j>size of standpipe to be used is generally based on experience with the ••!equipment used and soils tested. In order to accelerate testing, air pres£sure may be applied to the standpipe to increase the hydraulic gradient.

(2) Perforated metal or plastic disks and circular wire !screens, 35 to 100 mesh, cut for a close fit inside the permeameter.

(3) Class tubing, rubber or plastic tubing, stoppers, screw

clamps, etc., necessary to make connections as shown in Figure 3b.(4) Filter materials such as Ottawa sand, coarse sand, and

gravel of various gradations.(5) Deaired distilled water, prepared according to para-

graph 3b(6).(6) Manometer board or suitable scales for measuring levels

in piezometers or standpipe.(7) Timing device, a watch or clock with second hand.(8) Centigrade thermometer, range 0 to 50 C, accurate to 0.1

(9) Balance, sensitive to 0.1 g.

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30 Nov 70

(10) Oven (see Appendix I, WATER CONTENT - GENERAL).(11) Scale, graduated in centimeters.

£. Placement and Saturation of Specimen. Placement and satu-ration of the specimen shall be done as described in paragraph 3c_.Identifying information for the sample and test data shall be entered on

'» d*ta sheet similar to Plate VII-2.d_. Procedure. The procedure shall consist of the following steps:

(1) Measure and record the height of the specimen, L, andthe cross-sectional area of the specimen, A.

(2) With valve B open (see Fig. 3b), crack valve A andslowly bring the water level up to the discharge level of the permeameter.

(3) Raise thre head of water in the standpipe above the dis-charge level of the permeameter. The difference in head should not resultin an excessively high hydraulic gradient during the test. Close valvesA and B.

(4) Begin the test by opening valve B. Start the timer. Asthe water flows through the specimen, measure and record the height ofwater in the standpipe above the discharge level, ho, in centimeters, at

.time to, and the height of water above the discharge level, hf, incentimeters, at time t,. :

(5) Observe and record the temperature of the water in thepermeameter.

(6) Repeat the determination of permeability, and if the com-puted values differ by an appreciable amount, repeat the test until con-sistent values of permeability are obtained.

e. Computations. The computations consist of the following steps:(1) Compute the test void ratios as outlined in paragraph 3e(l).

(2) Compute the coefficient of permeability, k, by means ofthe following equation:

k= 2.303— —A t

VII-15

I" 'm

I

•4-

ill!Kdtti1;'-'a1


where a = inside area of standpipe, sq cmA = cross-sectional area of specimen, sq cm

L = length of specimen, cmt = elapsed time (tj - to), sec

h0 = height of water in standpipe above discharge level at :irt , cm . .Jo •••

h{ = height of water in standpipe above discharge level at timetf, cm ~

R_ = temperature correction factor for viscosity of water ob-tained from Table VII-1, degrees C

If a single standpipe of small diameter is used as shown in Figure 2, thiheight of capillary rise, hc, should be subtracted from the standpipereadings to obtain hQ and hj.

f. Presentation of Results. The results of the falling-headpermeability test shall be reported as described in paragraph 3_f.5. PERMEABILITY TESTS WITH SAMPLING TUBES. Permeabilitytests may be performed directly on undisturbed samples without removingthem from the sampling tubes. The sampling tube serves as the per-meameter cylinder. The method is applicable primarily to cohesionless;soils which cannot be removed from the sampling tube without excessivedisturbance. The permeability obtained is in the direction in which thesample was taken, i.e. generally vertical. The permeability obtained in a'vertical direction may be substantially less than that obtained in a hori- "

zontal direction.Permeability tests with sampling tubes may be performed under

constant-head or falling-head conditions of flow, depending on the esti-mated permeability of the sample (see paragraph 2a). The equipmentshould be capable of reproducing the conditions of flow in the constant-head or falling-head tests. It is important that all disturbed material ormaterial containing drilling mud be removed from the top and bottom ofthe sample. The ends of the sample should be protected by screens heldin place by perforated packers. The test procedure and computations are

VII-16

' *=i

> i


30 Nov 70

the same as those described previously for each test.PERMEABILITY TEST WITH PRESSURE CHAMBER. In the perme-

ability test with a pressure chamber, see Figure 7, a cylindrical specimenis confined in a rubber membrane and subjected to an external hydrostaticpressure during the permeability test. The advantages of this type oftest are: (a) leakage along the sides of the specimen, which would occurif the specimen were tested in a permeameter, is prevented, and (b) thespecimen can be tested under conditions of loading expected in the field.The test is Applicable primarily to cohesive soils in the undisturbed,

remolded, or compacted state. Complete saturation of the specimen, if itis not fully saturated initially, is practically impossible. Consequently,this test should be used only for soils that are fully saturated, unlessvalues of permeability are purposely desired for soils in an unsaturatedcondition. The permeability test with the pressure chamber is usuallyperformed as a falling-head test.

The permeability specimens for use in the pressure chamber generallyshould be 2.8 in. in diameter, as rubber membranes and eguipment forcutting and trimming specimens of this size are available for triaxialtesting apparatus (see Appendix X. TRIAXIAL COMPRESSION TESTS). Aspecimen length of about 4 in. is adequate. (The dimensions of a testspecimen may be varied if equipment and supplies are available to makea suitable test setup.) The pressure in the chamber should not be lessthan the maximum head on the specimen during the test. The other testprocedure and computations are the same as those described for thefalling-head test. The linear relation between permeability and void ratioon a semilogarithmic plot as shown in Figure 6 is usually not applicableto fine-grained soils, particularly when compacted. Other methods ofpresenting permeability-void ratio data may be desirable.7. PERMEABILITY TESTS WITH BACK PRESSURE.

SL. Description. Gas bubbles in the pores of a compacted or un-disturbed specimen of fine-grained soil will invalidate the results of the

.-/VII-17

m~ OT x. JS sr -.5


30 Nov 70

permeability tests described in the preceding paragraphs. It is knownthat an increase in pressure will cause a reduction .in volume of gas bub-bles and also an increased weight of gas dis-olved in water. To each de-

gree of saturation there corresponds a certain additional pressure (backpressure) which, if applied to the pore fluid of the specimen, will causecomplete saturation. The permeability test with back pressure is per-formed in a pressure chamber such as that shown in Figure 8, utilizingequipment that permits increasing the chamber pressure and pore pres-sure simultaneously, maintaining their difference constant. The methodis generally applicable to fine-grained soils that are not fully saturated.Apparatus and procedures have been described by A. Casagrandet andL. Bjerrum and J. Huder.t

l>. Procedure (see Fig. 8). The procedure shall consist of thefollowing steps:

(1) After having determined the dimensions and wet weightof the test specimen, place it in the triaxial apparatus, using the sameprocedure as for setting up a specimen for an R triaxial test with porepressure measurements except that filter strips should not be used(see para 7, APPENDIX X, TRIAXIAL COMPRESSION TESTS).

(2) Saturate the specimen and verify 100 percent saturationusing the procedure described in paragraph 7b, APPENDIX X, TRIAXIALCOMPRESSION TESTS. Burette "A" is utilized during this operation.

(3) With the drainage valves closed, increase the chamber

t Casagrande, A., "Third Progress Report on Investigation of StressDeformation and Strength Characteristics of Compacted Clays," SoilMechanics Series No. 70, Nov 1963, Harvard University, Cambridge,Mass., pp 30 and 31.

t Bjerrum, L. and Huder, J., "Measurement of the Permeability ofCompacted Clays." Proceedings, Fourth International Conference onSoil Mechanics and Foundation Engineering, London, Vol 1,Aug 1957, pp 6-8.

VII-19

Figure 8.. Schematic diagram of typical triaxlal compre.aion apparatus-,f°F;permeability to.t. with back.pra«iur«

EM 1110-2-1906Appendix VU

70

•JH

pressure to attain the desired effective consolidation pressure (chamberpressure minus back pressure). At zero elapsed time, open valves Eand F.

(4) Record time, dial indicator reading, and burette readingat elapsed times of 0, 15, and 30 sec, 1, 2, 4, 8, and 15 min, and 1, 2, 4,and 8 hr, etc. Plot the dial indicator readings and burette readings on anarithmetic scale versus elapsed time on a log scale. When the consoli-dation curves indicate that primary consolidation is complete, closevalves E and F.

(5) Apply a pressure to burette B greater than that inburette A. The difference between the pressures in burettes B and Ais equal to the head loss h; h divided by the height of the specimen afterconsolidation, L, is the hydraulic gradient. The difference between thetwo pressures should be kept as small as practicable, consistent with therequirement that the rate of flow be large enough to make accuratemeasurements of the quantity of flow within a reasonable period of time.Because the difference in the two pressures may be very small in com-parison to the pressures at the ends of the specimen, and because thehead loss must be maintained constant throughout the test, the differencebetween the pressures within the burettes must be measured accurately;a differential pressure gage is very useful for this purpose. The dif-ference between the elevations of the water within the burettes shouldalso be considered (1 in. of water = 0.036 psi of pressure).

(6) Open valves O and T. Record the burette readings at anyzero elapsed time. Make readings of burettes A and B and of temperature** various elapsed times (the interval between successive readings de-pends upon th'e permeability of the soil and the dimensions of the speci-men). Plot arithmetically the change in readings of both burettes versustime. Continue making readings until the two curves become parallel»nd straight over a sufficient length of time to accurately determine ther»te of flow (slope of the curves).

VII-21

EM 1UO-2-1906Appendix VII30 Nov 70

8 ! •

1

(7) If it is desired to determine the permeability at severalvoid ratios, steps 3 through 6 can be repeated, using different consolida-tion pressures in step 3.

(8) At the .end of the permeability determinations, close alldrainage valves and reduce the chamber pressure to zero; disassemblethe apparatus.

(9) Determine the wet and dry weights of the specimen.£. Computations. The computations consist of the following

• (1) Compute the test void ratios as outlined in para-steps

graph 3^(2) Computations of coefficients of permeability are the

same as those described for the constant-head permeability test.8. PERMEABILITY TESTS WITH CONSOLIDOMETER. A perme-ability test in a consolidometer (see Appendix VTfi. CONSOLIDATIONTEST) is essentially similar to that conducted in a pressure chamber,except that the specimen is placed within a relatively rigid ring and isloaded vertically. The test can be used as an alternate to the perme-ability test in the pressure chamber. The test is applicable primarilyto cohesive soils in a fully saturated condition. Testing is usually per-formed under falling-head conditions.

A schematic diagram of the consolidation apparatus set up for afalling-head permeability test is shown in Figure 9. Identifying informa-tion for the specimen and subsequent t'est data are entered on a data sheet £(Plate VH-3 is a suggested form). The specimen should be placed in thespecimen ring arid the apparatus assembled as outlined under Appen-dix Vm, CONSOLIDATION TEST. The specimen is consolidated underthe desired load and the falling-head test is performed as previouslydescribed. The

VII-22


30 Nov 70

Figure 9. Schematic diagram of falling-head device forpermeability test in consolidometer

net head on the specimen may be increased by use of air pressure; how-ever, the pressure on the pore water should not exceed 25 to 30 percentof the vertical pressure under which the specimen has consolidated. Dialindicator readings are observed before and after consolidation to permitcomputation of void ratios. The determination of the coefficient of perme-ability may be made in conjunction with the consolidation test, in whichcase the test is performed at the end of the consolidation phase under eachload increment. Computations are similar to those described for the

VII-23

N f i

jj

limij I

,

EM 1UO-2-1906Appendix VII30 Nov 70

falling-head test with the permeameter cylinder.

The permeability may also be determined indirectly from computations using data obtained during the consolidation tes'; however the as-sumptions on which the method is based are seldom satisfied, and conseSquently, the direct determination of permeability should be employedwhere reliable values of permeability are required.9. POSSIBLE ERRORS. Following are possible errors that would causinaccurate determinations of the coefficient of permeability:

a. Stratification or nonuniform compaction of cohesionless soils?If the specimen is compacted in layers,.any accumulation of fines at thesurface of the layers will reduce the measured coefficient of permeability*

b_. Incomplete initial saturation of specimen.c. Excessive hydraulic gradient. Oarcy's law is applicable only:

to conditions of laminar flow.d. Air dissolved in water. No other source of error is as

troublesome as the accumulation of air in the specimen from the flowing •?water. As water enters the specimen, small quantities of air dissolved Iin the water will tend to collect as fine bubbles at the soil-water interface'and reduce the permeability at this interface with increasing time. Themethod for detecting and avoiding this problem is described in paragraph3d_(6). (It should be noted that air accumulation will not affect the coef-ficient of permeability determined by the constant-head test if piezometertaps along the side of the specimen are used to measure the head loss.)

e. Leakage along side of specimen in permeameter. One majoradvantage to the use of the triaxial compression chamber for permeabilitytests (s-ee paragraphs 6 and 7) is that the specimen is confined by aflexible membrane which is pressed tightly against the specimen by thechamber pressure.

VII-24

1ii

EM 1110-2-1906Appendix V

30 Nov 7

CWCTWIT-HLAD PtSKEWJILITT TLTT

B1TV

Sacplc or Sp*cLa*a No.

•j Tiut pliu dry toll Dlaa*t<w of •pcclawa, ea

a tax* Ar»a of «p«el**a, •* ca

^ Dry 'Oil V» Initial bclfbt of •pteljM&, em

Specific frwrtty 0 InltUl vol of §p«, ee - Al

Vol of Mild*, ee • Vfl * G Yt Xaitlal void r»Uo -(V . V,)+ V§

DlJtanct b«tv««a plciOMtcr tap*, a

T««« Ho.

fcl«bt of BiwelMB, a L

Void r»tlo .(*L - Vj* V, •

JteadlAC of plM 1, e* i

Beadlnc tf pl*s 2, a b.

I«ad lMBt CM - B^ - hj h

Quantity of flovf ee 4

Oapa«d tla*, »«e t

Vat«r t«p*f*tax«, °C T

TlaeMlty eorwctioa factor"' *t

Cocfflelcot of p«a*abllityj2^ kg)

*»•

1

1> 11

0

A

L

T

t

^12

2. n

3

> }b

(1) Comctlea factor for n*eo.lry of v«tar at 20 C oMali»4 fro. t*U«'viZ-l.Q x L » K_

«»> " 3 , - l . x A . ? -

vten L • b*l«fat of Kp»LlMi or dlft«ae« WtvMa pl«ccact«r t«p* IT uMd.

PLATE VII-1

VII-25

1 .

VII-27

EM 1110-2-190630 Nov 70

APPENDIX X:

TRIAXIAL COMPRESSION TESTS

—— » DCVIATOR STREiia a, • CTj

a;

1. PRINCIPLES OF THE TRIAXIAL COMPRESSION TEST. The triaxial

compression test is used to measure the shear strength of a soil undercontrolled drainage conditions. In the basic triaxial test, a cylindrical

specimen of soil encased in a rubber membrane is placed in a triaxialcompression chamber, subjected to a confining fluid pressure, and thenloaded axially to failure. Connections at the ends of the specimen permitcontrolled drainage of pore water from the specimen. The procedurespresented herein apply only to the f

basic test conducted with limiteddrainage conditions, and do not in-

clude special types or variants of thistest. In general, a minimum of threespecimens, each 'under a differentconfining pressure, are tested to es-tablish the relation between shearstrength and normal stress. The testis called "triaxial" because the threeprincipal stresses are known andcontrolled. Prior to shear, the threeprincipal stresses are equal to thechamber fluid pressure. Duringshear, the major principal stress,7|, is equal to the applied axialstress (P/A) plus the chamberpressure, f^ (see Fig. 1). The ap-

SOILSPECIMEN

CMOSlSCCTIOMALAMI* or

IPCCmtH'A

plied axial stress, - ff istermed the "deviator stress." The

Figure 1. Diagram showingstresses during triaxial com-

pression test

X-l

EMAppendix X30 Nov 70

intermediate principal stress, o^, and the minor principal stress, 0-,-,-jare identical in the test, and are equal to the confining or chamber pres§jsure hereafter referred to as o-,.

A soil mass may be considered as a compressible skeleton of solidtjparticles. In saturated soils the void spaces are completely filled withijwater; in partially saturated soils the void spaces are filled with bothwater and air. Shear stresses are carried only by the skeleton of solidparticles, whereas the normal stress on any plane is carried by both the^solid particles and the pore water. In a triaxial test, the shear Strength'3is determined in terms of the total stress (intergranular stress plus p6r?|

.water pressure), unless (a) complete drainage is provided during the testgso that the pore pressure is equal to zero at failure, or (o) measurementsôf pore pressure are made during the test. When the pore pressure at -failure is known, the shear strength can be computed in terms of the stress

"^fcarried by the soil particles (termed effective or intergranular stress).În recent years, significant advances have been made in the techniques o£imeasuring pore pressures in the triaxial test and in the interpretation of;the data obtained; however, difficulties still exist in this respect. Pore'*pressure measurements during shear are seldom required in routineinvestigations, as the basic triaxial tests are sufficient to furnish shear'*?®

••as,strengths for the limiting conditions of drainage. Procedures for measuring-pore pressures in the triaxial test during shear are discussed elsewheretjjând are beyond the scope of this manual. '"'-Ipr2. TYPES OF TESTS. The three types of basic triaxial compression -~.^?.tests are unconsolidated-undrained, consolidated-undrained, and :;'is;consolidated-drained, subsequently referred to as the Q, R, and S tests,'A

•̂ •5?.respectively. As these names imply, they are derived from the drainage .££.

le test. The type of test is sel

t A. W. Bishop and D. J. Henkel, The Measurement of Soil Propertiesthe Triaxial Test. 2nd ed. (London, Edward Arnold Ltd., 1962).

X-2

EM 1HO-2-1906Appendix X

30 Nov 70

to closely simulate, or to bracket , the conditions anticipated in the field.In the basic tests, the initial principal stresses are equal; that is, no

attempt is made to duplicate stress systems in the field in which the prin-cipal stresses are not equal.

a_. Q Test. In the Q test the water content of the' test specimen\ is not permitted to change during the application of the confining pressure U '

or during the loading of the specimen to failure by increasing the deviator

stress. The Q test is usually applicable only to soils which are not f ree -draining,' that is, to soils having a permeability less than 10 X 10" cmper sec.

b. R Test. In the R test, complete consolidation of the testspecimen is permitted under the confining pressure. Then, with the *atercontent held constant, the specimen is loaded to failure by increasing thedeviator stress. Specimens must as a general rule be completely satu-rated before application of the deviator stress.

c. S Test. In the S test, complete consolidation of the testspecimen is permitted under the confining pressure and during the loadingof the specimen to failure by increasing the deviator stress. Consequently,

no excess pore pressures exist at the time of failure.3. APPARATUS, a. Loading Devices. Various devices may be used toapply c.xial load to the specimen. These devices can be classified as eitherapparatus in which axial loads are measured outside the triaxial chamberor apparatus in which axial loads are measured inside the triaxial chamberby using a proving ring or frame, an electrical transducer, or a pressurecapsule. Any equipment used should be calibrated to permit determinationof loads actually applied to the soil specimen.

Loading devices can be further grouped under controlled-strainor controlled-stress types. In controlled-strain tests, the specimen isstrained axially at a predetermined rate; in controlled-stress tests, pre-determined increments of load are applied to the specimen at fixed inter-vals of time. Controlled-strain loading devices, such as commercial

X-3

EM 1110-2-1906Appendix X30 Nov 70

testing machines, are preferred for short-duration tests using piston-ttest apparatus. If available, an automatic stress-strain recorder may beused to measure and record applied axial loads and strains.

b_. Triaxial Compression Chamber. The triaxial compression;chamber consists primarily of a headplate and a baseplate separated by \transparent plastic cylinder.! A drawing of a typical triaxial compressiolifchamber for 1.4-in-.-djameter specimens is shown in Figure 2. Chamber^'

andthroinle1

drai

so t

surttie i

Figure 2. Details of typical triaxial compression chamber

T Adequate safety precautions should be taken, or the transparent plastic/gagcylinder should be replaced by a metal cylinder, if chamber pressures"'i?|5Ein excess of 100 psi are used. " ciSS

1X-4

EM 1110-2-1906Appendix X

30 Nov 70

dimensions and type will vary depending on the size of specimen testedand on pressure and load requirements. The baseplate has one inlet

; through which the pressure liquid is supplied to the chamber and twoinlets leading to the specimen base and cap to permit saturation anddrainage of the specimen when-required. The headplate has a vent valve

• 90 that air can be forced out of the chamber as it is filled with the pres-sure fluid. The cylinder is held tightly against rubber gaskets by bolts ortie rods connecting the headplate and baseplate.

In piston-type test apparatus in which the axial loads, are mea-sured outside the triaxial compression chamber, piston friction can havea significant effect on the indicated applied load, and measures should betaken to reduce friction to tolerable limits. Pistons generally should con-sist of ground and polished case-hardened steel rods with diameters be-tween 1/4 and 1/2 in. for testing 1.4-in.-diameter specimens; heavierpistons are required for larger specimens. .The following measures havebeen found to reduce piston friction to tolerable amounts.

(1) The use of linear ball bushings as shown in Fi-gure 2. Theunique design cf these bushingspermits unlimited axial move-ment of the piston with a mini-mum of friction. Leakage aroundthe piston is reduced by means ofO-rings, Quad-rings, flexible

diaphragms, or other devices. Aseal incorporating O-rings isshown in Figure 2. The benefi-cial effects of using linear ballbushings in comparison withsteel bushings are demonstrated 'by the data shown in Figure 3.

I '•> j -^

I ————

LATINA4. roNCt (Mf "* •

Figure 3. Effect of lateral force onpiston friction in triaxial compres-

sion apparatusThe amount of lateral force

EM 1110-E-1906Appendix X30 Nov 70

transmitted to the piston, if the specimen cap tends to tilt during a

cannot be determined; however, the data shown in Figure 3 indicate thattthe resulting piston friction would be negligible even for relatively large!lateral forces.

(2) Rotation of the piston within the bushings during the ap'pjf?

cation of the deviator stress. (Commercial devices are available to rotatethe piston during the test.) This method is very effective in reducingtion; however, a more complex design of the specimen cap is necessary,-^and vjiless the piston is rotated continuously, appreciable friction would ^still develop during longtime tests. When linear ball bushings are used,~>£the piston should never be rotated except under special conditions desig. jnated by the manufacturer.

Although these measures will reduce piston friction tonegligible amounts during the course of the test, it is . Iways preferableto measure the actual piston friction before the start of the test. Thiscan readily be done by starting the axial load application with the bottomof the piston raised slightly above the top of the specimen cap. Thus anystarting friction or residual friction, as indicated by the load necessary,to move the piston down into contact with the cap, can be subtractedthe measured load.

c. Specimen Caps and Bases. Specimen caps and bases should :?<tbe constructed of a lightweight noncorrosive material and should be of "-"''the same diameter as the test specimen in order to avoid entrapment ofair at the contact faces. Solid caps and bases should be used for the Qtest to prevent drainage of the specimens. Caps and bases with porous - -

metal or porous stone inserts and drainage connections, as shown in '•Figure 4, should be used for the R and S tests. The porous insertsshould be more pervious than the soil being tested to permit effectivedrainage. For routine testing, stones of medium porosity are satisfac-tory. The specimen cap should be designed to permit slight tilting withthe piston in contact position, as shown in Figure 4.

X-6

EM 1110-Z-1906Appendix X

30 Nov 70

o. WES TYPE b. HARVABO TYPE

Figure 4. Details of typical 1.4-in.-diameter specimen capsshowing drainage connections and piston seats

d_. Rubber Membranes. Rubber membranes used to encase thespecimen should provide reliable protection against leakage, yet offerminimum restraint to the specimen. Commercially available rubbermembranes having thicknesses ranging from 0.0025 in. (for soft clays) to0.010 in. (for sands or for clays containing sharp particles) are generallysatisfactory for 1.4-in.-diameter specimens. Rubber membranes about0.010 in., or greater in thickness are suitable for larger specimens.Membranes should be carefully inspected prior to use, and if any flaws orpinholes are evident, the membranes should be discarded. The use of twothin membranes separated by a thin film of silicone grease will afford

protection against leakage through an undetected pinhole and will minimizethe possibility of air leakage from the chamber fluid into the specimenduring tests of relatively long duration. Since no rubber membrane is

X-7


completely impervious, the use of special membranes or chamber fluidsmay sometimes be necessary, such as during periods of undrained shearthat exceed a few hours. The membrane is sealed against the cap andbase by rubber O-rings or rubber bands. L'eakage around the ends of themembrane, where it is sealed against the cap and the base, as well as •.'through fittings, valves, etc., can develop unless close attention is givento details in the manufacture and use of the apparatus.!

£. Equipment for Preparing Specimens. (1) Cohesive soils. A"specimen trimming frame is recommended for preparing specimens of '^most cohesive soils. The specimen is held in a vertical position betweentwo circular plates containing pins which press into the ends of the speci-men to prevent movement during trimming. The edges of the trimmingframe act as vertical guides for the cutting equipment and control the final^r.diameter of the specimen. Details of a typical trimming frame for 1.4-in.^jtdiameter specimens are shown in Figure-5. Wire saws and knives of

various sizes and types are used with the trimmer (see Fig. 7, p. 12).Split or solid cylinders with a beveled cutting edge can also be used totrim specimens. The use of a motorized soil lathe may be advantageousin reducing the time required for preparing specimens of certain types of 5^soils. A miter box or cradle (see Fig. 8, p. 13) is required to trim the I'^ffspecimen to a fixed length and to insure that the ends of the specimen are*£^parallel with each other and perpendicular to the axis of .the specimen. :£u£T

(2) Cohesionless soils. A forming jacket consisting of a splitvmold which incloses a rubber membrane is required for Cohesionless soils.'The inside diameter of the mold minus the double thickness of the mem- .:;.brane is equal to the diameter of the specimen required. A funnel or spe- '_•'cial spoon (see Fig. 5 of Appendix VII, PERMEABILITY TESTS) for £placing the material inside the jacket and a tamping hammer or vibrat

T S. J. Poulos, Report on Control of Leakage in the Triaxial Test, Soil /^Mechanics Series No. 71', Harvard-University: (Cambridge; Mass.,March 1964). • • - . • • : , . • • . , , - . - . • . • .

X-8


30 Nov 70

CLrVATTON

Figure 5. Details of a trimming frame for preparing1.4-in.-diameter specimens

X-9

JII

,1JI


equipment for compacting the material are necessary.(3) Soils containing gravel. Large-size forming jackets,

dimensions of which will depend on specimen size requirements subserquently described, are necessary for preparing specimens of material <taining gravel. Special compacting equipment is also necessary for suesoils, depending on the type of soil and the procedures used.

I. Equipment for Using Back Pressure to Saturate Specimens.Special equipment required forsaturating specimens by usingback pressures is described inparagraph 6a_.

g_. Miscellaneous Equip-ment. Other items of equipme:needed for the triaxial compres-sion tests are as follows:

(1) Membranestretcher. A cylindrical tube,larger in diameter than the soilspecimen, which has a tube con- ;nected to its side for application iof a vacuum. Details of a mem--

>f

H"•Vji*-

Figure 6. Details of a membranestretcher for 1.4-in.-diameter

specimens

brane stretcher for 1.4-in.-diameter specimens are' shownFigure 6. :,j;

(2) Pressure r e se r - : ' ~~voir, generally a metal tank. The -reservoir is filled with the fluid(usually deaired water) for apply-,;ing the chamber pressure and >s':v~*provided with a pressure regula-''*tor and a Bourdon gage. The

X-10

EM 1110-2-1906I Appendix XS 30 Nov 70

IFregulator should be capable of controlling pressures to within *l/2 percent.

If though more precise methods of controlling and maintaining chamber pres-•1 tures are required for tests of long duration.

(3) Measuring equipment, such as dial indicators and calipers.Precise instruments should be used lor measuring the dimensions of aspecimen with the desired accuracy.

(4) Deaired water, distilled or demineralized.(5) Vacuum and air pressure supply.(6) Bourdon gages of various sizes and capacities.(7) A timing device, either a watch or clock with second hand.(8) Balances, sensitive to 0.01 g and'to 0.1 g.(9) Apparatus, necessary to determine water content and

specific gravity (see Appendices I. WATER CONTENT - GENERAL, andIV. SPECIFIC GRAVITY).4. PREPARATION OF SPECIMENS. Specimens shall have an initialheight of not less than 2.1 times the initial diameter, though the minimuminitial height of a specimen must be 2.25 times the diameter if the soilcontains particles retained on the No. 4 sieve. The maximum particlesize permitted in any specimen shall be no greater than one-sixth of thespecimen diameter. Triaxial specimens 1.4, 2.8, 4, 6, 12; and IS in. indiameter are most commonly used.

a_. Cohesive Soils Containing Negligible Amounts of Gravel.Specimens 1.4 in. in diameter are generally satisfactory for testing cohe-sive soils containing a negligible amount of gravel, while specimens of ••larger diameter may be advisable for undisturbed soils having markedstratification, fissures, or other discontinuities. Depending on the type of

, sample, specimens shall be prepared by either of the following procedures:(1) Trimming specimens of cohesive soil. A sample that is

uniform in character and sufficient in amount to provide a minimum of threespecimens is required. For undisturbed soils, samples about 5 in. in diam-eter are preferred for triaxial tests using 1.4-in.-diameter specimens.

X-ll

EM 1110-Z-1906Appendix X30 Nov.70

Specimens shall be prepared in a humid room and tested as soon as poasibl?thereafter to prevent evaporation of moisture. Extreme care shall bein preparing the specimens to preclude the least possible disturbance tojstructure of the soil. The speci.nens shall be prepared as follows:

(a) Cut a section of suitable length from the sample.'Arule, the specimens should be cut with the long axes parallel to the longof the sample; any influence of stratification is commonly disregarded.However, comparative tests can be made, if necessary, to determine the

effects of stratification. When a 5-in.-diameter";undisturbed sample is to be used for 1.4-in:'-,diameter specimens, cut the sample axially into"quadrants using a wire saw or other convenient!cutting tool. Use three of the quadrants for • -y^pspecimens; seal the fourth quadrant in wax andpreserve it for a possible check test.

(b) Carefully trim each spec.7;men to the required diameter, using a tr-ming frame or similar equipment (see Fig/-7)Use one side of the trimming frame for

Figure 7. Prepared triaxial specimen, trimming frame,and cutting tools

X-1Z


30 Nov 70

preliminary cutting, and the other side for final trimming. A specimenafter trimming is also shown in Figure 7. Ordinarily, the specimen is

trimmed by pressing the wire saw or trimming knife against the edgesof the frame and cutting from top to bottom. In trimming stiff or varvedclays, move the wire saw from the top and bottom toward the middle ofthe specimen to prevent breaking off pieces at the ends. Remove anysmall shells or pebblesencountered during the

. trimming operations.Carefully fill voids onthe surface of the speci-men with remolded soil

obtained from the trim-mings. Cut specimen tothe required length(usually 3 to 3-1/2 in.for 1.4-in.-diameterspecimens and 6 to 7 in.for 2.8-in. -diameterspecimens) using a mi-ter box, as shown inFigure 8.

(c) Fromthe soil trimmings, ob-tain 200 g of material for specific gravity and water content determi-nations (see Appendixes I, WATER CONTENT - GENERAL, and IV,SPECIFIC GRAVITY).

(d) Weigh the specimen to an accuracy of ±0.01 g for 1.4-in.-diameter specimens and ±0.1 g for 2.8-in.-diameter specimens.

(e) Measure the height and diameter of the specimen to anaccuracy of ±0.01 in. Specimen dimensions based on measurements of the

Figure 8. Squaring ends of specimen withmiter box

X-13

EM HlO-2-1906Appendix X30 Nov 70

M

trimming frame guides and miter box length are not sufficiently accurThe average height, Ho, of the specimen should be determined from ;

least four measurements, while the average diameter should be deter-;mined from measurements at the top, center, and bottom of the specimjas follows:

2D

whereD{ = diameter at topDc = diameter at centerDb = diameter at bottom

(2) Compacting specimens of cohesive soil. Specimens of_compacted soil may be trimmed, as described in paragraph 4a_(l), from^samples formed in a compaction mold (a 4-in.-diameter sample is satis-Sfactory for 1.4-Ln.-diameter specimens), though it is preferable to com-• '-*-,pact individual specimens in a split mold having inside dimensions equal •to the dimensions of the desired specimen. The method of compacting the isoil into the mold should duplicate as closely as possible the method that .

';(-?-15will be used in the field. In general, the standard impact type oftion (see Appendix VI, COMPACTION TESTS) will not produce the same "^ '^'soil structure and stress-deformation characteristics as the kneadingaction of the field compaction equipment. Therefore, the soil shouldpreferably be compacted into the mold (whether a specimen-size or astandard compaction mold) in at least six layers, using a pressing orkneading action of a tamper having an area in contact with the soil of less --than one-sixth the area of the mold, and thoroughly scarifying the surface^of each layer before placing the'next. The sample shall be prepared ac-cording to paragraph 2b of Appendix VI, COMPACTION TESTS, thoroughlygmixed with sufficient water to produce the desired water content, and then'c

X-14

EM 1110-2.-1906.Appendix X

30 Nov 70

ij. s tored in an airtight container for at least 16 hr. The desired density maybe produced by either (1) kneading or tamping each layer until the accumu-lative weight of soil placed in the mold is compacted to a known volume or(2) adjusting the number .of layers, the number of tamps per layer, andthe force per tamp. For the latter method of control, special constant-force tampers (such as the Harvard miniature compactor for 1.4-in. -diameter specimens! or similar compactors for 2.8-in.-diameter andlarger specimentst) are necessary. After each specimen compacted tofinished dimensions has been removed from the mold, proceed in accor-dance with steps (c) through (e) of paragraph 4a_(l).

b. Cohesionless Soils Containing Negligible Amounts of Gravel.Soils which possess little or no cohesion are difficult if not impossible totrim into a specimen. If undisturbed samples of such materials are avail-able in sampling tubes, satisfactory specimens can usually be obtained byfreezing the sample to permit cutting put suitable specimens. Samplesshould be drained before freezing. The frozen specimens are placed inthe triaxial chamber, allowed to thaw after application of the chamberpressure, and then tested as desired. Some slight disturbance probablyoccurs as a result of the freezing, but the natural stratification andstructure of the material are retained. In most cases, however, it ispermissible to test cohesionless soils in the remolded state by formingthe specimen at the desired density or at a series of densities which willpermit interpolation to the desired density. Specimens prepared in this

* >!*•--.

t A. Casagrande, J. M. Corso, and S. D. Wilson, Report to WaterwaysExperiment Station on the 1949-1950 Program of Investigation of'Effect of Long-Time Loading on the Strength of Clays and Shales atTZonstagt Water Content, Harvard University (Cambridge, Mass., July1950). ;

t A.: Casagrande and R. C. Hirschfeld, Second Progress Report on Inves-tigation of Stress-Deformation and Strength Characteristics of Com-

cted Clays, Soil Mechanics Series No. 65, Harvard UniversityCambridge, Mass., April 1962).

pa(C

X-15


manner should generally be 2.8 in. in diameter or larger, depending onthe maximum particle size. The procedure for forming the test specimen"!shall consist of the following steps:

(1) Oven-dry and weigh an amount of material sufficient to

provide somewhat more than the desired volume of specimen.(2) Place the forming jacket, with the membrane inside, over?

the specimen base of the triaxial compression device.(3) Evacuate the air between the membrane and the inside

face of the forming jacket.(4) After mixing the dried material to avoid segregation,

place the specimen, by means of a funnel or the special spoon, inside the <5forming jacket in equal layers. For 2.8-in.-diameter specimens, 10 layer siof equal thickness are adequate. Starting with the bottom layer, compact :-.-veach layer by blows with a tamping hammer, increasing the number of --iai

"'•^5£Jblows per layer linearly with the height of the layer above the bottom y.layer.t The total number of blows required for a specimen of a given • fimaterial will depend on the density desired. Considerable experience is . gcusually required to establish the proper procedure for compacting a mate-.';rial to a desired uniform density by this method. A specimen formed • :,:properly in the above-specified manner, when confined and axially loaded,^will deform symmetrically with respect to its midheight, indicating that a .-51uniform density has been obtained along the height of the specimen. ..'•''

(5) As an alternate procedure,'the entire specimen may be .•>£placed in a loose condition by means of a funnel or special spoon. The :

desired density may then be achieved by vibrating the specimen in theforming jacket to obtain a specimen of predetermined height and corre-sponding density. A specimen formed properly in this manner, when

t Liang-Sheng Chen, "An investigation of stress strain and strengthcharacteristics of cohesionless soils by triaxial compression tests,"Proceedings, Second International Conference on Soil Mechanics andFoundation Engineering, vol. V (Rotterdam, 1948), pp. 35-43.


30 Nov 70

1,,-onfined and ixially loaded, will deform symmetrically with respect to itsmidheight.

(6) Subtract weight of unused material from original weightof the sample to obtain weight of material in the specimen.

(7) After the forming jacket is filled to the desired height,place the specimen cap on the top of the specimen, roll the ends of themembrane over the specimen cap and base, and fasten the ends withrubber bands or O-rings. Apply a low vacuum to the specimen throughthe base and remove the forming jacket.

(8) .Measure height and diameter as specified in paragraph

£. Soils Containing Gravel. The size of specimens containing appre-ciable amounts of gravel is governed by the requirements of paragraph 4. If thematerial to be tested is in an undisturbed state, the specimens shall be prepared\ccording to the applicable requirements of paragraphs 4a_ and4b_, with the sizeof specimen based on an estimate of the largest particle size. In testing com-pacted soils, the largest particle size is usually known, and the entire sampleshould be tested, whenever possible, without removing any of the coarser parti-cles. However,it may be necessaryto remove the particles larger than a cer-tain size to comply with the requirements for specimen size, though such practicewill result in lower measured values of the shear strength and should be avoidedif possible. Oversize particles should be removed and, if comprising morethan 10 percent by weight of the sample.be replaced by an equal percentage byweight of material retained on the No. 4 sieve and passing the maximum allow-able sieve size. The percentage of material finer than the No. 4 sieve thus re-mains constant (see paragraph 2b_ of Appendix VI, COMPACTION TESTS).It will generally be necessary to prepare compacted samples of material con-taining gravel inside a forming jacket placed on the specimen base. If thematerial is cohesionless, it should be oven-dried and compacted in layersinside the membrane and forming jacket using the procedure in paragraph 4b_as a guide. When specimens of very high density are required, the

iii

X-17


samples should be compacted preferably by vibration to avoid rupturing themembrane. The use of two membranes will provide additional insurance'-?against possible leakage during the test as a result of membrane rupture.;the sample contains a significant amount of fine-grained material, the soilusually must possess the proper water content before it can be compacted^?

the desired density. Then, aspecial split compaction mold is-used for forming the specimen. -^The inside dimensions of the ' " .mold are equal to the dimensions'of the triaxial specimen desired. £?No membrane is used inside themold, as the membrane can bereadily placed over the compacted'specimen after it is removedfrom the split mold. The specimen should be compacted to thedesired density in accordancewith paragraph 4a(2).5. Q TEST. a_. Procedure^ -."...,The procedure for the Q test shall';;'

* •.*%consist of the following steps: • ~f^

(1) Record all identW'1''"-fying information for the sampleproject number or name, boring•number, and other pertinent data,bn a data sheet (see Plate X-D- •'•

(2) Place one of the ..*£&• ̂ ''•*!•.

prepared specimens on the base, "".g(3) Place a rubber ~:';;5jp

membrane (see Fig. 9) in the •' 'S-

figure 9. Placing rubber membraneover a 2.8-in.-diameter specimen

using a membrane stretcher

X-18

EM 1110-2-1906"Appendix X

30 Nov 70

membrane stretcher, turn both ends of the membrane over the ends of the

stretcher, and apply a vacuum to the stretcher. Carefully lower thestretcher and membrane over the specimen as shown in Figure 9. Placethe specimen cap on the top of the specimen and release the vacuum on themembrane stretcher. Turnthe ends of the membranedown around the base and uparound the specimen cap andfasten the ends with O-ringsor rubber bands. With 1.4-

' in. -diameter specimens ofrelatively insensitive soils,it is easier to roll the mem-brane over the specimen asshown in Figure 10.

(4) Assemblethe triaxial chamber andplace it in position in theloading device. Connectthe tube from the pres-sure reservoir to the baseof the triaxial chamber.With valve C (see Figure 11}on the pressure reservoir closed and valves A and B open, increase thepressure inside the reservoir and allow the pressure fluid to fill thetriaxial chamber. Allow a few drops of the pressure fluid to escapethrough the vent valve (valve B) to insure complete filling of the chamberwith fluid. Close valve A and the vent valve.

(5) :With valves A and C closed, adjust the pressure regu-lator to preset the desired chamber pressure. The range of chamberpressures for the three specimens will depend on the loadings expected

Figure 10. Rolling rubber membraneover a 1.4-in.-diameter specimen

X-19

EM 1110-Z-1906Appendix X30 Nov 70

IFigure 11. Schematic diagram of triaxial compression apparatus

for Q test •;:^i

in the field. The maximum confining pressure should be at least equal to .-..-the maximum normal load expected in the field in order that the shear •-strength data need not be extrapolated for use in design analysis. Recordthe chamber pressure on data sheets (Plates X-l and X-2). Now openvalve A and apply the preset pressure to the chamber. Application of thechamber pressure will force the piston upward into contact with the ram of.:-..

:e. Thisading i upvacting on the cross-sectional area of the piston minus the weight of thepiston minus piston friction.

X-20


30'Nov70

"I

(6) Start the test with the piston approximately 0.1 in. abovethe specimen cap. This allows compensation {or the effects of pistonfriction, exclusive of that which may later develop as a result of lateralforces. Set the load indicator to zero when the piston comes into contactwith the specimen cap. In this manner the upward thrust of the chamberpressure on the piston is also eliminated from further consideration.Contact of the piston with the specimen cap is indicated by a slight move-ment of the load indicator. Set the strain indicator and record on thedata sheet (Plate X-2) the initial dial' reading at contact. Axially strainthe specimen at a rate of about 1 percent per minute (for plastic mate-rials) and about 0.3 percent per minute (for brittle materials that achievemaximum deviator stress at about 3 to 6 percent strain); at these ratesthe elapsed time to reach maximum deviator stress would be about15 to 20 min.

(7) Observe and record the resulting load at every 0.3 per-cent strain for about the first 3 percent and, thereafter, at every 1 per-cent, or for large strains, at every 2 percent strain; sufficient readingsshould be taken to completely define the shape of the stress-strain curve sofrequent readings may be necessary as failure is approached. Continue thetest until an axial strain of 15 percent has been reached, as shown inFigures 12a, 12b, and 12d; however, when the deviator stress decreasesafter attaining a maximum value and is continuing to decrease at 15 percentstrain (Fig. 12c), the test shall be continued to 20 percent strain.

(8) For brittle soils (i.e., those in which maximum deviatorstress is reached at 6 percent axial strain or less),, tests should be per-formed at rates of strain sufficient to produce times to failure as setforth in paragraph 5a(6) above; however, when the maximum deviatorstress has been clearly defined, the rate may be increased such that theremainder of the test is completed in the same length of time as that takento reach maximum deviator stress. However, for each group of testsabout 20 percent of the samples should be tested at the rates set forth

X-21

EM 1HO-2-1906Appendix X30 Nov 70

T IMAXIMUM OCVIATOA

I I

10

a-15 20

•MAXIMUM QfYUTOaSTKCSS

•mro*-/UI.TIMATC DCVIATOKsrnfss

1 IO 15AXIAL- STRAIN, -I.

«&

10b.

15 20

Figure 12. Examples of stress-strain curves .:-..^jj

X-22


30 Nov 70

in paragraphs Sa(6) and 5a(7) above.(9) Upon completion of axial loading, release the chamber .

pressure by shutting off the air supply with the regulator and openingvalve C. Open valve B and draw the pressure fluid back into the pres-sure reservoir by applying a low vacuum at valve C. Dismantle the tri-axial chamber. Make a sketch of the specimen, showing the mode of

failure.(10) Remove the membrane from the specimen. Tor 1.4-

in.-diameter specimens, carefully blot any excess moisture from thesurface of the specimen and determine the water content of the whole

X-23


IJ

specimen (see Appendix I, WATER CONTENT - GENERAL). For 2.8-in?diameter or larger specimens, it is permissible to use a representative '.Jportion of the specimen for the water content determination. It is esseh-tiai that the final water content be determined accurately, and weighings^should be verified, preferably by a different technician.

(11) Repeat the test on the two remaining specimens at differ!ent chamber pressures, though using the same rate of strain.

b. Computations. The computations shall consist of the following^steps:

(1) From the observed data, compute and record on the datajsheet (Plate X-l) the initial water content (see Appendix I, WATER CON-TENT - GENERAL), volume of solids, initial'void ratio, initial degree ofsaturation, and initial dry density, using the formulas given in Appendix II,UNIT WEIGHTS, VOID RATIO. POROSITY. AND DEGREE OF SATURATION^'-

i?v(2) Compute and record on the data sheet (Plate X-2) the axial '<••.:

strain, the corrected area, and the deviator stress at each increment of "%••:-f*

strain, using the following formulas: ;V%

Axial .strain, c = ——AHo

Corrected area of specimen, A , so, cm =1 - e

Deviator stress, tons per sq ft = • •X 0.465

where AH = change in height of specimen.during test, cmH = initial height of specimen, cm. (Where a significant de-

crease in specimen volume occurs upon application of thechamber pressure, as in partially saturated .soils, theheight of the specimen after application of the chamberpressure should be used rather than the initial height.)

A = initial area of specimen, sq cm

:£miX-24


30 Nov 70

P = net applied axial load, Ib (the actual load applied to speci-men after correction for piston friction and for the upwardthrust of the fluid pressure in the triaxial chamber)

(3) Record the time to failure on the data sheet (Plate X-Z) .(4) The rubber membrane increases the apparent strengtn of

the specimen. InvestigationsT with specimens 1.5 in. in diameter andmembranes 0.008 in. thick, (or instance, indicate the increase in deviatorstress to be 0.6 psi at 15 percent axial strain. The correction, <r r , to bemade to the measured deviator stress for the effect of the rubber mem-brane is computed as follows:

irD M e(l - c)

where Do = initial diameter of specimenM = compression modulus of the rubber membranec = axial strain

AQ = initial cross-sectional area of the specimen

The compression modulus may, without great error, be assumed to beequal to that measured in extension. An apparatus for determining theextension modulus of rubber is described in another work.t In tests ofvery soft soils the membrane effect may be significant, and in these testsit is advisable to compute or estimate the correction and deduct it fromthe maximum deviator stress. For most soils tested using membranes ofstandard thickness, the correction is insignificant and can be ignored.

c. Presentation of Results. The results of the Q test shall berecorded on the report form shown as Plate X-3. Enter pertinent infor-mation regarding the condition of the specimen or method of preparing the

t Bishop and Henkel, op. cit.', pp. 167-171.

X-25

Jfl


specimen under "Remarks." Plot the deviator stress versus the axial ;strain for each of the specimens as shown in Figure 12. The peak or

maximum deviator stress represents "failure" of the specimen; whendeviator stress increases continuously during the test, the deviator strat 15 percent axial strain shall be considered the maximum deviatorstress. When the deviator stress decreases after reaching a maximum,^the minimum deviator stress attained before 15 percent axial strain shall']be considered the ultimate deviator stress, as shown in Figures 12c and12d. Construct Mohr stress circles on an arithmetic plot with shearstresses as ordinates and normal stresses as abscissas. As shown inFigure 13, the applied principal stresses, <TI and <r^, are plotted on Iabscissa, and the Mohr circles are drawn with radii of one-half the maxi-^j

I'I ' fl\mum deviator stresses 1——-——I and with their centers at values equaJ-

to one-half the sums of the major and minor principal stresses

Plot a Mohr circle, or a sufficient segment thereof, for each specimen in ;

T|

Figure 13. Construction of Mohr's circle of stress

X-Z6

EM «-l0^2-1906"Appendix X30 Nov 70

Ti

an

STREHCTH CNVfLOPC- 0 = 0

a. UNDISTURBED SOIL, COMPLETELY SATURATED £

. •ONDIST_URBfgg_SOtC^PARTIA LLY SATURATE

ENVELOPE ORAWH THROUGH fO/HTS Of CIRCLESREPRESENTING STRESSES ON FAILURE PLANE ASDEFINED Br Ot. WHERE «*•*}' + •£-

•••• NORMAL STRESS C," T/SQ FT "

c. COMPACTED SOIL

Figure 14. Examples of strength envelopesfor Q tests

X-28

EM 1110-E-t906Appendix X

30 Nov 70

(to those used in the R test), apply 3-psi chamber pressure to the speci-jmen with all drainage valves closed. Allow a minimum of 30 min for[stabilization of the specimen pore water pressure, measure AH, and[begin back-pressure procedures as given in paragraphs 7bJ2) through<7b(5). After verification of saturation, and remeasurement of &H, closecall drainage lines leading to the back pressure and pore water measure*.ment apparatus. Holding the maximum applied back pressure constant,' increase the chamber pressure until the difference between the chamber' pressure and the back pressure «quals the desired effective confiningpressure (see paragraph 5a_(5)). Then proceed as outlined in paragraphs5a_(6) through 5a_(il).7. R TEST. All specimens must be completely saturated before appli-cation of the deviator stress in the R test. A degree of saturation over98 percent can be considered to represent a condition of essentially com-plete saturation; if pore water pressures are to be measured during shear,however, the specimens must be 100 percent saturated. Computations of

X-Z9

EM 1UO-2-1906Appendix X30 Nov 70

the degree of saturation based on changes of volume and water contentare oi'ten Imprecise, so complete saturation of a specimen should beassumed only when an increase of the chamber fluid pressure will causean immediate and equal increase of pressure in the pore water of thespecimen. In general, it is preferable to saturate the soil after the speci-

mens have been prepared, encased in membranes, and placed within thecompression chamber, using back pressure. A back pressure is anartificial increase of the pore water pressure which will increase thedegree of saturation of a specimen by forcing pockets of air into solutionin the pore water. The back pressure is applied to the pore water simul-taneously with an equal increase of the chamber pressure so that theeffective stress acting on the soil skeleton is not changed. In other words,the pressure differential across the membrane remains constant duringthe back pressure saturation phase. Thus, when the back.pressure is in-creased sufficiently slowly to avoid an excessive pressure differentialwithin the specimen itself, the degree of saturation will be increasedwhile the volume of the specimen is maintained essentially constant.Figure IS gives the back pressure theoretically required to produce adesired increase in saturation if there is no change in specimen vol-ume. It is important to note that the relation shown in Figure 15 isbased on an assumption that the water entering the specimen containsno dissolved air.

a_. Apparatus. In addition to the apparatus described in para-graphs 3a_ through 3£, the following equipment are necessary for R testsutilizing back pressure for saturation:

(1) Air reservoir and regulator for controlling the backpressure, similar to those used to control the chamber pressure.

(2) Bourdon gage attached to the back pressure reservoir tomeasure the applied back pressure. As relatively large back pressuresand chamber pressures are sometimes required, it is essential that these

two pressures be measured accurately to insure that the precise

X-30


30 Nov 70

Figure 15. Back pressure required to attain variousdegrees of saturation

difference between them is known. A differential pressure gaget willpermit this difference to be measured directly.

(3) Calibrated burette or standpipe capable of measuringvolume changes to within 0.1 cc for 1,.4-in.-diameter specimens, 0.5 ccfor 2.8-in.-diameter specimens, and 1 cc for 6-in.-diameter specimens.This burette is connected in the back pressure line leading to the top of

John Lowe, 111, and Thaddeus C. Johnson, "Use of back pressure to in-crease degree of saturation of triaxial test specimens," ASCE ResearchConference on Shear Strength of Cohesive Soils, University of Colorado(Boulder, Colo., June i960).

m \

mm

X-31


the specimen to measure the volume of water added to the specimen dur-ing saturation and volume changes of the specimen during consolidation.If the water added to the specimen becomes saturated with air, a higherback pressure will be required than that given in Figure 15. Therefore,precautions should be taken to minimize aeration of the saturation waterby reducing the area of the air-water interface or by separating the airand water with a rolling rubber diaphragm.! A relatively long (over6-foot) length of thick-walled, small-bore tubing between the burette andthe specimen will also reduce the amount of air entering the specimen.Adequate safety precuations should be taken against breakage of the buretteunder high pressures.

(4) Electrical pressure transducer or no-flow indicator withwhich the pressure of the pore water at the bottom of the specimen can bemeasured without allowing a significant flow of water from the specimen.This is an extremely difficult measurement to make since even a minuteflow of water will reduce the pressure in the pore water; yet the measuringdevice must be sensitive enough to detect small changes in pressure.Electrical pressure transducers, while relatively expensive, offer almostcomplete protection against flow, are simple to operate, and lend them-selves to the automatic recording of test data. Several types of manuallybalanced pressure-measuring systems employing a no-flow indicator arebeing used successfully,t though a full discussion of their relative merits

T H. B. Seed, J. K. Mitchell, and C. K. Chan, "The strength of compactedcohesive soils," ASCE Research' Conference on Shear Strength of Cohe-sive Soils, University of Colorado (Boulder, Colo., June 1960).

t Bishop and Henkel, op. cit., pp. 5Z-63, 206-207.'A. Andersen, L. Bjerrum, E. DiBiagio, and B. Kjaernsli, TriaxialEquipment Developed at the Norwegian Geotechnical Institute, Publica-tion No. 21, Norwegian Geotechnical Institute (Oslo, 1957).A. Casagrande and R. C. Hirschfeld, First Progress Report on Investi-gation of Stress-Deformation and Strength Characteristics of CompactedClays, Soil Mechanics Series No. 61. Harvard University (Cambridge,Mass., May 1960).

X-32

EM U10-Z-1906"Appendix X

30 Nov 70

shortcomings is not possible here.

b. Procedure. The procedure for the R test utilizing backssure for saturation shall consist of the following steps:

(1) Proceed as outlined in paragraphs 5a_(l) through 5a(4),uh the exception that specimen bases and caps with porous inserts and

.inage connections should be used and back pressure equipment shouldincluded as shown in Figure 16. Saturated strips of filter paper (suchWhatman's No. 54) placed beneath the membrane and extending from

e base along three-fourths of the specimen length will reduce the timequired for saturation and consolidation. These strips must neithererlap and form a continuous circumferential coverage of the specimen

m

Figure 16. Schematic diagram of typical triaxial compressionapparatus tor rX and S tests

X-33

I

1

'1

S

H


nor form a continuous path between the base and the cap. Place saturatedfilter paper disks having the same diameter as that of the specimen be-tween the specimen and the base and cap; these disks will also facilitate r«moval of the specimen af ter the test. The drainage lines and the porousinserts should be completely saturated with deaired water. The drainagelines should be as short as possible and made of thick-walled, small-boretubing to insure minimum elastic changes in volume due to changes inpressure. Valves in the drainage lines (valves E, F, and G in Figure 16)should preferably be of a type which will cause no discernible change ofinternal volume when operated (such as the Teflon-packed ball valve madeby the Whitey Research Tool Co.). While mounting the specimen in thecompression chamber, care should be exercised to avoid entrapping anyair beneath the membrane or between the specimen and the base and cap.

(2) Estimate the magnitude of the required back pressure byreference to Figure IS or other theoretical relations. Specimens shouldbe completely saturated before any appreciable consolidation is per-mitted, for ease and uniformity of saturation as well as to allow volumechanges during consolidation to be measured with the burette; there-fore, the difference between the chamber pressure and the back pres-sure should not exceed S psi during the saturation phase. To insure thata specimen is not prestressed during the saturation phase, the back pres-sure must be applied in small increments, with adequate time betweenincrements to permit equalization of pore water pressure throughout thespecimen.

(3) With all valves closed, adjust the pressure regulators toa chamber pressure of about 7 psi and a back pressure of about 2 psi.Record these pressures on the data sheet (Plate X-4). Now open valve Ato apply the preset pressure to the chamber fluid and simultaneouslyopen valve F to apply the back pressure through the specimen cap. Im-mediately open valve G and read and record the pore pressure at thespecimen base. When the measured pore pressure becomes essentially

4X-34

EM 1UO-Z-1906Appendix X

30 Nov 70

star.t. close valves F and Ct and record the burette reading.(4) Using the technique described in step (3), increase the

• mber pressure and the back pressure in increments, maintaining the_k pressure at about 5 psi less than the chamber pressure. The size of

?<-h increment might be 5, 10, or even 20 psi, depending on the compres-ility of the soil specimen and the magnitude of the desired consolidation

ressure. Open valve G and measure the pore pressure at the base im-diately upon application of each increment of back pressure and observe

r. pore pressure until it becomes essentially constant. The time requiredx_ stabilization of the pore pressure may range from a few minutes to

/eral hours depending on the permeability of the soil. Continue addingnrrements of chamber pressure and back pressure until, under any incre-

:nt, the pore pressure reading equals the applied back pressure im-nediately upon opening valve G.

(5) Verify the completeness of saturation by closing valve F»nd increasing the chamber pressure by about 5 psi. The specimen shall' t be considered completely saturated unless the increase in pore pres-_~re immediately equals the increase in chamber pressure., (6) When the specimen is completely saturated, hold the max-

lum applied back pressure constant and increase the chamber pressurentil the difference between the chamber pressure and the back pressurejuals the desired consolidation pressure. Open valve F and permit the

specimen to consolidate (or swell) under the consolidation pressure.live E may be opened to allow drainage from both ends of the specimen.

.vt increasing intervals of elapsed time (0.1, O.Z, 0.5, 1, Z, 4, 8, 15, and"O min, 1, 2, 4, and 8 hr, etc.), observe and record (Plate X-5) the burette

eadings and, if practicable, the dial indicator readings (it may be neces-,sary to force the piston down into contact with the specimen cap for each

i If an electrical pressure transducer is used to measure the pore pres-, sure, valve G may be safely left open during the'entire saturation

procedure.

X-35


reading). Plot the burette readings (and dial indicator readings, i£ taken)

versus the logarithm of elapsed time, as shown in Figure 5 of AppendixVIII, CONSOLIDATION TEST. Allow consolidation to continue until amarked reduction in slope of the curve shows that iOO percent primaryconsolidation has been achieved.

(7) Close valve G, unless pore pressure measurements areto be made during shear, and valves E and F, and proceed according toparagraphs 5a(6) through 5a(lO), except use a rate of strain for the Rtest of about O.S percent per minute (for plastic materials) and about0.3 percent per minute or less for brittle materials that achieve a maxi-mum deviator stress at about 3 to 6 percent strain; the strain rate usedshould result in a time to maximum deviator stress of approximately30 min. Relatively pervious soils may be sheared in 15 min. Theserates of strain do not permit equalization of induced pore pressurethroughout the specimen and are too high to allow satisfactory pore pres-sure measurements to be made at the specimen ends during shear.fTherefore, these rates of strain are applicable only'to R tests in whichno pore pressure measurements are made during shear. Where porepressure measurements are mads at the ends of the specimens as in Rtests, the time to reach maximum deviator stress should generally be atleast 120 min; considerably longer time may be required for materialsof low permeability. For brittle soils (i.e., those in which the maximumdeviator stress is reached at 6 percent axial strain or less), after themaximum deviator stress has been clearly defined, the rate of strainmay be increased so that the remainder of the test is completed in thesame length of time as that taken to reach maximum deviator stress.However, for each group of tests in a given test program, at least20 percent of the samples should be tested to final axial strain at ratesof strain outlined in the first sentence of this paragraph.

c. Computations. The computations shall consist of the follow-

ing steps:(1) From the observed data, compute and record on the data

sheet (Plate X-l) the initial water content, volume of solids, initial void

t Bishop and Henkel, op. cit., pp. 192-204.

X-36


30 Nov 70

ratio, initial degree of saturation, and initial dry density, using the formu-

las previously presented.(2) Compute the cross-sectional area of the specimen after

completion of consolidation according to the formula: tHQ

Area of specimen after consolidation, A , sq cm » A

or if the specimen is or has been completely saturated during the test, usethe more accurate formula:

V - V - AVo a wArea of specimen after consolidation, A , so cm = —— =3 ——— — 7; ———c rl - an

where V = initial volume of specimen, ccV = initial volume of air in specimen, ec » .V - V - V

V - V - V = initial volume of specimen minus volume of solids minus° s w initial volume of water

AV = change in volume of water in the specimen during the sat-w uration and consolidation phases of the test, cc. This

value may be computed from the change in weight of thespecimen before and.after the test or from the burettereadings from the start of saturation on to the end ofconsolidation

H = initial height of specimen, cmAH = change in height of specimen during consolidation, cm

(3) Using the computed dimensions of the specimen after con-solidation and assuming that the water content after consolidation is thesame as the final water content, compute the void ratio and degree of satu-ration using formulas previously presented.

(4) Compute and record on the data sheet (Plate X-2) theaxial strain, the corrected area, and the deviator stress at each incrementof strain, using the following formulas:

t This formula is based on the assumption that axial and radial strainsare equal during consolidation.

X-37

u

u

J


Axial strain, c =

Corrected area of specimen, A sq cm = 1 - c

Deviator stress, tons per sq ft = -7——— x 0.465Acorr

where H = height of specimen after consolidation, cm = H - ^*o

P = net applied axial load, Ib (see paragraph 5b_(2))(5) Record the time to failure on the data sheet (Plate X-2). S(6) Correct the maximum de viator stress, if necessary, for

the effect of membrane restraint (see paragraph 5b_(4,'. .. r-:

d. Presentation of Results. The results of the R test shall be~»":?presented on the report form shown as Plate X-3, as described in para-V.$graph 5c_. A sketch of each specimen after failure should be shown above ,vsthe Mohr circles. If pore pressure measurements were made duringshear, plot the induced pore pressure versus axial strain for each speci- •-•.men below the stress-strain curves. The procedures below should be fol- ,-lowed in drawing strength envelopes:

(1) Undisturbed specimens. For undisturbed specimens,strength envelopes should be drawn tangent to the Mohr circles as shownin Figures 17a and 17b.

(2) Compacted specimens. For compacted specimens,strength envelopes should be drawn through points on the Mohr circlesrepresenting stresses on the failure plane as shown in Figure 17c.8. S TEST. The S test using triaxial equipment, as a rule, shallbe performed only with relatively pervious soils. The consolidation • -P'/tSj.--of triaxial specimens of relatively impervious soils proceeds so slowthat the time required to complete an S triaxial test inhibits its use

X-38

EM H10-2-1906Appendix X

30 Nov 70

a. UNDISTURBED SOIL, NORMALLY CONSOLIDATED

IB.

STRCNGTH CNV£LOff-~

T b. UNDISTURBED SOIL, OVER-CONSOLIDATED

£NVtLOt>£ DKAITH THROUGH POINTS OH CIRCLESKEPRCSCNTING STRCSSCS OH fAILURE PLANE ASDCflMCO BY O. WH£RC a.:^i'

NORMAL STRESS ff, T/SQ FT

c. COMPACTED SOIL

Figure 17. Examples of strength envelopesfor R tests

EM Ill(r=rri9o6Appendix X

30 Nov 70

ne grained impervious^ct "hear equipment (se

owever, if schedul

n S triaxial tests of .'*s f om S direct shear.;?ious and contains gra1

prr nt, considerationore pressure measure-r . £th -irameters within a.- c tnpletely saturated ;

rfi -m the R test, as ^fjj>ry for the S test,!ui will not be necessary^, .

^ •**•'led-strain testing should. W!lei stress testing should "]

. ^•3t shall consist of i

- back pressure, proceed v>r ervious soils which>^ iter percolatingad omit the back pres- 'oceed as follows:gr phs 5a_(i) throughI c.ps >vith porous insertsapnaratus should include: \ th a vacuum connectiononless soil prepared as.d rainage lines (includingl

...'fipss than S psi) should be .'-^

to si\p|

regulaapply i

througthe wato the

discor.head tclose

.nto c-livelycontrtstress

and juload aTheoifor farequi.the cltainecevapopossi!face i

t Bii

en base and cap (with valves D and G closed)

assembling and filling the triaxial chamber.valves A and C closed, adjust the pressuresure of about 5 psi and then open valve A to

mber.ses £ and C closed, maintain a low vacuum:imen cap. Then open valve D and elevatethat a hydrostatic head of i to 2 ft is applied

saturation water rises into the burette,ie burette. Permit seepage under the smallof flow into the burette is constant, and then

and F open (see Fig. 16), lower the pistoncap and increase the axial load at a rela-drained condition exists at failure withter each increment of load with controlled-direct shear test, considerable experiencequired in determining the proper rate of axialIX, DRAINED (S) DIRECT SHEAR TEST),available T for estimating the time required1 precautions may be necessary for tests.tion in excess of a few hours to insure thatas the back pressure, if used) is main-re fluctuations are minimized, and thatwater in the burette is reduced as much asE oil o-r dyed kerosene over the water sur-le evaporation.1 indicator and burette readings at

pp. 1Z4-127, 204-206.

X-41

I\

fl


increasing intervals of elapsed time under each increment of load. For.'irelatively impervious soils, plot either or both of these readings versusthe logarithm ot elapsed time, as shown in Figure 5 of Appendix VU1,CONSOLIDATION TEST, to establish when primary consolidation has been":essentially completed for each increment of load. Record the final dial 4-^indicator and burette readings for each axial load increment on a formsimilar to Plate X-6 prior to applying the next increment. With controlled-strain loading, periodically observe and record (Plate X-6) the resulting-digi,load and the dial indicator and burette readings; sufficient readings should]be taken to completely define the shape of the stress-strain curve. Con-'Htinue the test until an axial strain of 15 percent has been reached; however^when the deviator stress decreases after attaining a maximum value andis continuing to decrease at 15 percent strain, the test shall be continuedto 20 percent strain (see Tig. 12).

(4) Upon completion of axial loading, close valves E and Fand proceed as outlined in paragraphs 5a_(8) through 5a_(10), except measure.£,the specimen diameter, as described in paragraph 4a_(l)(e), after the com-.-^pression chamber has been dismantled. While considerable difficultybe encountered in measuring the diameter of the specimen after the test, r :"~such measurements will permit the most reliable computations of thespecimen properties at failure.

c. Computations. The computations shall consist of the follow-ing steps:

(1) From the observed data, compute and record on the datasheet (Plate X-l) the initial water content, volume of solids, initial voidratio, initial degree of saturation, and initial dry density using the for-mulas previously presented.

(2) Compute the cross-sectional area of the specimen, A ,after completion of consolidation using the formulas presented in para-graph 6c(2).

(3) Using the dimensions of the specimen after consolidation

and the c

ratio aucviously i


30 Nov 70

and the changes in volume as measured with the burette, compute the voidratio and degree of saturation after consolidation using the formulas pre-viously presented.

(4) Compute and record on the data sheet (Plate X-6) theaxial strain, the corrected area, and the deviator stress corresponding tothe final readings under each increment of load for controlled-stress load-

ing or for convenient intervals of strain for controlled-strain loading usingthe following formulas:

m

Axial strain, c *A H

Area of specimen corrected for A ,. AA ,j . , A so cm s T— « — ~5r—strain and volume change, corr, n 1 - Cc

Deviator stress, tons per sq ft = -j-;——— x 0.465Acorr

where C - correction for volume change during shear =

Af - area of specimen after test based on measurements

.D?= 0.7854 D

A = area of specimen at end of test computed on basis ofconstant volume

t

P = net applied axial load, Ib (see paragraph 5b(2))

X-43

*ri*tf


(5) Record the time to failure on the data sheet (Plate X-6).

(6) Correct the maximum deviator stress, if necessary, forthe effect of membrane restraint (see paragraph 5b_(4)).

d_. Presentation of Results. The results of the S test shall bepresented on ".he report form shown as Plate X-3, as described in para-graph 5c. If volume changes of the specimens during shear were mea-sured, plot the volumetric strain versus axial strain for each specimenbelow the stress-strain curves.

'•*9. POSSIBLE ERRORS. Following are possible errors that wouldcause inaccurate determinations of strength and stress-deformation ;characteristics: "

a. Apparatus. (1) Leakage of chamber fluid into specimen.Such leakage might occur through or around the ends of the membrane orthrough the drainage connections and it would decrease the effective stressin a specimen during undrained shear. Very little leakage is needed tocause a very large change in effective stress, and the longer the period of .undrained shear, the greater the amount of leakage. (Leakage will notinfluence the effective stress during periods of specimen drainage, but it -•»=-will introduce errors in volume change measurements.) _.

(2) Leakage of pore water out of specimen. This leakagemight occur through fittings or valves and it would increase the effectivestress in a specimen during undrained shear.

(3) Permeability of porous inserts too low.(4) Restraint caused by membrane and filter paper strips.(5) Piston friction.

b. Preparation of Specimens, (1) Specimen disturbed whiletrimming. Disturbance of the natural soil structure does not alwaysresult in strength measurements which are too low, that is, on the safeside; disturbed specimens will consolidate more under the effective con- .,solidation pressure in R or S tests and the measured strengths will be ..£too high. ...... .<•§

X-44


30 Nov 70

(2) Specimen disturbed while enclosing with membrane. Thetechniques al placing the membrane around the specimen illustrated inFigures 9 and 10 may not be satisfactory lor sensitive undisturbed soilssince the specimen would-tend to be flexed while binding the membrane tothe unsupported cap. Alternatively, the specimen can be set upon aninverted cap clamped to a ringstand and the membrane placed over thespecimen and bound to the cap; then the specimen and cap can be invertedonto the base and the lower end of the membrane secured.

(3) Specimen dimensions not measured precisely. Dial gagesor micrometers are helpful in obtaining precise measurements. When thespecimen diameter is measured after being enclosed by the membrane,twice the thickness of the membrane must be subtracted from the measure-ment. The cross-section area of large specimens may be determinedmost satisfactorily from circumference measurements.

e:. Q Test. (1) Changes in specimen dimensions upon applica-tion of chamber pressure. Partially saturated specimens will compressunder the chamber pressure so the change in height, AH , due to theapplication of chamber height should be recorded. When this change inheight is significant, the area of specimen before shear, A , should becomputed according to the formula:

Ho 'H

as given in paragraph 6c_(2).(2) Rate of strain too fast.(3) Water content determination after test not representative.

Friction .between the soil and the cap and base restrains the radial defor-mation at the ends of the ipecimen and this end restraint induces a non-uniform pore pressure distribution which, in turn, causes pore watermigration within the specimen. For relatively impervious soils, a

j

.J

I

EM lliO-a-1906Appendix X30 Nov 70

significant migration of pore water could occur only in a test of long duration (such as S and some R tests); however, for more pervious soils,appreciable redistribution of water content can occur within the shortduration of a Q test. Therefore, it may be desirable to determine thewater content of the end sections (about 1/6 of the height at each end)separately from the middle portion. Correlations of strength with water :

content should be based on the water content of the middle portion, thoughthe dry weight of the entire specimen is needed to compute the initial soilproperties.t

jL- R Test. (1) Back pressure increments too large in relation"'to effective consolidation pressure.

(2) Back pressure increments applisd too rapidly.(3) Chamber and back pressures not precisely maintained

during consolidation phase. Variations in either or both of these pres-sures (often much larger than the difference between them) can result inoverconsolidation of the specimen.

(4) Specimen not connpletely consolidated before shearing._ —... —ryj Rate •ofTtraih too fast. " " " " '

(6) Excessive variations in temperature during shear. Anincrease in temperature will decrease the effective stress in a specimenduring undrained shear. This danger, obviously, increases with the dura-tion of the test.

(7) Specimen absorbed water from porous inserts at end oftest. As in a consolidation test or a direct shear test, the specimen willabsorb water from the porous inserts and drainage lines at the end of theR or S test no matter how rapidly the apparatus is disassembled and thespecimen removed. To obtain an accurate water content determination at

t A. Casagrande and S. J. Poulos, Fourth Report on Investigation ofStress-Deformation and Strength Characteristics of Compacted Clays,Soil Mechanics Series No. 74, Harvard University (Cambridge, Mass.,October 1964).

EM'HiO-2^1906'Appendix X

30 Nov 70

the end of the test, the specimen should be allowed to swell completelyunder a small (Z or 3 psi) chamber pressure and the increase in volumemeasured by means of the burette. This volume change can then be usedto correct the water content measured after the test.

e_. S Test. (1) Rate of strain or rate of loading too fast.(2) Inaccurate volume change measurements during shear.

Where volume changes are measured using a burette, inaccuracies mayresult f rom incomplete saturation of the specimen, leakage, evaporation,or temperature fluctuations.

:|

X-47

f fOcalgnaUorc DIS4 -13

—» •—rDM4

•*—•-'——sSSf^S;

Standard Teal Method lorSPECIFIC GRAVITY OF SOILS'

(hit Maadard ii iii.nl midti Ihc tied driifMI|IM D114; Ihc MMWCICI iMimdimly Mhr4«a ihc dciifMilMi Udkalca Iht rat-.fiul ad»Ki«« «. as «« eiic <T n4w». Ihc rut <T laa Ifmo. A. «.«*« h acmlhacl kdiolct Ik )cai *(U»itw.\ »pcnciwi tpMto. 1,1 Micald •• editorial ehanti |I«« she lall IcvUn «itaepmal. '"

•̂1.2 The values staled in acceptable mart

units arc lo be regarded as the standard. *Jl.j — • ---••—•• —— i-~J** luitat

I.Scop.I.I This test method coven determination of —ihe specific gravity of soils by means of a pye- '-J ThiiatmlarjmarImotthturdoam-

nnmcler. When the soil is composed of panicles I"'"1'- •(""to"* end tv/M/vnevu. TMf ilruaWlancr lhan ihc No. 4 (4.7i-mm) sieve. Ihe <«"" «•• purport la aUr,u all of lh, iota, mlim-lhnd outlined in Test Method C 127 shall be "~J -*"•••—» '• '*« rbmuM

> .....__ .».. .̂ ;i ;. r̂tmnn**d of Mrtic'rf*

U. Significance and Use4.1 The specific gravity of a soil is uicd in

osl every equation expressing the phase rcla-oftihip of iir. water, and solids in • given vol-M of material.U The term "solid particles." as used in gco-

ktMMcal engineering, is typically assumed to•KM naturally occurring mineral particles thatin aot very soluble in water. Therefore, thetycciftc travity of materials containing entra-iKwt matter (such as cement, lime. cic.). water-

—» Uuch » sodium chloride), andiaas containing mailer with i specific gravity ofjnslrtan one, typically requite special treatment[• i qualified definition of ipccitk (cavity.

weight, II'. .re determined laic. (Note 4) Theseof »'. ltuli"cJ "'"'"' '

nu-lhnd outlined in Test Metho saiiiltowed. When the soil is composed of paniclesIwilh larger and scnalkc than the No. 4 sieve, the•ample shall be separated on ihc No. 4 licvc andihc appropriate test method used on each por-tion. The specific gravity value for the soil shallIK the weighted avcraie of the two values (NoteII When UK specific gravity value is 10 be usedin calculations in connection with Ihc hydrome-icr portion of Method D 421, it is intended thatihc specific gravity test be made on that portionnf the soil which passes the No. 10 (2.00-mm)sieve.

More I— The wtilhled average specific iraih,Hild be calculated »sin| Ihc folloMni equation:

C"" R, ~fTIOOG, lOOCi

rtWi rhri purport la tureu a Qlrte jeleiia aiHxIattJ u-Vln Us me. ll It iHi rtipuaMil>- rf irnonrr run lau iKm/an/ lo ctmnll uf

f .,«/ hcM ^«ira

[i. Atparalus. 3.1 /Vcmwiicrrr—Either a volumetric flaskjsriag a capacity of al kasl 100 mL or a slop-

rtered bolllc having a capacity of al kasl SO mL[(Note 2). The stopper shall Ix of Ihc same ma-

• ^-< -. th» hniite. and of sucn jiKC ani] ihnpc

I

where:!•'.., • weighted avcraie specific gravity of soils

composed of panicles larger and smalkrthan the No. 4 (4.7)-mm) skvc,

H, - percent of soil panicles retained on theNo. 4 sieve,

f, - pccccnl of soil panicles passinf Ihc No. 4sieve,

(ii • apparent specific gravity of soil paniclesretained on the No. 4 sieve as determinedbyTcslMclhodCI27,and

tii - specific gravity of soil panicles passing ihcNo. 4 sieve as dclcrmincd by this Icslmethod

2. Applicable Document2.1 ASTM Standards: (,C 127 Tcsl Method for Specific Gravity 1*4

Absorption of Coarse Aggregate1 ( 'C 670 Practice for Preparing Precision Suit,

menu for Test Methods for ConslrwiwMaterials1

D 422 Mclhod for Panicle-Size Analysis ttSoils'

E UDcfinilioruofTermsReiatingtoDcfuirjand Specific Gravity of Solids. Liquids. artGases*

3. Definition -II specific gravity—the ratio of the mass ofi

unit volume of a material al a stated tcmpeniurt-to the mass In air of the same volume of gas-fra jdistilled water al a stated temperature (per DctV'nitionsEU). j

* TMi uu ntctkod b midcr the jaM.idki.oii of ASTM Ca**l|in«.>ll*.SoaiwlR«k.rtui>Kd.rT«rapo,,il?att,^;

.- -"..AI-^T...^ n^kby..ndCkMirfCI.»

in. tsibiUivdL.*,:Lut pitiiQKt't&tm

'0104.0). 1Vol(HM.! IVol I1.0S. I

'««it can be easily inserted .„ _ ......** neck of Ihc bottle, and shall have a sm........ttVough Us center lo permit the emission of airI tad lurplus water.ff Noil 2—The UK of either ihc volumetric Hattx 01I'te Hoppcred boilk U • mailer of individual preference.I km U jentfal. ihc (Usk ihould tx used when a largerr»*|ik than can be tiicd in the stoppered bouk ist'an4c4 due to maximum grain tut of ihc sampk.i i.l Italancc—Either a balance sensitive to[ft.01 g for use with the volumetric flask, or ablancc sensitive lo 0.001 g for use with the

: Mppcfcd Mi He.

ioISoiH ,|M olilio* innnd Nov. II. IHI. PnUbhed Ju«i) :

ai l u D 1)4.0. Lul »vtou'f*t*m

» o* innn ov. .1114. Oriliuai luwd u D 1)4.0.1)1)4. II |l<

•^«,^/««a V^ITMJ.WWj. Vo. .•^..W look 44SniSo*J*lM. VcX 11.01.

i t. Calibration ul I'ycnomeler[^. a.l The pycnometer shall be cleaned, dried,nithed. and ihc weight recorded. The pycnom-(lei shall be filled with distilled walcr (Noic ))cucntially al room Icmpcraturc. The weight of

i lac pycnomclcr and walcr, If., shall be dcicr-atined and recorded. A thermometer shall be

[WneiJ in Ihc walcr and ils icmpcralurc T, dc-lcrmincd lo the nearest whole degree.

NOTI 3—Kcroiine is a bcmr wctiini aicni than•Her for most soils and may be used in place of ditiilkdvalcr for ovcn-drkd samples.

6.2 From ihc weight IK. dclcrmincd at theobserved temperature T, » table of values ofweights H'. shall be prepared for a scries of

Dcratr*-* tiul arr likely lo prevail when'•* :•-"."-\ . '-, ~ .- ^

IK,

where:II', • weight of pycnontctcr and walcr, g,| |M'/ ~ weight of pycuomcter. g. I |7*i « obscrvctt temperature of water," C,' and7', • any other desired temperature. * CA

NOTE 4—This method [troviilci a procedure Imoil convenient for latxwaiorici makint manyminaiioni with the ttmc pycnomcier. It i> capplicahle to a iin|k dcicrtninaiion. Drin|in| tt< .nomclcr and conicntt to sonic dcii|natcd temrtctalwhen weights Wt and I*', arc taken, requires iabU time, h ii much more convenient 10 PK.-labk ofwci|hlt II'. for vat-ioul lempcratuict likclprevail when wci|hli IK., ate taken. It it imponanl .wci|hu II'. and W* be baled nn water al Ihc u<tcmficraiurc. Values for the relative ikniily of waieiIcmpcraiurei from It 10 WC ate tivcn in Tahlc I.

7. SampliriK7.1 The soil to be used in specific gravity lest

may contain its natural moisture or be oven-dried. The weight of the test sample on an cdry basis shall be at least 2i g when the volume.|nc flask is to be used, and at least 10 g when tht]stoppered bottle is to be used.

7.2 Sttniptct Containing Natural A/mtiWhen the sample contains its natural moisture!the weight of Ihc soil. H'» on an oven-dry basilshall be determined at the end of the test b|evaporating the water in an oven maintained'at2.10 ±9T (t 10 ±5'C) (Note 3). Samples bf claysoils containing their natural moisture contentshall IK dispersed in distilled water before placingin the flask, using the dispersing equipment spec-ified in Mclhod D 422 (Note 6).

D O\'t'ti-l)fir<l .Si-iMi/iiY.i—When an oven*ilrittl sample is to be used, ihc umplc shall hedried for at least 12 h. or to consiuni weight, inan oven maintained at 230 ±9T (110 ±5*C)(Note 5). cooled in a desiccator, and weighedupon removal from the desiccator. The umplcshall then be soaked in distilled water for at least

12 h.Mutt i—Dryint of certain totlt al I lO'C may brim

ahoul lois of moisture of contpntiiion or hydraiion,•rul in loch caiei Jryirtj .hall he done, if iktirct). inroJuccO air prcuuic and at a kj*ti lempcraiure.

Note 6—The niinimuni volume of ilurry that canbe prepared hy Ihc diipc'tint Ci|Ui|tmeul i|xxilied inMiihoJ U 4)) it iwth that a MY) nil D.i.k u needed ».ilw pycnoniciei.

I. I'coctdiircI.I h«cc the umplc in Ihc pycnomelcr. lak-

ini care not lo lose any of Ihc toil in can Ihcwci|hl of Ihe umplc has been delermincd. Adddistilled water 10 fill Ihe volumetric Itaik aboulthrcc-rourtht full or the stoppered bottle abouthair full.

8.2 Remove entrapped air by either of thefollowini methods: (/) subject Ihe contents lo apartial vacuum (air pressure not eacecdinf 100mm ll|) or (!) boil lenlly for at least 10 minwhile occasionally rolling Ihe pycnomelcr lo as-lisl in Ihe removal or Ihe air. Subject Ihe contents10 reduced air pressure cilhcr by connccllnf, Ihepycnomelcr directly lo an aspiralor or vacuumpump, or by use of a bell jar. Some soils boilviolently when subjected lo reduced air pressure.11 will be necessary in those cases lo reduce theair pressure al a slower rale or lo use • larierflask. Cool samples that ire healed lo roomtemperature.

1.3 Fill the pycnomelcr with distilled walcr,clean the outside and dry wtlh a clean, dry cloth.Determine Ihe weithl oC the pycnometcr andconlenls. H^ and Ihc temperature in detreesCelsius. T.. of Ihe contents as described in Sec-tion i.

9. Calculation and Report4.1 Calculate the specific jravily of Ihe soil,

hated on walcr at a lemperalurc T,, as follows:Soccinc lfa.iiy. TJT. - \VJ\W. t (IK. - Hy|

where:It'. - wci|hlof sample of ovcnilry soil, |.II'. - wci|hl of pycnomcler filled wiih water al

temperature T. (Note 7). t.MA - weithl of pycnomclcr Tilled with walcr

and soil al temperature T.. i. andT, • temperature of Ihc contents of ihe pyc-

nomctcr when weight If* was deter-mined. ' C.

Nnrr. 7—This value ihill be lakcn from Ihe ubkn( v.luti at If. prepared in accordance mill «.], forIhc temperature pfcvailini when wei|hl M\ wu uttcn.

9.2 Unkss otherwise required, specific gravityvalues reported shall be based on water >: 10'C.

*( «*A «fetaj. «

TMl MMkfJ tl utjai M /»UiM « Mf i jmr *; r ikr /rffMMi jMr itrJkMrW

The value based on walcr al 20culalcd from Ihe value based oobserved lemperalurc 7., as follow*.Specific gravity. 7V20C-

where:K - • number found by dividirt

densily-of.water al Icntperalrelative density of water al2C C• range of temperatures arc iI. I

9.) When II Is desired lo rcpogravity value baaed on walcr al

M ATTJWdyiUlJMr lerMnl mmmlHtt, ••AM MM «*

TAR1.E I R«Ull«t DvMlif *f Wmt i*4 CM*«I!M FMIM

specific gravity value may beliplying ihe specific gravity value at7°, by Ihc relative density of walcr al Ir- 1 U..̂

9.4 When any portion of Ihe original usi)of soil is eliminated in the preparation oTJhcfcsample. Ihe portion on which incites! hai i*made shall be reported. I !• •»

: Ujj10. Precision and Bias . . ,,

10.1 Criteria for judging ihe aieptjbilspecific gravity lesl results obtained byjlhiilimclhod on material passing the Noj VMsieve are given as follows (Note 8)r '; I „•.

TtM.penl.ttt.*CII1*10111111141)It

111119»

hcUi.vt DcftutjroTWiict

O.t9ltl<40.9910470.9*11)4)0.49101 ))0.99710190.99717010.997 lilt0.99707700 M6I IlkO.mUSIO.miill0.99197*1OWJ47IO

ConceitFKW

I.OOCH1.000LOOM0.9990.99*

.. 0.9990.9990.9910.9910.991O.W«09970.997

MtK

'

«r AM.-* / ixAti ..(c 1

r«w IWHUHTWI «ttf fnrfn- rwr/irf , .MI ifamiwm JW lito fnw rMMwnnMi Aurr •>* r.vnni

/*-. /V/OJ

npmcM. ret(K«ll»cl)i.limiii M *wftec4 U rnokc C A70.

r»hcHV« *nU» MI MM ••••UMc *t Ihc f*t

Nitti K— The Tiiuru |ivcn In Column 2 utllamlard devutiom thai hive been round lo be ipp*1priaic Tor (he milcrialt dcKribcd in Colwm* I. Tkt|fi|ufcj |ivtn in Column 3 m (he limiu Ibil ilnot be exceeded by Ihc difference between the nof two (Kopei ly conducted icm. i • |

\ 1 I

ATTACHMENT THREE

WARZYNFLEXIBLE WALL

FALLING HEAD/RISING HltOPERMEABILITY TEST RESULTS

PflOJECT:

LOCATION:

rrwM-r • P.O. BOX •««. M.

T«»t No.JobNo_Oat* __

:{\

SAMPLEDEPTHSOIL DESCRIPTION

SAWLE DIAMETER (en)SAMPLE AREA, A (on2)SAMPLE LENGTH. L (on)MOISTURE CONTEKT. *DRY DENSITY (PCF)MAXIMUM GRADIENTNET CONFININGPRESSURE (PSI)

INITIAL FINAL INITIAL FINAL INITIAL

•

FINAL

COEFFICIENT OF PERMEABILITY, k (on/sec)RUN NO. 1

234. .56789

10AVERAGE k.

FORMULA: k

(en/see)

• 2.3 a L logio hQ. Where a « cross-sectional area of standplpe,2 At hi t • time for water level to fall from

Initial height, tyj. to final height, hjother terms are defined above)

REMARKS:

APPENDIX E-8

LOW LEVEL DETECTION TCL ORGANICS (COHPUCHEH)

STANDARD OPERATING PROCEDURE

FOR

THE ANALYSIS OF VOLATILE ORGANICS WITH LOW DETECTION LIMITS

IN RESIDENTIAL WELL WATER SAMPLES

USING GAS CHROMATOGRAPHY/MASS SPECTROMETRY

BYCOMPUCHEM

Prepared October 1987Revised January 1989

Revised May, 1989

ANALYSIS OF VOLATILE QRGANICS WITH LOW DETECTION LIMITS

El

PURGE AND TRAP GAS CHROMATOGRAPHY/MASS SPECTROMETRY METHOD

REVISED JANUARY 1989Revised May, 1989

1.0 SCOPE AND APPLICATION

1.1 This standard operating procedure describes the methodfor the analysis of volatile organics in private well,municipal water supply and domestic well samples.

1.2 This is a purge and trap gas chromatography/massspectrometry (GC/MS) method applicable to the determi-nation of 38 compounds (See Table 1) in municipal watersupply, and private well water samples.

1.3 The required method detection limit (MDL) for eachcompound is listed in Table 1.

1.4 This method is restricted to use by or under the super-vision of analysts experienced in the operation ofa purge and trap system, and gas chromatography/massspectrometry, and in the interpretation of mass spectra.Each analyst must demonstrate the ability to generateacceptable results with this method using the proceduredescribed in Section 10.

2.0 SUMMARY OF METHOD

2.1 An inert gas is bubbled through a 20-ml water samplecontained in a specially designed purging chamber atambient temperature. The purgeables are efficientlytransferred from the aqueous phase to the vapor phase.The vapor is swept through a sorbent trap where thepurgeables are trapped. After purging is completed, thetrap is heated and backflushed with the inert gas to

TABLE 1

TARGET COMPOUND LIST (TCL) AND QUANTITATION LIMITS (QLs)

(FOR RESIDENTIAL WELL WATER SAMPLES)

VOLATILE ORGANICS CAS NUMBER

BenzeneBromdichloromethaneBromoformBromomethaneCarbon TetrachlorideChlorobenzeneChloroethaneChloroformChloromethaneDibromochloromethane1 , 1-Dichloroethane1 , 2-Dichloroethane1 , 1-Dichloroethene1 ,2-Dichloroethene (Total)1 , 2-DichloropropaneCis-1 ,3-DichloropropeneTrans-1 , 3-DichloropropeneEthyl BenzeneMethylene Chloride (*)1,1,2, 2-TetrachloroethaneTetrachloroetheneToluene (*)1,1, 1-Tr ichloroethane1 ,1 ,2-Tr ichloroethaneTrichloroetheneVinyl ChlorideAcroleinAcetone (*)AcrylonitrileCarbon Bisulfide2-Butanone ( * )Vinyl Acetate4-Methyl-2-Pentanone2-HexanoneStyrenem-Xylene **

71-43-275-27-475-25-274-83-956-23-5

108-90-775-00-367-66-374-87-3

124-48-175-34-3

107-06-275-35-4

78-87-510061-01-510061-02-6

100-41-475-09-279-34-5

127-18-4108-88-3

71-55-679-00-579-01-675-01-4

107-02-867-64-1

107-13-175-15-078-93-3

108-05-4108-10-1519-78-6100-42-5108-38-3

1.51.51.51.51.51.51.51.51.51.51.51.51.51.51.52.01.01.51.01.51.51.51.51.51.51.5

25.05.0

25.03.05.05.01.55.01.01.5

0-Xylene ** 95-47-6 1.5p-Xylene ** 106-42-3 1.5

NOTE: * Common laboratory solvent. Control limits for blanks are 5the method detection limits.

** m-Xylene, o-Xylene and p-Xylene are reported as a total ofthree.

desorb the purgeables onto a gas chromatographic column.The gas chromatograph is temperature programmed toseparate the purgeables which are then detected withmass spectrometer.

3. 0

3.1 Impurities in the purge gas, organic compounds outgasingfrom the plumbing ahead of the trap, and solvent vaporsin the laboratory account for the majority of contamina-tion problems. The analytical system must be demonstratedto be free from contamination under the conditions of theanalysis by running laboratory reagent blanks. The use ofnon-telfon plastic tubing, non-telfon thread sealants, orflow controllers with rubber components in the purge andtrap system should be avoided.

3.2 Samples can be contaminated by diffusion of volatileorganics through the septum seal into the sample duringshipment and storage. A trip blank sample prepared fromorganic-free water and carried through the sampling andhandling protocol can serve as a check on such contami-nation.

3.3 Contamination by carry-over can occur whenever high leveland low level samples are sequentially analyzed. To reducecarry-over, the purging device and sample syringe must berinsed with reagent water between sample analysis.Whenever an unusually concentrated sample is encountered,it should be followed by an analysis of reagent water tocheck for cross contamination. It may be necessary towash the purging device with a detergent solution, rinseit with, distilled water, and then dry it in a 105"Coven between analysis. The trap and other parts of thesystem are also subjected to contamination; therefore,frequent bakeout and purging of the entire system maybe required.

4.0 SAFETY PRECAUTIONS

4.1 The toxicity or carcinogenicity of chemicals used inthis method has not been precisely defined, eachchemical should be treated as a potential health hazard,and exposure to these chemicals should be minimized.Each laboratory is responsible for maintaining awarenessof OSHA regulations regarding safe handling of chemicals

used in this method. A reference file of material datahandling sheets should also be made available to allpersonnel involved in the chemical analysis. Additionalreferences to laboratory safety are available for theinformation of the analysts.

4.2 The following parameters covered by this method have beententatively classified as known or suspected human ormammalian carcinogens: benzene, 1,4-dichlorobenzene, hexac-hlorobutadiene, tetrachloroethene, trichloroethene, carbontetrachloride, bis-2-chloroisopropyl ether, 1,2-dichloroethane,1,1,2,2,-tetra-chloroethane, 1,1,2-trichloroethane, chloroform,1,2-dibromo-methane, and vinyl chloride. Primary standards ofthese toxic compounds should be prepared in a hood. NIOSH/MESA approved toxic gas respirator should be worn when theanalysts handle high concentrations of these toxic compounds.

5.0 APPARATUS AND MATERIALS

5.1 Sample Containers

Forty milliliter (40-ml) screw cap glass vials withPTFE-faced silicone septum seals should be used. Washvials and seals with detergent, rinse with tap water,then distilled water, and dry at 105°C, allow to coolin area known to be free of organic vapors.

5.2 purge and Trap System (Tekmar LSC-2 or equivalent)

5.2.1 Purging Device

The all glass purging device must be capable ofaccepting 20-ml samples withn a water column atleast 5-cm deep. A glass frit installed at thebase of sample chamber allowing purging gas topass through the water column as finely dividedbubbles with a diameter of 3 cm at the origin.

5.2.2 Volatile Trap

The trap must be at least 25 cm long and have aninside diameter of at least 0.105 inches. Thetrap must contain the following amounts ofadsorbents: 1/3 of 2,6-diphenylene oxide polymer,1/3 of silica gel, and 1/3 of coconut charcoal.Prior to daily use, the trap is conditioned for10 minutes at 220°C while backflusing with an

inert gas flow of at least 20 ml/min. The trapeffluent is vented to the room through a charcoaltrap.

5.2.3 Desorber

The desorber must be capable of rapidly preheat-ing the trap to 180°C, then desorbing the trapto the GC column while maintaining the temperatureof 180°C.

5.3 GC/MS SYSTEM

5.3.1 Gas Chromatoaraph (Hewlet Parkard 5993 GC orEquivalent)

Gas chromatograph must be capable of temperatureprogramming and achieving an initial columntemperature of 30°C - 45°C. Variable constantdifferential flow controllers capable ofmaintaining constant flow rates throughout thedesorption and temperature program should be used.

5.3.2 Gas Chromatographic Column

Eight Ft. long x 1/8 O.D. glass column, packaedwith 1% SP-1000 on Carbopack B (60/80 mesh) orequivalent.

5.3.3 Mass Spectrometer (Finnicran 5100 MS or equivalent)

Must be capable of scanning from 20 to 260 amuevery 7 seconds or less, utilizing 70 V (nominal)electron energy in the electron impact ionizationmode, and producing a mass spectrum which meet allthe criteria in Table 3 when 50 ng of 4-bromo-fluorobenzene (BFB) is injected through the GC inlet

5.3.4 GC/MS Interface

GC to ms interface constructed of all glass orglasslined materials should be used. Glass canbe deactivated by silanizing with dichlorodi-methylsilane.

5.3.5 Data System

A computer system must be interfaced to the mass

spectrometer that allows the continuous acquisitionand storage on machine-readable media of all massspectra obtained through the duration of thechromatographic program. The computer must havethe software that allows searching any GC/MS datafile for spectra m/z (masses) and plotting suchm/z abundance versus time or scan number.Software must also allow integrating theabundance in any Extracted Ion Current Profile(EICP) between specific time or scan numberlimits.

5.3.6 Svrinae and Svrinoe Valves

5.3.6.1 Syringes - 5-ml and 25-ml glasshypodermic with luerlock tip (two each).

5.3.6.2 Micro Syringes - 25- and 100-ul.

5.3.6.3 Gas Syringes - 1.0 and 5.0 ml gas tight,with shut-off valve.

5.3.7 Miscellaneous

5.3.7.1 Standard Storage Containers - 3.7 mlscrew cap amber vilas.

5.3.7.2 Mininert Valves - Screw cap.

6.0 REAGENTS

6.1 Methanol, demonstrated to be free of analytes (spike100 ul into 25 ml of reagent water and analyze. Resultshould be less than detection limits.).

6.2 Reagent water, producing less than detection limits ofthose compounds that are monitored. Prepared by boilingdistilled or natural waters for 15 minutes followed by1 hour purge with inert gas while temperature is heldat 90°C or carbon filtered. Store in clean, narrowmouthed crip top PTFE-lined septa bottles.

6.3 stock Standards - Commerical mixed stock solutionsare available (Supelco Purgeeables A, B, and C) thatcontain most of the compounds of interest at a concen-tration of 0.2 mg/ml. Stock solutions must be preparedfrom neat, as folows for those compounds not included

in the commerical mixes(NOTE 1).

6.3.1 Place 24.4 ml of methanol in a 25-ml volumetricflask. Allow flask to stand unstoppered for 10minutes or until all alcohol-wetted surfaceshave dried, and then tare.

6.3.2 using a 100-ul syringe, add 50 mg of assayedreference material to the flask. Be sure thatthe drops fall directly into the alcoholwithout contacting the neck of the flask.Retare the flask and add 50 mg of the nextcompound. Repeat the process until all compoundshave been added.

6.3.3 Dilute to volume, and stopper. Mix by invertingflask several times. The resulting solution willcontain each analyte at a concentration of2.0 mg/ml.

6.3.4 Store stock standard solutions in 3-ml vialsequipped with PTFE mininert valve tops at 0°C.All standards must be replaced each month.

NOTE 1: The following compounds must be made from neat:Cis-1,2-dichloroethene, trans-1,2-dichloroethene,0-xylene, m-xylene, p-xylene, 1,3-dichloro-benzene, 1,4-dichlorobenzene, styrene,1,2-dichlorobenzene.

6.4 Secondary Dilution Standards

Using stock standards to prepare secondary dilutionstandards in methanol."The secondary dilution standardsare prepared at concentrations that can be easily dilutedto prepare aqueous calibration standards that willbracket the working range of the method.

6.4.1 To prepare secondary dilution standards, place9.0 ml of methanol into a 10-ml volumetric flask.

6.4.2 Inject exactly 250 ul of the speclco purgeable Aand purgeable B stock solution, and 250 ul ofthe stock solution prepared from neat (6.3) intothe methanol. When the standard solution is

prepared as above, the solution will contain eachanalyte at a concentration of 5 ng/ul.

6.4.3 Separate secondary dilution standard mixtureshould be prepared weekly for the gases from theSupelco purgeable C mix.

6.4.4 Store secondary dilution standards in 3-ml glassvials equipped with PTFE mininert valve screwtops. Storage conditions and time described forstock standary solutions (6.3.4) also apply to thesecondary dilution standard solutions.

6.5 Working Aqueous Calibration Standards

Using the secondary dilution standards to prepare fivecalibration standards at concentrations of 5, 10, 20,40 and 60 ug/L for all volatile compounds except theacrolein and acrylonitrile, which should be atconcentrations of 25, 50, 75, 100 and 125 ug/L.

6.6 Continuing Calibration Check Standard

Prepare the aqueous continuing calibration checkstandard solution at concentration of 20 ug/L for allcompounds except acrolein and acrylonitrile, whichshould be at concentration of SO ug/L.

6.7 Sample matrix Spiking Solution

Prepare a matrix spiking solution containing allcompounds of interest in methanol using the proceduresdescribed in Section 6.3 and 6.4. It is recommendedthat the secondardy dilution standard be prepared at aconcentration of 50 ug/mL for all compounds exceptacrolein and acrylonitrile, which shall be at aconcentration of 125 ug/mL. The addition of 10 uL ofsuch standard solution to 25 mL of reagent water orsamples would be equivalent to 20 ug/L. store at o"c.The sample matrix spiking solution should be discardedafter 1 month.

6. 8 Internal Standard Solution

Prepare a spiking solution containing Bromochloromethane,1,4-Difluorobenzene, and chlorobenzene-d5 in methanolusing the procedures described in Section 6.3 and 6.4.It is recommended that the secondary dilution standardbe prepared at a concentration of 50 ug/mL of eachinternal standard compound. The addition of 10 uL ofsuch a standard to 25 mL of sample or calibrationstandard would be equivalent to 20 ug/L.

6 .9 Surrogate Spike Standard Solution

Prepare a surrogate spiking solution containingToluene-d8, Bromofluorobenzene, and 1,2-dichloro-ethane-d4 in methanol using the procedures describedin Section 6.3 and 6.4. It is recommended that thesecondary dilution standard be prepared at a concentra-tion of 50 ug/mL of each surrogate spike compound.The addition of 10 uL of such as standard to 25 mL ofsample or calibration standard would be equivalent to20 ug/L.

6.10 4-BORMOFLUOROBENZENE (BFB) Solution

Prepare a 25 ug/mL solution of bromofluorobenzene inmethanol. This solution would be used for MS tuning.

7.0 SAMPLE COLLECTION. PRESERVATION. AND STORAGE

7.1 Sample collection

7.1.1 Collect all samples in duplicated 40-ml glassvials). Fill sample bottles to overflowing.No air bubbles should pass through the sampleas the bottle is filled, or be trapped in thesample when the bottle is sealed.

7.1.2 When sampling from a water tap, open the tap andallow the system to flush until water temperaturehas stabilized (usually about 10 minutes). Adjustthe flow to about 500 ml/min. and collectduplicate samples from the flowing system.

7.1.3 When sampling from an open body of water, filla 1-quart wide-mouth bottle or 1-liter beakerwith sample from a respresentative area, and

carefully fill duplicate sample bottles fromthe container.

7.2 Sample Preservation

7.2.1 Adjust the pH of the duplicate samples to <2 bycarefully adding one drop of 1:1 HC1 for each20 ml of sample volume (See Reference No.6). Sealthe sample bottles, PFTE-face down, and shakevigorously for one minutes.

7.2.2 The samples must be chilled to 4°C on the dayof collection and maintained at that temperatureuntil analysis. Field samples that will not bepackaged for shipment with sufficient ice toensure that they will be at 4°C on arrival atthe laboratory.

7.3 Sample storage

7.3.1 Store samples at 4°C until analysis. The samplestoragearea must be free of organic solvent vapors.

7.3.2 Analyze all samples within 7 days of collection.Samples not analyzed within this period must bediscarded and replaced.

8.0 CALIBRATION AND STANDARDIZATION

8.1 Tuning and GC/MS Calibration

8.1.1 The laboratory must establish that a given GC/MSsystem meet the standard spectral abundancecriteria prior to initiating any on-going datacollection. The GC/MS system must be hardwaretuned to meet the abundance criteria listed inTable 4 for a maximum of a 50 ng injection of4-Bromofluorobenzene (BFB). Add 50 ng of BFBsolution to 20 ml of reagent water and analyzealone. BFB should NOT be analyzed simultaneouslywith any calibration standards or blanks. Thiscriteria must be demonstrated dialy or for eachtwelve-hour (12) time period. If required,background substraction must be straight forwardand designed only to eliminate column bleedor instrument background.

8.1.2 BFB criteria MUST be met before any standards,samples or blanks are analyzed.

8.1.3 Any action taken which may results in effectingthe tuning criteria for BFB, the tune must beverified irrespective of the twelve-hour tuningrequirement.

8.1.4 The laboratory shall document the GC/MS tuningand mass calibration each time the system is tuned.

8. 2 Calibration of GC/MS system

8.2.1 Initial Internal Standard Calibration

8.2.1.1 Prior to the analysis of samples andrequired blanks and after tuningcriteria have been met, the GC/MS systemmust be initially calibrated at a minimumof five concentrations to determine thelinearity of response utilizing theinitial calibration standard solutionscontaining all compounds listed in Table 2.Once the system has been calibrated,the calibration must be verified afterthe initial calibration and each twelve(12)hours time period for each GC/MS system.

TABLE 2

CHARACTERISTIC IONS FOR VOLATILE ORGANIC COMPOUNDS

Parameters Primary Ion Secondary Ions

ChloromethaneBromomethaneVinyl ChlorideChloroethaneMethylene ChlorideAcetoneCarbon Disulfide1 ,1-Dichloroethene1 ,1-Dichloroethane1 ,2-DichloroetheneChloroform1 , 2-Dichloroethane2-Butanone1,1, 1-Tr ichloroethaneCarbon TetrachlorideVinyl AcetateBromodi Chloromethane1,1,2, 2-Tetrachloroethane1 ,2-DichloropropaneTrans-1 , 3-DichloropropeneTrichloroetheneDibromochloromethane1,1, 2-Tr ichloroethaneBenzeneCis-1 , 3-DichloropropeneBromoform2-Hexanone4-Methyl-2-pentanoneTetrachloroetheneTolueneChlorobenzeneEthyl BenzeneStyreneTotal Xylenes

5094626484437696639683627297

1274383836375

130129

977875

1734343

16492

112106104106

52966466

49, 51, 865878

61, 9865, 83, 85, 98, 100

61, 9885

64, 100, 9857

99, 117, 119119, 121

8685

85, 131, 133, 16665, 114

7795, 97, 132

208, 20683, 85, 99, 132, 134

-77

171, 175, 250, 252, 25458, 57, 100

58, 100129, 131, 166

911149178, 10391

The primary ion should be used unless interferences are present,in which case, a secondary ion may be used.

TABLE 3

VOLATILE INTERNAL STANDARDS WITH CORRESPONDING TCL ANALYTES

ASSIGNED FOR QUANTITATION

Bromochloromethane 1,4-Difluorobenzene Chlorobenzene-ds

ChloromethaneBromomethaneVinyl ChlorideChloroethane

Methylene ChlorideAcetoneCarbon Bisulfide1,1-dichloroethene1,1-dichloroethane

1,1,1-TrichloroethaneCarbon TetrachlorideVinyl AcetateBromodichloromethane

1,2-DichloropropaneTrans-1,3-dichloropropeneTrichloroetheneDibromochloromethane1,1,2-Trichloroethane

1,2-Dichloroethene(Total)BenzeneChloroform Cis-1,3-dichloropropene1,2-Dichloroethane Boroform2-Butanone1,2-Dichloroethane-d4

(surrogate)

2-Hexanone4-Methyl-2-PentanoneTetrachloroethene1,1,2,2-tetra-

chloroethaneTolueneChlorobenzeneEthylbenzeneStyreneXylene (total)Bromofluorobenzene

(Surrogate)Toluene-ds(surrogate)

TABLE 4

p-BROMOFLUOROBENZENE (BFB) KEY IONS AND ABUNDANCE CRITERIA

Mass Ion Abundance Criteria

50759596

173174175176

15.0 - 40.0 % of the base peak30.0 - 60.0 % of the base peakBase peak, 100 % relative abundance5.0 - 9.0% of the base peakLess than 1.00% of the base peakGreater than 50.0% of the base peak5.0 - 9.0% of mass 174Greater than 95.0%, but less than 101.0%

of mass 174.

NOTE: BFB criteria MUST be met before any samples, sample extracts,blanks, or standards are analyzed.

8.2.1.2 Prepare calibration standards by spikingfive portions of 20 ml reagent waters withvarious amount of secondary dilutionstandard solution (6.4) to yield thefollowing specific concentrations: 5, 10,20, 40, and 60 ug/L for all compoundsexcept acrolein and acrylonitrile, whichhave the specific concentrations at 25,50, 75, 100 and 125 ug/L.

Internal standards and surrogate spikestandards will be added to each eachcalibration standard solutions to yield aconcentration of 20 ug/L.

8.2.1.3 Analyze each calibration standard solutionand tabulate the area of the primarycharacteristic ion againt concentrationfor each compound including all requiredinternal standards and surrogate standardcompounds. The relative retention time(RRT) of each compound in each calibrationrun should agree within 0.06 RRT units.

8.2.1.4 Use Table 4 and Equation 1 to calculatethe relative response factor (RRF) foreach compound at each concentration level.

RRF = ———— x ———————— Equation 1Ais Cx

Where,

Ax = Area of the characteristic ion forthe compound to be measured.

Ais = Area of the characteristic ion forthe specific internal standardsfrom Table 2.

cis = Concentration of the internalstandard (ng/UL) .

Cx = Concentration of the compound tobe measured (ng/uL) .

8.2.1.5 Use equation 2 and the relative responsefactors (RRF) from the initial calibra-tion to calculate the relative standarddeviation (%RSD) for compounds labelledas calibration check compounds in Table 4.

SD%RSD = ————————— X 100 Equation 2

X

Where,

RSD = Relative Standard Deviation

SD = Standard Deviation of initialrelative response factors(per compound).

Where : SD = / 2_ —————————— E<?- -

X = Mean of initial relativeresponse factors (per compounc

The %RSD for each individual calibrationcheck compound must be less than or equalto 30.0%. This criteria must be met forthe initial calibration to be valid.

8.2.1.6 System Performance Check

A system performance check must be performecto insure that minimum average relativeresponse factors are met before the calibra-tion curve is used. This is done by analyzirfive system check compounds (SPCCs):Chloromethane, 1,1-dichloroethane, bromoforr1,1,2,2-tetrachloroethane, and chlorobenzemThe minimum acceptable RRF for these compouiis 0.300 (0.100 for bromoform, and 0.200 foi1,1,2,2-tetrachloroethane).

8.2.1.7 The initial calibration is valid only after

both the %RSD for calibration check compoundand the minimum RRF for SPCC have been met.Only after both of these criteria are met casample analysis begin.

8.3 Continuing Calibration Check

8.3.1 A calibration standard(s) containing all volatileorganics listed in Table 2, including all requiredsurrogate compounds, must be analyzed each twelvehours during analysis. The concentration of eachcompound in the continuing calibration check (CCC)is 20 ug/L except acrolein and acrylonitrile(50 ug/L). Compare the relative response factordata from the standards each twelve hours with theaverage relative response factor from the initialcalibration for a specific instrument. A systemperformance check must be made each twelve hours.If the SPCC criteria are met, a comparison ofrelative response factors is made for all compounds.

8.3.2 After the system performance check is met, useequation 4 to calculate the percent difference(% difference) for all calibration check compoundsin Table 4 in order to check the validity of theinitial calibration.

8.3.2.1 Calculate the percent difference usingEquation 4.

RRFj - RRFC%Difference = ———————————— x 100 Eq. 4

RRFj

Where

RRFj = Average relative response factorfrom initial calibration.

RRFC = Relative response factor fromcurrent calibration check.

8.3.2.2 If the percent difference for any compoundis greater than 20%, the laboratory shouldconsider this a warning limit. If thepercent difference for each CCC is less

than or equal to 25.0%, the initialcalibration is assumed to be valid. If thecriteria are not met (>25.0% difference ),for any one of the calibration checkcompound, corrective action MUST be taXen.Problems similar to those listed underSPCC could affect this criteria. If nosource of the problem can be determinedafter corrective action have been taken,a new initial five points calibration MUSTbe generated. These criteria MUST be metbefore sample analysis begins.

9.0 QUALITY CONTROL

9.1 Each laboratory that uses this method is required tooperate formal quality control program. The minimumrequirements of this program consists of an intialdemonstration of laboratory capability and an ongoinganalysis of spiked samples to evaluate and documentdata quality. The laboratory must maintain records todocument the quality of data that is generated. Ongoingdata quality checks are compared with establishedperfromance criteria to determine if the results ofanalysis meet the performance characteriztics of themethod. A quality control check standard must beanalyzed to confirm that the measurements wereperformed in an in-control mode of operation.

9.1.1 The analyst must make an initial, one-time,demonstration of the ability to generateacceptable accuracy and precision with thismethod. This ability is established as aredescribed in Section 9.2

9.1.2 In recognition of advances that are occurring inchromatography, the analyst is permitted certainoptions (detailed in Section 10.2.2) to improvethe separation or lower the cost of measurements.Each time such a modification is made to themethod, the analyst is required to repeat theprocedure in Section 9.2 .

9.1.3 Each day, the analyst must analyze a reagentwater blank to demonstrate that interferencesfrom the analytical system are under control.

9.1.4 The laboratory must, on an ongoing basis,demonstrate through the analyses of qualitycontrol check standards that the operation ofthe measurement system is in control. Thefrequency of the check standard analyses isequivalent ot 10% of all samples analyzed but atleast two samples per month. Using thefollowing procedure to analyze a quality controlcheck sample for all analytes of interestat 10 ug/L:

9.1.4.1 Prepare a QC check sample by adding50 ul of QC check sample concentrateto 20 ml of reagent water in a glasssyringe.

9.1.4.2 Analyze the QC check sample according toSection 10, and calculate the recoveryfor each analyte. The recovery must bebetween 60% and 140% of the expectedvalues.

9.1.4.3 If the recovery for any analyte fallsoutside the designated range,the analytehas failed the acceptance criteria.A check standard containing each analytethat failed must be re-analyzed.

9.1.5 On a weekly basis, the laboratory must demonstratethe ability to analyze low level samples. Thefollowing procedure should be used:

9.1.5.1 Prepare a low level check sample byspiking 10 ul of QCcheck sampleconcentrated to 25 ml of reagent waterand analyze according to the methodin Section 10.0 .

9.1.5.2 For each analyte, the recovery must bebetween 60% and 140% of the expected value.

9.1.5.3 When one or more analytes fail the test,the analyst must repeat the test onlyfor those analytes which failed to meetthe criteria. Repeated failure, however,will confirm a general problem with themeasurement system. If this occurs,locate

and correct the source of the problem andrepeat the test for all compounds ofinterest beginning with 9.1.5.1.

9.1.6 The laboratory must maintain performance recordsto document the quality of data that is generated.The following procedure should be performed:

9.1.6.1 It is recommeded that the laboratoryadopt additional quality assurancepractices for use with this method. Thespecific practices that are most productivedepend upon the needs of the laboratoryand the nature of the samples. As a minimum,field duplicate samples must be analyzedto assess the precision of the environmentalmeasurements.

9.2 To establish the ability to generate acceptable accuracyand precision, the analyst must perform the followingoperations.

9.2.1 A quality control check sample concentrate containingeach analyte at a concentration of 500 times the MDLin methanol is required. The QC check sample must beprepared by the laboratorry using stock standardsprepared independently from those used for calibratio

9.2.2 Analyze seven 20-ml QC check samples at 2 ug/Laccording to the method beginning in Section 10.0 .Each sample is produced by injecting 10 ul of QCcheck sample concentrate into 25 ml of reagent waterin a glass syringe through the syringe valve.

9.2.3 Calculate the average recovery (X) in ug/L, and thestandard deviation of the recovery (S) in ug/Lfor each analyte using the seven results. Calculatethe MDL for each analyte as specified in Reference 2.The calculated MDL must be less than the spike level.

9.2.4 For each analyte, (X) must be between 90% and 110% ofthe true value. Additionally, s must be <35% of X.If s and X for all analytes meet the criteria, thesystem performance is acceptable and analysis ofactual samples can begin-. If any s exceeds theprecision limits or any X falls outside the rangefor accuracy, the system performance is unacceptablefor that analyte.

NOTE: The larger number of analytes present asubstantial probability that one or more willfail at least one of the acceptance criteriawhen all analytes are analyzed.

9.2.5 When one or more of the analytes tested fail at leastone of the acceptance criteria, the analyst mustproceed according to Section 9.2.2 only for theanalytes which fialed the test.

10.0 PROCEDURE OF SAMPLE ANALYSIS

10.1 DAILY GC/MS PERFORMANCE TESTS

10.1.1 At the beginning of each day that analyses areto be performed, the GC/MS system must bechecked to see if acceptable performance criteriaare achieved.for 4-Bromofluorobenzene (BFB).The performance test must be passed before anysamples, blanks, or standard are analyzed.

10.1.2 At the beginning of each day, inject 2 ul(50 ng) of BFB solution directly onto the column.Alternatively, add 2 ul of BFB solution to20.0 ml of reagent water or calibration standardand analyze the solution according to Section 8.1Obtain a background-corrected mass spectrum ofBFB and confirm that all the key m/z criteria inTable 4 are achieved. If all the criteria arenot achieved, the analyst must re-tune the massspectrometer and repeat the test until allcriteria are achieved.

10.2 INITIAL CONDITIONS

10.2.1 Acquire GC/MS data for perfomance tests,standards and samples using the followinginstrumental conditions:

Electron Energy : 70 V (Nominal)

Mass Range : 35 to 300 amu

Scan Time : To give at least 5 scansper second, but not to exceed2 seconds per scan.

10.2.1. The operating conditions for the gaschromatograph are summarized under Section10.4.2.2 . Table 1 and Table 2 list theretention times and MDL that can be achievedunder these conditions. Other columns orchromatographic conditions may be used if therequirements of Section 9.0 are met.

10.3 SAMPLE INTRODUCTION AND PURGING

10.3.1 Adjust the purge gas (nitrogen or helium) flowrate to 40 ml/min. Attach the trap inlet tothe purging device and open the syringe valveon the purging device.

10.3.2 Remove the plungers from two 25-ml syringes andattach a closed syringe valve to each. Warm thesample to room temperature, open the sample (orstandard) bottle, and carefully pour the sampleinto one of the syringe barrels to just short ofoverflowing. Replace the syringe plunger, invertthe syringe, and compress the sample. Open thesyringe valve and vent any residual air whileadjusting the sample volume to 20.0 ml. Add10 ul of the internal standard spiking solution(Section 6.8) and 10 ul of the surrogate spikingstandard solution (Section 6.9) to the samplethrough the syringe valve. Close the valve. Fillthe second syringe in an identical manner fromthe same sample bottle. Reserve the secondsyringe for a reanalysis if necessary.

10.3.3 Attach the sample syringe valve to the syringevalve on the purging device. Be sure that thetrap is cooler than 25oC, then open the samplesyringe valve and inject the sample into thepurging chamber. Purge the sample for 11.0 ±0.1min at ambient temperature.

10.4 SAMPLE DESORPTION

The mode of sample desorption is determined by the typeof capillary column employed for the analysis. Whenusing a wide-bore capillary column, follow thw desorptionconditions of Section 10.4.1 . The conditions for usingnarrow-bore capillary column is described in Section 10.4

10.4.1 Sample Desorption for Wide-Bore Capillary Column

Undre most conditions.this type of column must beinterfaced to MS through a all-glass jet separator

10.4.1.1 After the 11-minute purge, attach thetrap to the chromatograph, adjust thepurge and trap system to the desorbmode and initiate the temperatureprogram sequence of the gas chromatograpand start data aquisition. Introducethe trapped materials to the GC columnby rapidly heating the trap to 180°Cwhile backflushing the trap with an inergas at 15 ml/min for 4.0 + 0.1 min.While the extracted sample is beingintroduced into the gas chromatograph,empty the purging device using the samplsyringe and wash the chamber with two25-ml flushes of reagent water. Afterthe purging device has been emptied,leave the syringe valve open to allowthe purge gas to vent through the sampleintroduction needle.

10.4.1.2 Gas Chromatography - Hold the columntemperature at 10°C for 5 minutes,then program at 6°C/min to 160°Cand hold until all analytes eluted.

10.4.1.3 Trap Reconditioning - After desorbingthe sample for 4 min, recondition thetrap by returning the purge and trapsystem to the purge mode. Wait 15seconds, then closed the syringe valveon the purging device to begin gas flowthrough the trap. Maintain the traptemperature at 180°C. After approxi-mately 7 minutes, turn off the trapheater and open the syringe valve tostop the gas flow through the trap.When the trap is cool, the next samplecan be analyzed.

10.4.2 Sample Desorption for Narrow-Bore Capillary Column

Under normal operating conditions, most narrow-

bore capillary columns can be interfaceddirectly to the MS without a jet separator.

10.4.2.1 Sample Desorption

After the 11 minutes purge, attachthe trap to the cyrogenically cooledinterface at -15°C and adjust thepurge and trap system to the desorbmode. Introduce the trapped materialsto the interface by rapidly heatingthe trap to 180°C while backflusingthe trap with an inert gas at 4 ml/minfor 5.0+0.1 min. While the extractedsample is being introduced into theinterface,empty the purging deviceusing the sample syringe and rinse thechamber with two 25-ml flushes ofreagent water. After the purgingdevice has been emptied, leavethe syringe valve open to allow thepurge gas to vent through the sampleintroduction needle. After desorbingfor 5 minutes, flash heat the interfaceto 250°C and quickly introduce thesample onto the chromatographic column.Start the temperature program sequence,and initiate data acquisition.

10.4.2.2 Gas Chromatograph

Hold the column temperature at lO^Cfor 5 minutes, then program at 6°C/minto 70°C and then at 15°C/min to145°C.

10.4.2.3 Trap Reconditioning

After desorbing the sample for 5minutes, recondition the trap byreturning the purge and trap system tothe purge mode. Wait 15 seconds, thenclose the syringe valve on the purgingdevice to begin gas flow through thetrap. Maintain the trap temperatureat ISO^C. After approximately 15minutes, turn off the trap heater andopen the syringe valve to stop the gas

flow through the trap. When the trapis cool, the next sample can be analyzec

10.5 TERMINATION OF DATA ACQUISITION

When sample components have eluted from the GC, terminateMS data acquisition and store data files on the data systtstorage device. Use appropriate data output software todisplay full range mass spectra and appropriate EICPs.If any ion abundance exceeds the system working range,dilute the sample aliquot in the second syringe withreagent water and analyze the diluted aliquot.

11.0 QUALITATIVE IDENTIFICATION

11.1 IDENTIFICATION PROCEDURES CRITERIA

Tentatively identify a sample component by comparison ofits mass spectrum (after background substraction) to areference spectrum in a collection. Use the follwoingcriteria to confirm a tentative identification:

11.1.1 The GC retention time of the sample componentmust be within 10 seconds of the time observedfor that sample compound when a calibrationsolution was analyzed.

11.1.2 All ions that are present above 10% relativeabundance in the mass spectrum of the standardmust be present in the mass spectrum of thesample component and should agree within absolute10%. For example, if an ion has a relativeabundance of 30% in the standard spectrum, itsabundance in the sample component should be inthe range of 20 to 40%.

11.1.3 Identification is hampered when sample componentsare not resolved chromatographically and producemass spectra containing ions contributed by morethan one analyte. Because purgeable organiccompounds are relatively small molecules andproduce comparatively simple mass spectra, thisis not a significant problem for most methodanalytes. When GC peaks obviously represent morethan one sample component (i.e., broadened peakwith shoulder(s) or valley between two or more

maxima), appropriate analyte spectra and backgrounspectra can be selected by examining EIcPs ofcharacteriztic ions for tentatively identifiedcomponents. When analytes coelute (i.e., onlyone GC peak is apparent), the identificationcriteria described in Section 11.1.2 can be metbut each analyte spectrum will contain extraneousions contributed by the coeluting compound.

11.1.4 Structural Isomers that produce very similarmass spectra can be explicity identified only ifthey have sufficiently different GC retentiontimes. Acceptable resolution is achieved if theheight of the valley between two isomer peaks isless than 25% of the sum of the two peak heights.Otherwise, structural isomers are identified asisomeric pairs.

12.0 CALCULATION

12.1 When an analyte has been identified, the quantitationof that analyte should be based on the integratedabundance from the EICPs of the primary characteristicm/z given in Table 2. If the sample produces aninterference for the primary m/z, use a secondarycharacteristic m/z to quantitate. Instrument calibrationfor secondary ions is performed, as necessary, usingthe data and procedures described in Section 8.2.

12.2 Calculate the concentration in the sample using thecalibration curve or average response factor (RF)determined in Section 8.2.2 and Equation 3 :

(As) <Cis>Concentration (ug/L) = ————————————— Equ. 3

(Ais) (RF)

Where,

As = Area of the characteristic m/z for theanalyte to be measured;

Ais = Area of the characteristic m/z for theinternal standard;

Cis = Concentration of the internal standard,in ug/L.

12.3 Report results in ug/L. All QC data obtained shouldbereported with the sample results.

13.0 DATA REPROTING REQUIREMENTS

13.1 All reports and documentation must be legible,single-sided, and clearly labelled and paginated.

13.2 The sample data package must be consecutivelypaginated and shall include the cover pages, sampledata, and the raw data as they are described in thefollowing:

13.2.1 Cover Pages for the data package, includingthe project name; laboratory name; fieldsample number cross-referenced with laboratoryID number ; comments describing in details anyproblems encountered in processing the samplesin the data package; and validation andsignature by the Laboraotry Manager.

13.2.2 Sample Data

Sample data shall be reported using the OrganicAnalysis Data Reporting Forms (Attachment I)for all samples, arranging in increasingalphanumeric sample number order, followed bythe QC analysis data, Quarterly verification ofinstrument parameters forms, raw data, and copiesof the sample preparation logs.

13.2.2.1 FORM I ( Organic Analysis Data Sheet)

13.2.2.2 FORM I (Tentatively Identified Compound

13.2.2.3 FORM II (Surrogate Recovery)

13.2.2.4 FORM III (Matrix Spike/Matrix SpikeDuplicate Recovery)

13.2.2.5 FORM IV (Method Blank Summary)

13.2.2.6 FORM V (GC/MS Tuning and Mass

Calibration)

13.2.2.7 FORM VI (Initial Calibration Data)

13.2.2.8 FORM VII (Continuing Calibration Data)

13.2.2.9 FORM VIII (Internal Standard AreaSummary)

13.2.2.10 Raw Data

Raw data shall includes ReconstructedIon Current (RIC) Chromatogram, Massspectrum (with and without backgroundsubstraction for all compoundsquantified,mass spectrum of tentativelyidentified compound including the mostmatched library standard spectra, anyinstrument printouts, etc.

14.0 REFERENCES

14.1 A. Alford-Stevens, J.W. Eichelberger, W.L. Budde,"Purgeable Organic Compounds in Water by Gas Chroma-tography/Mass Spectrometry, Method 524." EnvironmentalMonitoring and Support Laboratory, U.S. EnvironmentalProtection Agency, Cincinnati, Ohio, February 1983.

14.2 Glaser, J. A., D. L. Foerst, G.D. McKee, S.A. Quave, andW.L.Budde, "Trace Analyses for Wastewaters," Environ. Sci.Technol., 15, 1426, 1981.

14.3 "The Determination of Halogenated Chemicals in Water bythe Purge and Trap Method, Method 502.1, "EnvironmentalProtection Agency, Environmental Monitoring and SupportLaboratory, Cincinnati, Ohio 45268, April, 1981.

14.4 "Volatile Aromatic and Unstaturated Organic Compounds inWater by Purge and Trap Gas Chromatography, Method 503.1,"Environmental Protection Agency, Environmental Monitoringand Support Laboratory, Cincinnati, Ohio, April, 1981.

14.5 Bellar, T.A. and J.J. Lichtenberg, "The determination ofSynthetic Organic Compounds in Water by Purge andSequential Trapping Capillary Column Gas Chromatography,"U.S.Environmental Protection Agency, Environmental

Monitoring and Support Laboratory, Cincinnati, Ohio,4526£

14.6 Ho. J.S. Method Performance Data for Method 502.2,Unpublished Report, September, 1986.

14.7 "Gas Chromatographic Analysis of Purgeable Halocarbon ancAromatic Compounds in Drinking Water Using Two Detectorsin series," Kingsley, B.A., Gin, C., Coulson, D.M. , andThomas, R.F., Water Chlorination, Environmental Impactand Health Effects, Volume 4, Ann Arbor Science.

14.8 "EPA Method Validation Study 23, Method 601 (PurgeableHalocarbon)," U.S. Environmental Protection Agency,Environmental Monitoring and Support Laboratory,Cincinnati, Ohio 45268.

VOLATILE ORGANICS ANALYSIS DATA SHEET

Lab Max*:Field Sample Humber_Matrix: water

Saaple vol: _

Level: (lov/aed) _

Column: (pack/cap) ___

CAS NO. COMPOUND

Lab Saaple ID:Lab File ZD:Date Received:Date Analysed:Dilution Factor:

CONCENTRATION UNITS:

74-87-3————"Chloronethane____74-83-9—————-BroBoaethane____75-01-4——————Vinyl Chloride___75-00-3——————Chl ore* than*____75-09-2——————Methylene Chloride67-64-1———————Acetone75-15-0——————Carbon Di»ulfide_75-35-4———————1,1-Dichloroethene75-34-3——————l,l-Dichloro*thane_______540-59-0—————1,2-Dichloroethene (total)_67-66-3——————Chlorofora________107-06-2——————1,2-Diehloroethane__78-93-3——————2-Butanone_________71-55-6——————1,1,1-Trichloroethane5«-23-5-—————Carbon T*trachl«rid« '108-05-4—————Vinyl Acetate75-27-4———•——BreaodiehleroB«thane '_78-87-5————-1,2-Dichloropropane___10061-01-5——--ci«-l,3-Dichloropropene79-01-6——————Trichloroethene______'_124-48-1————-DibroBochloroBethane__79-00-5——————1,1,2-Trichloroe thane_71-43-2——————Bentene _________10061-02-6———tran»-l.3-Dichloropropene75-25-2——————Broaofor-_________108-10-1—————4-Methyl-2-Pent«none591-78-6——————2-Hexanone_______127-18-4—————Tetraehloroethene________79-34-5——————1,1,2,2-Tetrachloroethane__108-88-3—————Toluene_______________108-90-7—————Chlorobeniene__________100-41-4—————Ethylbensene___________100-4 2-5—————Styrene_________________1330-20-7————Xylene (total)__________

FORM I VOA

VOLATILE ORCMIICS ANALYSIS DATA SHEETTENTATIVELY IDENTIFIED COKPOUHDS

Lab Male:________Lab Sanple I.D. _Matrix: waterSaaple Vol:Level: (lov/m«d)

Column: (pack/cap)

Number TICc found:

Field Saaple Humber_

Lab m« ID: _Date Received: __

Date Analysed: _Dilution Factor:

CONCENTRATION UNITS:(ug/L

CAS NUMBER

1.2.3.4.5.6.7.8.9.10.11.12.13.14.15.16.17.18.19.20.21.22.23.24.25.26.27.28.29.30.

COMPOUND NAME XT

'

EST. CONC. 0

FORM I VOX-TIC

WATER VOLATILE SURROGATE MCOVTRY

Lab Mac*:

I F i e l dI SAMPLE MO.

Oil.02|.031.°«LOS)06|.07|OS |09|"10|"L121

V7 I"

20|.21122|

26)27|.281.291.301.

SI I 82 | S3 (OTHER |TOT|(TOL)I|(BFB)I|(DCZ)I| |OOT|

QC LIMITSSI (TOL) • Tolu«n«-<J8 (88-110)62 (BFB) • Broaofluorobenzene (86-115)S3 (DCE) • l,2-Dichloroethane-d4 (76-114)I Column to be used to flag recovery value*• Values outside of contract required QC liaits

D Surrogates diluted out

page _ of _FORM II VOA-1

MATER VOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY

Lab N«»e:Lab Sample I.D. _. Field Sample Number

Matrix Spike - 1FA Suple Mo.s

COMPOUND

1 . 1-DichloroetheneTrichloroetheneBenzeneTolueneChlorobenzene

SPIKEADDED(ug/L)

SAMPLECONCENTRATION

<ug/L)MS

CONCENTRATION(ug/L)

MS | O.C |% | LIMITS]

REC f! REC. |

161-1451171-1201176-1271176-1251175-13011 1

COMPOUND

1 , 1-DichloroetheneTrichloroetheneBenzeneTolueneChlorobenzene

SPIKEADDED(ug/D

MSDCONCENTRATION

(ug/L)MSD%

REC f%

RPD f

1OC LIMITS |RPD | REC. |

14 |61-145|14 |71-120|11 |76-127|13 |76-125|13 |75-130|

1 1

t Column to be u»ed to flag recovery and RPD value* with an asterisk

* Values outside ef QC liaits

RPD:____ out efSpike Recovery:__

__ outside Haltsout of ____ outside limits

COMMENTS:

FORM III VOA-1

VOLATILE METHOD BLANK SUMMARY

Lab Mas*:

Lab Fil« ID: _

Date Analysed:Matrix: ' ' water

Xnstruaent ZD:

Lab Saaple ID:

Ti»e Analyzad:

Level:(lew/aad)

THIS METHOD BLANK APPLIES TO TOE FOLLOWING CAMPLES, MS AND MSD:

1 Field| SAMPLE NO.1 —— — —— —— •—

Oil0210310410510£|0710810911011111ZI131141151161171181191201211221231241251261271281291301

LABSAMPLE ID

'

LABFILE ID

TIMEANALYZED

COMMENTS:

page _ of _FORM IV VOA

VOLATILE ORGANIC CC/MS TUNING AMD MASSCALIBRATION - BROMOFLUOROBENZENE (BFB)

Lab Maae:________

Lab Sanple I.D. _

Lab File ID: __Instrument ID: __

Matrix: •-. Vater

Field Sample HumberBFB Injection Dete:_

BTB Injection Ti»e:_Level :(lov/»«<J) Column:(peck/cap)

»/•50759596

173174175176177

ION ABUNDANCE CRITERIA

15.0 - 40.0% ef Base 9530.0 - CO.Ot Of Bau 95Bas« p«ak. 1001 r*l«tlv« abund«nc«5.0 - 9.0* of •&*• 95Less than 2.0* of mass 174Greater than 50.0% of M» 955.0 - 9.0% Of MM 174Greater than 95.0%, but le*c than 101.0% of mass 1745.0 - 9.0% of *••( 176

t RELATIVEABUNDANCE

( )1

( 11( Jll( »2I

11-Value is % mass 174 2-Value is % Bass 176

THIS TUNE APPLIES TO THE FOLLOWING SAMPLES, MS, KSD, BLANKS, AND STANDARDS:

1 Field| SAMPLE NO.

Oil02103 J04105106107108109110111112113114115)161171HI191201211221

LABSAMPLE ID

LABFILE ID

•

DATEANALYZED

TIMEANALYZED

page _ of _FORM V VOA

VOLATILE ORGANICS XMITIAX. CALIBRATION DATA

Lab Maaa:

Instrument ID: Calibration Dat«(»):_Matrix: w*t«r; __ X«val: (low/Bad) .___ Column: (pack/cap) ___Kin fRF for SPCC(f) - 0.300 (0.350 for BroBofon) tax %XSD for CCC{«) • 30.0»|LAB FILE ID:JRW100-____I___________

RRF20 • KRT50 •RRTJOO-

COMPOUND

| ChloroB«thane_|Bronoa«than« ~jvinyl Chloride_| Chloro«than«_|K*thyl«na Chlorida_|Ac«ton«_(Carbon Diaulfidaj1,l-Dichloro«than«il.l-Pichlero«thana"j1,2-Dichloro«th*n« (total)_jChloroform11,2-Dichloro«than«j 2-Butanena ~11,1,l-Trlchloro«than«_(Carbon T«tr»chlorid«_^(Vinyl Acatat«_|BrOBod i chloroB*than«11,'2-t)lcTiloroprop«n« '|elB-l,3-Dlchloroprop«na _|Trlchloro«th«n«jDibroBochlorox*thana__(1,1,2-Trichloroathan«_(Bcnz«n«_11 ran«-1.J-Dichloroprctxnaj Broaoforv

-K«thyl-2-?«ntanona_|2-Haxanon* ~|T«trachloro«th«n«_(1,1,2,2-T«trachloro«than«_(Tolucn*|Chlorobansan*IEthylb«nsana_^|Styr«na_(Xylana (total)I-(Tolu«n«-d8( BroBofluorobcnz«nt_____

, 2-Dlchloro«than«-d4_

|HRriOO|RW150|RW200|

——FORM VI VOX'

USD

VOIATXIC CONTXNDXNC CALXBKATXOM CHICK

Lab Kaaa:

Xnatroant ID: Calibration Data: Tiaa:Xnlt. Calib. Data(a):_lab Fila ID: ________

Matrix: *mt«r __ J*val: (lew/Bad) _ Colon: (pack/cap) j__Kin WUT50 for SFCC(f) - 0.300 (0.250 for Broaofora) Max %0 for CCC(*) - 25.0%

I COMPOUND

| CbloroBathana_|BroBOiathana(Vinyl Chloridl(CMoroathana(Kcthylana Cblorida_|Aeatona_(Carbon Diaulflda|l,l-Dichloroathanaj1,l-Dichloro«thana~11,2-Dichloro«Uiana (total)_jcblorofo ~j1,2-Diehloroathana|2-Butanonaj1,1,1-Trlchloroathana(Carbon Tatraehlerlda_^(Vinyl Acatat*|Broaod ichloromathana11.2-Dichloropropana 'j cia-1,3-Dlchloroprop«na(Trlehloroath«n«I Dibro»ochlcro»«th«n«_(1,1,2-Trlchloro«thana_jBanxan*_j tran»-l. 3-DicMeropropana(Broaofo:j 4-Mathyl-2-Pantanonaj 2-Haxanona_Tatrachloroatbana1,1,2,2-Tatraehloroathana_ToluanaChlorobanxana|Ethylbansana__jstyrana_(Xylana (total)|Toluana-d8________j BroBofluorobancanaIl,2-Dichloroatbana^3T"I________________I

KRF (wtrso %D

roni vii VOA

VOLATILE ZXTZRHAL STMtDMU) AREA nMMARY

Lab *•••:

Lab ril* ID (Standard)I

XMtnaant ZD: _____Matrix: Vmtar Lavali(lov/m*a)

Data Analycad:___*i»a Analycad:___

_ Celnnt: (pack/cap)

12 HOUR CTD

OPPER LIMIT

LOWER LIMIT

FieldSAMPLEMO.

"I.021.031.0<l.051.06 1.071.081.•»l.101.111-

XSl(BCM)KT

»2(DFB)ARZA

ZCl(CBZ) |AREA || RT

1*1-l«l-I'l-l«l."I.301-211.

IS1 (BCM) - Bro«ochloro»«th»n«162 (DFB) • 1,4-Di'luorobantanaISJ (CBZ) • Chloreb«ncana-d5

CPPER LIMIT • 4 100%ef intamal Btandard arat.LOWER LIMIT - - 50*of intarnal Btandard arta.

I Colmn naad to flag intarnal standard araa valuac with an attarickef _

FORM VIII VOA

COVER FACE - INORGANIC ANALYSES DATA PACKAGE

I*b Hue: ___________________

Field Cupic No. lab Caaple ZD.

Were ICP intereleaent corrections applied? Yes/No

Were ICP background corrections applied? Yes/NoIf yes-were raw data generated beforeapplication of background corrections? Yes/No

Comments:

Release ef the data contained In this hardcopy data package and in thecomputer-readable data «ubaitted on floppy diskette has been authorized bythe Laboratory Manager or the Manager's designee, as verified by thefollowing signature.

Lab Manager: _________________Date:

COVER PACE - ID


FORTHE ANALYSIS OF SEMIVOLATILE ORGANICS IN DRINKING WATER

WITH LOW DETECTION LIMITS

USING GAS CHROMATOGRAPHY/MAS SPECTROMETRY

BY COMPUCHEM

Prepared December, 1988Revised May, 1990

Quality Assurance Notice

CompuChem follows the attached Semivolatile SOP with modification to Section 6.11.1 of theSOP, continuing calibration check standard solution. CompuChem Laboratories will use the80 ng/ul concentration for the continuing calibration check standard solution for benzoic acid,2,4,5-trichlorophenol, 4,6-dinitro-2-methylphenol, 4-nitrophenol, pentachlorophenol and 3isomers of nitroanaline instead of 40 ng/ul originally specified.


The Analysis of Semivolatile Organics in Drinking Water

With Low Detection Limits

By Gas Chromatography/Mass Spectrometry

1.0 SCOPE AND APPLICATION

This method covers the analysis of the semivolatile organicslisted in TABLE 1 in drinking water (private well/municiplewell) samples using gas chromatography/mass spectrometry(GC/MS). The required method detection limits of this methodis lower than that of the standard GC/MS scan of semivolatileorganics. Modifications are made to achieve these lowdetection limits. The level of surrogate spike standard andmatrix spike standard are proportionatel reduced.


2.1 Two separate one liter aliquots of sample are extractedwith methylene chloride at a pH greater than 11 forbase/neutral fractions and again at pH less than 2 foracid fraction, using separataory funnel techniques.

2.2 For each aliquot of sample, the acid fraction and thebase/neutral fractions are combined and concentrateddown to 0.5 ml. This concentrated extract is thenanalyzed using a GC/MS system. The analytes of interest,which are separated by GC, are measured by a massspectrometer detector in the electron impact (EC) mode.

2.3 The retention time and mass spectra are the criteria ofqualitative identification of analytes. The quantiationions used for quantifying each analyte are listedin TABLE 2.


3.1 The toxicity or carcinogenicity of chemicals used inthis method have not been precisely defined. Each

TABLE 1

TARGET COMPOUND LIST (TCL) AND QUANTITATION LIMITS (ug/L)

(FOR RESIDENTIAL WELL WATER SAMPLES)

SEMIVOLATILES GAS NUMBER OUANTITATION LIMITS

Bis(2-chloroethyl) etherPhenol2-Chlorophenol1 ,3-Dichlorobenzene1 , 4-Dichlorobenzene1 ,2-DichlorobenzeneBenzyl AlcoholBis(2-chloroisopropyl) ether2-Methyl PhenolHexachloroethaneN-NitrosodipropylamineNitrobenzene4-MethylphenolIsophorone2-Nitrophenol2 , 4-Dimethy IphenolBis(2-chloroethoxyl) Methane2 , 4-Dichlorophenol1 ,24-TrichlorobenzeneNaphthalene4-ChloroanilineHexachlorobutadieneBenzole Acid2-Methyl Naphthalene4-Chloro-3-Methy IphenolHexachlorocyclopentadiene2 , 4 , 6-Trichlorophenol2,4, 5-Tr ichlorophenol2-Chloro NaphthaleneAcenaphthyleneDimethyl Phthalate2 , 6-DinitrotolueneAcenaphthene3-NitroanilineDibenzofuran2 , 4-Dinitrophenol2 ,4-Dinitrotoluene

111-44-4108-95-2

95-57-8541-73-1106-46-7

95-50-1100-51-6

39638-32-995-48-767-72-1

621-64-798-95-3

106-44-578-59-188-75-5

105-57-9111-91-1120-83-2120-82-191-20-3

106-47-887-68-365-85-091-57-659-50-777-47-488-06-295-95-491-58-7

208-96-8131-11-3606-20-2

83-32-999-09-2

132-64-951-28-5

121-14-2

1.52.02.02.02.02.52.02.51.02.01.52.51.02.52.02.02.52.02.02.02.02.5

20.02.01.52.01.51.51.51.51.51.01.52.51.0

(15.0)1.0

NOTE: Values in parenthesis are estimated.

SEMIVOLATILES

2-Nitroanl ine4-NitrophenolOiethyl phthalate4-Chlorophenyl phenyl etherFluorene4-Nitroanil Ine4, 6-Dinitro-2-methyl phenolN-N itrosodi phenyl ami ne4-Bromophenyl phenyl etherHexachlorobenzenePentachlorophenolPhenanthreneAnthraceneDi-n-butyl phthalateFluoranthenePyreneButyl benzyl phthalateBenzo(a)anthraceneChrysenebis(2-Ethylhexyl)phthalateDi-n-octyl phthalateBenzo(b)fluorantheneBenzo(k)fluorantheneBenzo(a)pyreneIndeno(l,2,3-cd)pyrene0 i benzf a, h) anthraceneBenzo(g,h, i)perylene

TABLE 1(CONTINUED)

CAS NUMBER

88-74-4100-02-784-66-2

7005-72-386-73-7

100-01-06534-52-186-30-6

101-55-3118-74-187-86-585-01-8

120-12-784-74-2

206-44-0129-00-085-68-756-55-3

218-01-9117-81-7117-84-0205-99-2207-08-950-32-8

193-39-553-70-3

191-24-2

QUANTITATION LIMITS

1.02.01.01.01.03.0

15.02.02.02.02.01.03.02.02.02.04.02.02.01.02.02.02.02.04.03.04.0

SGW/dlk/BJC[dlk-402-69]13727-MD

TABLE 2

CHARACTERISTIC IONS FOR SEMIVOLATILE ORGANICS PARAMETERS

Parameter______________Primary Ion________Secondary Ion(s)

Phenol 94 65, 66Bis(2-chloroethyl)Ether 93 63, 952-Chlorophenol 128 64, 1301.3-Dichlorobenzene 146 148, 1131.4-Dichlorobenzene 146 148, 113Benzyl Alcohol 108 79, 771,2-Dichlorobenzene 146 148, 1132-Methylphenol 108 107Bis(2-chloroisopropyl)Ether 45 77, 794-Methylphenol 108 107N-Nitroso-Dipropylamine 70 42, 101, 130Hexachloroethane 117 201, 199Nitrobenzene 77 123, 65Isophorone 82 95, 1382-Nitrophenol 139 65, 1092,4-Dimethylphenol 107 121, 122Benzole ;,cid 122 105, 77Bis(2-Chloroethoxy(Methane 93 95, 1232,4-Dichlorophenol 162 164, 981,2,4-Trichlorobenzene 180 182, 145Naphthalene 128 129, 1274-chloroaniline 127 129Hexachlorobutadiene 225 223, 2274-Chloro-3-Methylphenol 107 144, 1422-Methylnaphthalene 142 141Hexachlorocyclopentadiene 237 235, 2722,4,6-Trichlorophenol 196 198, 2002,4,5-Trichlorophenol 196 198, 2002-Chloronaphthalene 162 164, 1272-Nitroaniline 65 92, 138Dimethyl Phthalate 163 194, 164Acenaphthylene 152 151, 1533-Nitroaniline 138 108, 92Acenaphthene 153 152, 1542,4-Dinitrophenol 184 63, 1544-Nitrophenol 109 139, 65Dibenzofuran 168 1392,4-Dinitrotoluene 165 63, 1822,6-Dinitrotoluene 165 89, 121Diethylphthalate 149 177, 150

4-chlorophenyl-phenylether 204 206, 142Fluorene 166 165, 1674-Nitroaniline 138 92, 1084,6-Dinitro-2-Methylphenol 198 182, 77N-Nitrosodiphenylamine 169 168, 1674-Bromophenyl-phenylether 248 250, 141Hexachlorobenzene 284 142, 249Pentachlorophenol 266 264, 268Phenanthrene 178 179, 176Anthracene 178 179, 176Di-n-Butylphthalate 149 150, 104Fluoranthene 202 101, 100Pyrene 202 101, 100Butylbenzylphthalate 149 91, 2063,3-Dichlorobenzidine 252 254, 126Benzo(a)anthracene 228 229, 226Bis(2-Ethylhexyl)phthalate 149 167, 279Chrysene 228 226, 229Di-n-Octyl phthalate 149Benzo(b)Fluoranthene 252 - 253, 125Benzo(k)Fluoranthene 252 253, 125Benzo(a)Pyrene 252 253, 125Indeno(1,2,3-cd)Pyrene 276 138, 227Dibenz(a,h)Anthracene 278 139, 279Benzolg,h,i)Perylene 276 138, 277

chemical shall be treated as potential health hazardand exposure to these chemicals should be minimized.Each analyst is responsible for maintaining awarenessof OSHA regulations regarding safe handling ofchemicals used in this method. Additional referencesto laboratory safety are available for the infor-mation of the analyst.

3.2 The following parameters covered by this method havebeen tentatively classified as known or suspected,human or mammalian carcinogens : Benzo(a)anthracene,benzidine, 3 ,3-dichlorobenzidine, benzol a)pyrene,dibenzo(a.h) anthracene, and N-nitrosodimethylamine.Primary standards of these toxic compounds should beprepared in a well-vented hood. A NIOSH/MESA approvedtoxic gas respirator should be worn when the analysthandles high concentrations of these toxic compounds.

4.0 INTERFERENCES

4.1 Method interferences may be caused by contaminantsin reagents,solvents, glassware, and other samplesprocessing hardware, that lead to discrete artifactsor elevated baselines in the total ion currentprofiles (TICPs). All of these materials must beroutinely demonstrated to be free of interferencesunder the conditions of the analysis by runninglaboratory reagent blanks.

4.2 Matrix interferences may be caused by contaminantsthat coextracted from the sample. The extent of matrixinterferences will vary considerably from sample tosample. Matrix spike/matrix spike duplicate (MS/MSD)analyses will be done to determine the possible matrixinterferences.

5.0 APPARATUS AND INSTRUMENTS

5.1 Glassware

5.1.1 Separatory funnel - 2000 ml, with teflon stopper.

5.1.2 Drying column - 19 mm ID chromatographic columnwith coarse frit.

5.1.3 Concentrator tube - Kuderna-Danish, 10 ml,

graduated (Kontes K-570050-1025 or equivalent).Calibration must be checked at the volumeemployed in the test. Ground glass stopper isused to prevent evaporation of extracts.

5.1.4 Evaporative flask - Kuderna-Danish, 500 ml(Kontes K-503000-0500 or equivalent). Attach toconcentrator tube with springs.

5.1.5 Snyder column - Kuderna-Danish, Three-ball macro(Kontes K-503000-0121 or equivalent).

5.1.6 Snyder column - Kuderna-Danish, two-ball micro(Knotes K-50300-0219 or equivalent).

5.1.7 Vials - amber glass, 2 ml capacity with teflon-lined screw-cap.

5.1.8 Continuous liquid-liquid extractors - equipedwith teflon or glass connecting joints andstopcocks requiring no lubrication.

5.1.9 Silicon carbide boiling chips - approximately10/40 mesh. Heat to 400 degree C for 30 minutesor Soxhlet extract with methylene chloride.

5.2 Balance - analytical, capable of accurately weighing+0.00001 g.

5.3 Water bath - heated, with concentric ring cover,capable of temperature control ( +2°C ). The bathshould be used in a hood.

5.4 Nitrogen evaporation device equipped with a water baththat can be maintained at a temperature between 35 and40°C.

5.5 Gas chromatography/mass spectrometer system

5.5.1 Gas chromatography - an analytical systemcomplete with a temperature programmable gaschromatograph suitable for splitless injection,and all required-accessories including syringes,analytical columns, and carrier gases.

5.5.2 GC columns - 30 m x 0.25 mm (or 0.32 mm) IDbonded-phase silicon coated fused silicacaillary column (J&W Scientific DB-5 or

equivalent). A film thickness of 1.0 micro isrecommended because of its larger capacity.Alternately, a film thickness of 0.25 micro maybe used.

5.5.3 Mass spectrometer - capable of scanning from35 to 500 amu every l second or less, utilizing70 volts (nominal) electron energy in theelectron impact ionization mode and producinga mass spectrum which meets all criteria when50 ng of decafluorotriphenyl-phosphine (DFTPP)is injected through the GC inlet.

5.5.4 Data system - a computer system must beinterfaced to the mass spectrometer that allowsthe continuous acquisition and storage onmachine readable media of all mass spectraobtained throughout the duration of thechromatographic program. The computer must havea library of standard mass spectra, and havesoftware that allows library search of massspectra in both forward and reversed mode,searching of any GC/MS file for ions of aspecific mass and plotting such ion abundanceversus time or scan number. This type of plotis defined as an extracted ion current profile(EICP). Software must also be available thatallows integrating the abundance in any EICPbetween specified time or scan number limits.

6.0 REAGENTS

6.1 Reagent water - reagent water is defined as a water inwhich an interferent is not observed at or above themethod detection limit of each parameter of interest.

6.2 Sodium hydroxide solution (10 N) - dissolve 40 ganalytical grade NaOH in reagent water and diluteto 100 ml.

6.3 Sodium thiosulfate - (ACS) granular.

6.4 Sulfuric acid solution (1+1) - slowly add 50 mlconcentrated H2S04 (sp.gr. 1.84) to 50 ml ofreagent water.

6.5 Acetone and methanol - pesticide residue analysis grade

or equivalent quality.

6.6 Sodium sulfate - (ACS) powdered, anhydrous, purified byheating at 400°C for four hours in a shallow tray,cool in a desicator, and store in a glass botle.

6.7 Methylene Chloride - Pesticide residue analysis gradeor equivalent.

6.8 Surrogate standard spike solution

6.8.1 Surrogate standards are added to all investigativesamples, matrix spike/matrix spike duplicatesamples, laboratory duplicate samples,blanks andcalibration standard slutions. The surrogatestandard spiking solution should include thefollowing compounds:

Nitrobenzene-ds Phenol-dgTerphenyl-di4 2,4,6-tribromophenol2-fluorobiphenyl 2-fluorophenol

6.8.2 Prepare a surrogate standard spike solution thatcontains the base/neutral compounds ata concentration of 20 ug/ml, and the acidcompounds at 40 ug/ml. Store the spike solutionsat 4°C in teflon-sealed containers. The solutionshould be checked frequently for stability. Thesesolutions must be replaced after three months orsooner if comparison with quality control checksamples indicate a problem.

6.9 Base/Neutral and Acid Matrix Standard Spiking Solution

6.9.1 The matrix standard spiking solution shouldconsist of the following compounds:

Base/Neutrals _____Acids_____

1,2,4-Trichlorobenzene PentachlorophenolAcenaphthene Phenol2,4-Dinitrophenol 2-ChlorophenolPyrene 4-Chloro-4-MethylphenolN-Nitroso-di-n- 4-Nitrophenol

propylamine1,4-Dichlorobenzene

6.9.2 Prepare a spiking solution in methanol thatcontains all of the compounds in 6.8.1 at aconcentration of 20 ug/ml for base/neutrals,and at 40 ug/mL for acids. Store the spikingsolutions at 4°C (+2°C) in Teflon-sealedcontainers. The solutions shall be checkedfrequently for stability. These solutions shallbe replaced after twelve months, or sooner, ifcomparison with quality control check samplesindicates a problem.

6.10 Internal Standards

6.10.1 The internal standard solution consists of thefollowing compounds:

1,4-dichlorobenzene-d4 Naphthalene-dsAcenaphthene-dio Phenanthrene-dioChrysene~diL2 Perylene-di2

6.10.2 Prepare the internal standard solution bydissolving 200 mg of each compound in 50 ml ofmethylene chloride. It may be necessary, however,to use 5-10% benzene or toluene in this solutionand a few minutes of ultresonic mixing to dissolveall the constitutes. The resulting solution willcontain each standard compound at a concentrationof 4000 rig/ml. A 10 ul portion of this solutionshould be added to 1 ml of sample extract ( or5 ul to 0.5 ml extract). This will give aconcentration of 40 ng/ul of each compound.

6.11 Calibration standard solution

6.11.1 Initial Calibration standard solutions -

Prepare calibration standard solutions at aminimum of five concentration levels. Eachcalibration standard solution shall contain eachcompound of interest and each surrogate standard.The concentration of the initial calibrationstandard solutions shall be at 5, 10, 20 50, and100 ng/uL ( or mg/L) for all semivolatiles exceptthe following compounds: Benzoic acid, 2,4-dinitrophenol, 2,4,5-trichlorophenol, 4,6-dinitro-2-methylphenol, 4-nitrophenol, pentachlorophenol,and all three iosmers of nitroaniline, which

will have concentrations at 20, 50, 80, , and120 ng/ul (or mg/L).

Great care must be taken to maintain theintegrity of all standard solutions, store allstandard solutions at -10°C to -20°C inscrew-cap amber bottles with teflon liners.Fresh standards shall be prepared every twelvemonths at a minimum. The continuing calibrationstandard shall be prepared weekly and stored at4°C (+2°C).

6.11.2 Continuing Calibration Check Standard solution -

Prepare a continuing calibrtation check standardsolution at a concentration of 20 ng/uL for allbase/neutral and acids compounds except benzoicacid, 2,4,5-trichlorophenol, 4,6-dinitro-2-methylphenol, 4-nitrophenol, pentachlorophenoland three isomers of nitroaniline, which will beat a concentration of 40 ng/uL. The continuingcalibration check standard solution shall containeach surrogate standard.

7.0 PROCEDURES

7.1 Sample Storage and Holding Time

7.1.1 Procedure for Sample Storage

7.1.1.1 The samples must be protected fromlight and refrigerrated at 4°C fromthe time of receipt until sampleextraction and analysis.

7.1.2 Holding Time

7.1.2.1 The extraction of water samples shouldbe completed within 5 days VSTR(validated time of sample receipt.)

7.2 Sample Extraction - Separatory Funnel

7.2.1 Two separate one liter of water samples will beextracted respectively using the separatoryfunnel.The extraction scheme is described as below.

7.2.1.1 Place entire sample of one liter bottleinto a 2-liter separatory funnel (Note:if the liter bottle is not completelyfilled, mark the sample level on theoutside of the bottle so that thevolume of sample used for extractioncan be measured later by filling itwith reagent water.). Rinse the bottleand cap with reagent water, and add itto the sample.

7.2.1.2 Add 250 ul of surrogate standard spikingsolution into the separatory funnel andmix it well. (For matrix spike samples,add 250 ul of matrix spiking solutionto each 1-liter portion of sample.) Checkthe pH of the sample with wide range pHpaper and adjust it to pH greater than11 with 10 N sodium hydroxide.

7.2.1.3 Add 60 ml of methylene chloride to theseparatory funnel and extract the sampleby shaking the funnel for 2 minutes, withperiodic venting to release excesspressure. Allow the organic layer toseparate from the water phase fora minimum of 10 minutes. If the emulsioninterface between layers is more than one-third of the volume of the solvent layer,the analyst must employ mechanicaltechniques to complete the phaseseparation. The optimum technique dependson the sample, and may include stirring,filtration of the emulsion through glasswool, centrifugation, or other physicalmethods. Collect the methylene chlorideextract in a 250 ml Erlenmeyer flask.

7.2.1.4 Add a second 60-ml portion of methylenechloride to the sample in the separatoryfunnel and repeat the extraction procedurea second time, combining the extracts in

the erlenmeyer flask. Perform a thirdextraction in the same maaner. Combinethe extracts in the erlenmeyer flask,and label the combined extract as thebase/neutral fraction. Continue theextraction for acid fraction in 7.2.5 .

7.2.1.5 Adjust the pH of the aqueous phase toless than 2 using sulfuric acid (1+1).Serially extract three times with 60-mlaliquots of methylene chloride, as per7.2.3 through 7.2.4 . Collect and combinethe extracts in a 250 ml erlenmeyerflask and label the combined extractas the acid fraction.

7.2.1.6 Assemble a Kuderna-Danish (K-D)concentrator by attaching a 10-mlconcentrator tube to a 500-mlevaporative flask.

7.2.1.7 Transfer the individual base/neutraland acid fractions by pouring extractsthrough separate drying column containingabout 10 cm of anhydrous granular sodiumsulfate, and collect the extracts in theseparate K-D concentrators. Rinse theerlenmeyer flasks and columns with 20to 30 ml of methylene chloride tocomplete the quantitative transfer.

7.2.1.8 Add one or two clean boiling chips andattach a three-ball snyder column tothe evaporative flask. Pre-wet thesnyder column by adding about 1 mlmethylene chloride to the top of thecolumn. Place the K-D apparatus on ahot water bath (80° to 90°C) sothat the concentrator tube is partiallyimmersed in the hot water, and the entirelower round surface of the flask isbathed with hot water vapor. Adjustthe vertical position of the apparatusand the water temperature as requiredto complete the concentration in 10to 15 minutes. At the proper rate ofdistillation, the ball of the columnwill actively chatter but the chambers

will not flood with condensed solvent.When the apparent volume of liquidreaches 1 ml, remove the K-D apparatusfrom the water bath and allow it todrain and cool for at least 10 minutes.Remove the snyder column and rinsethe flask and its lower joints intothe concentrator tube with 1-2 ml ofmethylene chloride. A 5-ml syringe isrecommended for this operation.

7.2.1.9 Nitrogen blowdown

Place the concentrator tube in a warmwater bath (35°C) and evaporate thesolvent volume to just below l mlusing a gentle stream of clean, drynitrogen filtered through a column ofactive carbon.Caution; New plastic tubing must NOTbe used between the carbon trap andthe sample, as it may introduceinterferences. The internal wall ofthe tube must be rinsed down severaltimes with methylene chloride duringthe operation and the final volumebrought to 0.5 ml with methylenechloride. During evaporation,the tubesolvent level must be kept below thewater level of the bath. The extractmust never be allowed to become dry.

7.3 Tuning and GC/MS Mass Calibration

7.3.1 It is necessary to establish that a given GC/MSmeets the standard mass spectral abundancecriteria before initiating any on-going datacollection. This is accomplished through thehardware tuning and the analysis of decafluoro-triphenylphosphine (DFTPP).

7.3.1.1 Each GC/MS system used for the analysisof semivolatile compounds must behardware-tuned to meet the abundancecriteria listed in TABLE 3 for a 50-nginjection of DFTPP.

DFTPP must be analyzed separately or

TABLE 3

CHARACTERISTIC IONS FOR SURROGATE AND INTERNAL STANDARDS FOR

SEMIVOLATILE ORGANIC COMPOUNDS

Parameters____________Primary Ion___________Secondary Ions

SURROAGES

Phenol-d5 99 42, 712-Fluorophenol 112 642,4,6-Tribromophenol 330 332, 141Nitrobenzene-ds 82 128, 542-Fluorobiphenyl 172 171Terphenyl 244 122, 212

INTERNAL STANDARDS

1,4-Dichlorobenzene-d4 152 115Naphthalene-ds 136 68Acenaphthene-dio 164 162, 160Phenanthrene-dio I88 94. 80Chrysene-a12 240 120, 236Perylene-di2 264 260, 265

as part of the calibration standard.The meeting the criteria of abundancemust be demonstrated daily and/or foreach 12 hour period, whichever is morefrequent, before samples can beanalyzed. DFTPP must injected to meetthis criteria.

7.3.1.2 Whenever corrective action is takenthat may change or affect the tuningcriteria for DFTPP (e.g., ion sourcecleaning or repair, etc.), the tunemust be verified irrespective of the12-hour tuning requirements.

Table 4. DFTPP Key Ions and Ion Abundance Criteria

____Mass_______Ion Abundance Criteria__________

51 30.0 - 60.% of mass 19868 Less than 2.0% of mass 6970 Less than 2.0% of mass 69

127 40.0 - 60.0% of mass 198197 Less than 1.0% of mass 198198 Base peak, 100% relative abundance199 5.0 - 9.0% of mass 198275 10.0 - 30.0% Of mass 198365 Greater than 1.0% of mass 198441 Present, but less than mass 443442 Greater than 40.0% of mass 198443 17.0 - 23.0% of mass 442

7.3.2 Calibration of the GC/MS System

7.3.2.1 Before the analysis of samples andrequired blanks, and after tuningcriteria have been met, the GC/MSsystem must be initially calibratedas a minimum of five concentrationsto determine the linearity of responseutilizing all compounds listedin Table 1. Once the system has beencalibrated, the calibration must beverified after initial calibration

ana after every 12-hour time periodfor each GC/MS system.

7.3.2.2 Prepare calibration standards to yieldthe following specific concentrations:

Initial calibration of semivolatilecompounds consists of five points at 5,10, 20,.50, and 100 total nanograms forall compounds except for the folllowingcompounds:

Benzole acid, 2,4-dinitrophenol, 2,4,5-tri-chlorophenol, 4,6-dinitro-2-methylphenol,4-nitrophenol, pentachlorophenol, and allthree nitroaniline isomers which will beinjected at 20,50, 80,and 120 totalnanograms.

7.3.2.3 Analyze each calibration standard andtabulate the area of the primarycharacterizitc ion (Table 2) againstconcentration for each compound includingall required surrogate and internalstandard compounds. The relative ret-ention times of each compound in eachcalibration run should agree within 0.06retention time units. Late elutingcompounds usually will have much betteragreement.

The relative response factors (RRFs) foreach compound at each concentration levelare calculated using Equation 1.

Equ. 1

= Area of the characteristic ionfor the compound to be measured.

Where:

( Ax ) x i

( A i s) x i

I Cis )

[ CX )

Ais = Area °f tne characteristic ionfor the specific internalstandards from Table 2 or 3.

cis = Concentration of the internalstandard in uint of ng/uL.

Cx = Concentration of the compoundto be measured in unit of ng/uL.

Using the relative response factors(RRFs) from the initial calibration,and Equation 2 to calculate the percentrelative standard deviation (%RSD) foreach compound from the calibrationcheck run.

SD%RSD = ———— X 100 Equ. 2

X

Where:

%RSD = Relative Standard Deviation

SD = Standard Deviation of initialresponse factors per eachcompound.

N ( Xi - X )Where: SD = ————— ———

i=l N - 1

X = mean of initial response factorsper each compound.

The %RSD for each individual compoundmust be less than or equal to 25%.This criteria must be met for theinitial calibration to be valid, andthe sequencial continuing calibrationcheck

7.4 GC/MS Analysis of Sample

7.4.1 The follwoing instrumental parameters arerequired for all performance tests and for allsample analysis:

Electron Energy - 70 volts (nominal)

Mass Range - 35 to 500 amu

Scan Time - 1 second per scan

7.4.2 Combine 0.5 ml of the base/neutral extract and0.5 ml of acid from water extract prior toanalysis.

7.4.3 Internal standard solution is added to eachsample extract. Add 10 ul of internal standardsolution (6.10) to each accurately measured1.0 ml of combined sample extract ( or 5 ul ofinternal standard solution to 0.5 ml ofbase/neutral extract or 0.5 ml of acid extractrespectively).

7.4.4 Analyze the 1.0 ml combined extract by GC/MSusing a bonded-phase silicone-coated fusedsilica capillary column. The recommended GCoperating conditions to be used are as follows:

Initial Column Temperature Hold- 30°C for 4 minutes

Column Temperature Program - 30-300°C at 8degree/min.

Final Column Temperature Hold - 300°C for 10 min.

Injector Temperature - 250 - 300°C

Transfer Line Temperature - 250 - 300°C

Source Temperature - According tomanufacturer'sspecification.

Injector-Grob-Type, Splitless

Sample volume - 1 - 2 uL

Carrier Gas - Helium at 30 cm/sec.

NOTE: Make any extract dilution indicated bycharacterization prior to the addition of

internal standards, if any further dilution ofwater extracts are made, additional internalstandards must be added to maintain the required40 ng/uL of each constituent in the extractvolume. If the concentration of any compoundexceeds the initial calibration range, theextract must be diluted and reanalyzed.Secondary ion quantitation is ONLY allowedwhen there are sample interferences with theprimary ion.

7.5 Qualitative Analysis

7.5.1 The compounds listed in Table 1 shall beidentified by an analyst competent in theinterpretation of mass spectra by comparison ofthe sample mass spectrum to the mass spectrumof a standard of the suspected compound. Thefollowing criteria must be satisfied in orderto verifythe identifications: (1) elution ofthe sample component at the GC relativeretention time as the standard component, and(2) correspondence of the sample component andstandard component mass spectra.

7.5.1.1 For establinshing correspondence ofthe GC relative retention time (RRT),the sample component RRT must comparewithin +0.06 RRT units of the RRT ofthe standard component. For reference,the standard must be run on the sameshift as the sample. If coelution ofinterfering components prohibitsaccurate assignment of the samplecomponent RRT from the total ionchromatogram, the RRT should beassigned by using extracted ion currentprofiles for ions unique to thecomponent of interest.

7.5.1.2 For comparison of standard and samplecomponent mass spectra, mass spectraobtained on the same GC/MS instrumentare required. Once obtained, thesestandard spectra may be used foridentification purposes, only if

the GC/MS instrument meets the DFTPPdaily tuning requirements. Thesespectra may be obtained from the runused to obtain reference RRTs.

7.5.1.3 The requirements for qualitativeverification by comparison of massspectra are as follows:

7.5.1.3.1 All ions present in thestandard mass spectra at arelative intensity greaterthan 10% (most abundant ionin the spectrum equals 100%)must be present in thesample spectrum.

7.5.1.3.2 The relative intensities ofions specified in (1) mustagree within plus or minus20% between the standard andsample spectra.

7.5.1.3.3 Ions greater than 10% inthe sample spectrum but notpresent in the standardspectrum must be consideredand accounted for by theanalyst making the comparison.All compounds meeting theidentification criteria mustbe reported with their spectra.For all compounds below theCRDL, report the actual valuefollowed by "J", e.g., "2J."

7.5.1.3.4 If a compound can not beverified by all of the criteriain 7.5.1.3.3, but in thetechnical judgement of the massspectral interpreatationspecialist,the identificationis correct, then the laboratoryshall report that identificationand proceed with quantitation.

7.6 Tentative Identification of Non-target compound/Unknown

Sample components.

A library search shall be executed for non-targetcompounds or unknown sample components for the purposeof tentative identification.The 1985 release of theNational Bureau of Standards Mass Spectral Library orthe most current release shall be used for this purpose.

7.6.1 Substances with responses equal to, or greaterthan 10% of the nearest internal standard arerequired to be searched in this fashion.Only after visual comparison of sample spectrawith the nearest library searches will the massspectral interpretation specialist assign atentative identification. NOTE: Computer generatedlibrary search routines must not use normalizationroutines that would misrepresent the library orunknown spectra when compared to each other.

7.6.2 The following criteria shall be used to makethe tentative identification:

7.6.2.1 Relative intensities of major ions inthe reference spectrum (ions greaterthan 10% of the most abundant ion)should be present in the sample specta.

7.6.2.2. The relative intensities of the majorions should agree within +20% .

7.6.2.3 Molecular ions present in referencespectrum should be present in samplespectrum.

7.6.2.4 Ions present in the sample spectrumbut not in the reference spectrum shouldbe reviewed for possible backgroundcontamination or presence of co-elutingcompounds.

7.6.2.5 Ions present in the reference spectrumbut not in the sample spectrum shouldbe reviewed for possible substractionfrom the sample spectrum because ofbackground contamination or co-elutingcompounds. NOTE: Data system libraryreduction programs can sometimes createthese discrepancies.

7.6.2.6 If in the technical judgement of themass interpreatation spectral specialist,no valid tentative identification canbe made, the compound shall be reportedas Unknown. The mass spectralspecialist should give additionalclassification of the unknown compound,if possible (i.e., unknown phthalate,unknown hydrocarbon, unknown acid type,unknown chlorinated compound, etc.).If probale molecular weights can bedistinguished, include them.

7.7 Quantitation

7.7.1 Components identified shall be quantified bythe internal standard method. The internalstandard used shall be the one nearest theretention time to that of a given analyte. TheEICP area of the characteristic ions of analyteslisted in Table 2 and Table 3 are used.

Internal standard responses and retention timein all samples must be evaluated during orimmediately after data acquisition. If theretention time for any internal standardchanges by more than 30 seconds from the latestdaily (12 hour) calibration standard, thecharomatographic system must be inspected formalfunctions, and corrections made as required.The extracted ion current profile (EICP) of theinternal standards must be monitored andevaluated for each sample, blank, matrix spike,and matrix spike duplicate. If the EICP area forany internal standard changes by more thana factor of two (-50% to +100%) , the massspectrometric system must be inspected formalfunction and corrections made as appropriate.If the analyses of a subsequent sample orstandard indicates that the system is functioningproperly, the corrections may not be required.The sample or standards with EICP areas outsidethe limits must be re-analyzed, and treatedaccording to 7.7.1.1 and 7.7.1.2 below.If correction is made, then the laboratory mustdemonstrate that the mass spectrometric systemis functioning properly. This must be accompaniedbythe analysis of a standard or sample that does

meet the EICP criteria. After corrections aremade, the re-analysis of samples analyzed whilethe system was malfunctioning is required.

7.7.1.1 If after re-analysis, the EICP areasfor all internal standards are insidethe required limits (-50% to +100%),then the problem with the first analysisis considered to have been within thecontrol of laboraotry. There only datafrom the analysis with EICP's withinthe required limits will be reported.

7.7.1.2 If the re-analysis of the sample doesnot solve the problem(i.e., the EICPareas are outside the required limitsfor both analyses), then the EICP dataand sample data from both analysesshall be reported. Distinguish betweenthe initial analysis and the re-analysison all data deliverables. Document inthe case narrative all inspection andcorrective action taken.

1.1.2 The relative response factor (RRF) from thedaily standard analysis is used to calculatethe concentration in the sample. Secondary ionsmay be used if interferences are present. Thearea of a secondardy ion can NOT besubstituted for the area of a primary ion unlessa relative response factor is calculated usingthe secondary ion. When compounds identified arebelow required quantitation limits (RQL) but thespectral meets the identification criteria,report the concentration with a "J."See Section 8.0 for calculation.

8.0 CALCULATION

8.1 When an analyte has been identified, the quantitationof that analyte shall be based on the integratedabundance from the EICPs of the primary characteristicion given in Table 2. If the sample produces aninterference for the primary ion, use a secondarycharacteriztic ion for quantitation. Instrumentcalibration for secondary ions shall be performed, asnecessary, using the data and procedures describedin Section 7.0.

8.2 Calculate the concentration in the sample using thecalibration curve or relative response factor (RRF)as determined in Section 7.3.2.3, and the followingequation:

Concentration (ug/L)<AX) <IS) <Vt>

s) (RRF) (V0) (

Where Ax = Area of the characteristic ion forthe compound to be measured.

Ais = Area of the characteristic ion forthe internal standard.

Is = Amount of internal standard injectedin nanograms (ng).

Vo = Volume of water extracted inmilliliter (ml)

Vi = Volume of extract injected (ul)

Vt = Volume of total extract (use 2000 ulor a factor of this when dilutionsare made. The 2000 ul is derivedfrom combining half of the 1 ml BNextract and half of the 1 ml ofA extract.)

8.3 Estimation of Tentatively Identified Compounds (TICs)

An estimated concentration for the non-targetcomponents tentatively identified shall be quantifiedby the internal standard method. For quantification,the nearest internal standard free of interferencesshall be used.

8.3.1 The equation for calculating concentrationsis the same as in Section 12.2 . Total areacounts (or peak heights) from the total ionchromatogams are to be used for both thecompound to be measured and the internalstandard. A relative response factor (RRF)of one (1) is to be assumed. The valuefrom this quantitation shall be qualified asestimated. This estimated concentration shallbe calculated for all tentatively identifiedcompounds as well as those identified asunknowns.

8.4 Calculate surrogate standard recovery on all samples,blanks and spike samples. Detemine if recovery iswithin limits and report on appropriate form. Thesurrogate standard recovery for each sample, blank,and spike samples are calculated as following:

SSRSurrogate Standard Recovery = —————————— x 10

SA

Where:

SSR = Surrogate spike sample result.

SA = Surrogate standard spike added fromsurrogate spike mix.

8.5 Matrix Spike/Matrix Spike Duplicate Analysis (MS/MSD)

8.5.1 Individual component recoveries of the matrixspike are calculated using the followingequations:

SSR - SRMarix Spike Percent Recovery = ———————— x 100

SA

Where:

SSR = Spike sample results.

SR = Spike result.

SA = Spike added from spiking mix.

8.5.2 Relative Percent Difference (RPD)

The relative percent difference for eachcomponent between the matrix spike and matrixspike duplicate are calculated using thefollowing equation:

D! - D2RPD = ———————————————————— X 100

( (D!> + <D2)> /2

Where:

RPD = Relative percent difference.

DI = First sample value.

D2 = Second sample value (duplicate)

9.0 QUALITY CONTROL REQUIREMENTS

9.1 The continuing calibration check shall be done dailybefore analysis of any samples, and once at thebeginning of each 12-hour shift to check the validityof the initial calibration. Calculate the percentdifference (%D) using the following equation:

RFj - RFC% Difference = ———————————————— x 100

RFj

Where:

RFj = Average response factor from initialcalibration.

RFc = Response factor from current continuing

calibration check standard.

The percent difference for any compound shall be lessthan 25%. If the criteria is not met (>25% difference),for anyone calibration check compound, correctiveaction must be taken. If no source of the problem canbe determined after corrective action has been taken,a new initial five point calibration must be generated.This criteria must be met before sample analysis begins.

9.2 Method Blank Analysis

9.2.1 A method blank is a volume of deionized,distilledlaboratory water carried through the entireanalytical scheme (extraction, concentration,and analysis). The method blank volume shall beapproximately equal to the sample volumes beingprocessed.

9.2.2 The method blank analysis shall be performed ata frequency of one per group of 20 of fewersamples of similar concentration. The methodblank associated with a specific group of samplesshall be analyzed on each GC/MS system used toanalyze that specific group of samples.

9.2.3 A method blank shall contain no greater thanfive times (5X) the required detection limit ofcommon phthalate esters, and shall containless than the required detection limit of anyother single semi-volatile compounds. If themethod blank exceeds this criteria, the sourceof contamination must be investigated, andappropriate corrective measures must be takenand documented before further sample analysisproceeds. All samples processed with a methodblank that is out of control must bereextracted and reanalyzed.

9.3 Surrogate Spike Recovery

9.3.1 Calculate surrogate spike percent recovery perSection 8.4. Surrogate spike recovery shall beevaluated for acceptance by determining whetherthe concentration (measured as percent recovery)falls inside the required recovery limits listedas follows:

SURROGATE SPIKE RECOVERY LIMITS

Low/MediumSurrogate Compound Water

Nitrobenzene-ds 35-1142-Fluorobiphenyl 43-116p-Terphenyl-di4 33-141Phenol-ds 10-942-Fluorophenol 21-1002 ,4 ,6-Tribromophenol 10-123

9.3.2 If recovery of any one surrogate compound ineither base/neutral or acid fraction is below 10%or recoveries of two surrogate compounds ineither base/neutral or acid fraction are outsidethe surrogate spike recovery limits (9.3.1),corrective actions shall be taken. If no sourceof problems is -determined after the correctiveactions are taken, reextract and reanalyze thesample.

9.4 Matrix Spike/Matrix Spike Duplicate Analysis (MS/MSD)

9.4.1 A matrix spike/matrix spike duplicate shall beperformed one per group of 20 or fewer samples ofsimilar concentrations.

9.4.2 The matrix spike percent recovery shall becalculated according to Section 8.5. The matrixspike recovery limits are listed as below:

Matrix Spike Recovery Limits

Fraction Matrix Spike Compound Limits

BN 1,2,4-Trichlorobenzene 39-98BN Acenaphthene 46-118BN 2,4-dinitrotoluene 24-96BN Pyrene 26-127BN N-Nitroso-Di-Propylamine 41-116BN 1,4-Dichlorobenzene 36-97

Acid Pentachlorophenol 9-103Acid Phenol 12-89Acid 2-Chlorophenol 27-123Acid 4-chloro-3-Methylphenol 23-97Acid 4-Nitrophenol 10-80

9.5 Sample Analysis

9.5.1 Sample can ONLY be analyzed upon successfulcompletion of the initial QC activities (7.3,9.1, 9.2, 9.3 and 9.5). When twelve (12) hourshave elapsed since the initial QC was completed,it is necessary to conduct an instrument tuneand calibration check analysis. Any major systemmaintenance such as source cleaning orinstallation of a new column, may necessitate aretune and recalibration.

9.5.2 Requirements for qualitative compoundidentification and quantitation specified in7.5 and 7.6 shall be followed.

10.0 DATA REPORTING REQUIREMENT

10.1 All reports and documentations shall be legible,single-sided, ana clearly labelled and paginated.

10.2 The sample data package shall be consecutivelypaginated and shall include the cover pages, sampledata, and the raw data as they are described in thefollowing:

10.2.1 Cover pages for the data package, includingthe project name, laboratory name, field

sample number cross-referenced with laboratoryID number, comments describing in detailsany problems encountered in processing thesamples, and validation and signature by theLaboratory Manager.

10.2.2 Sample Data

Sample data shall be reported using the OrganicAnalysis Data Reporting Forms (Attachment I) forall samples, arranging in increasing alphanumericsample number order, followed by QC analyses data,Quarterly verification of instrument parametersforms, raw data including copies of the samplecustody and sample preparation logs.

10.2.2.1 FORM IA (Semivolatile OrganicsAnalyses Data Sheet)

FORM IB (Semivolatile OrganicsAnalysis Data Sheet - continued)

FORM 1C (Semivolatile OrganicsAnalysis Data Sheet - TentativelyIdentified Compounds, Ties)

10.2.2.2 FORM II (Semivolatile SurrogateRecovery)

10.2.2.3 FORM III (Semivolatile Matrix Spike/Matrix Spike Duplicate Recovery)

10.2.2.4 FORM IV (Semivolatile Method BlankRecovery)

10.2.2.5 FORM V (Semivolatile GC/MS Tuningand Mass Calibration - Decafluorotri-phenylphosphine (DFTPP) )

10.2.2.6 FORM VI (Semivolatile InitialCalioration Data)

10.2.2.7 FORM VII (Semivolatile ContinuingCalibration Check Data)

10.2.2.8 FORM VIII (Semivolatile InternalStandard Area Summary)

10.2.2.9 Raw Data

Raw data shall include reconstructedIon currect (RIC) chromatogram, massspectra (with and without backgroundsubstraction) of each compoundquantified, mass spectrum of eachtentatively identified compound (TIC)including the best matched standardlibrary spectrum, any instrumentprintouts, copies of sample custodyrecords and sample preparation logs.

11.0 REFERENCES

SrXIVOLATILE ORCANICS ANALYSIS DATA SHZZT

Lab Naae:______________Lab Sample I.D. _______

JUtrix: ' water

Saaple . vol: _____, aLLevel: (low/aed) ___

Extraction: (SepF/Cont/Sonc)CPC Cleanup: (Y/N)__ pH:_

_. Field Sample Number.

CAS NO. COMPOUND

Lei Saaple ID: _

Lab rile ZD: _

Date Received: _

Date Extracted:_

Date Analysed: _

Dilution Factor:

CONCENTRATION UNITS:(ug/L .'. .

108-95-2——————Phenol_______________111-44-4—————bit(2-Chloroethyl) ether__•_95-57-8——————2-Chlorophenol_________541-73-1—————1,3-Dichlorobeniene______106-46-7——————1,4-Dlchlorobenzene_______100-51-6—————Benzyl alcohol_________95-50-1———————1,2-Dichlorobenzene______95-4B-7——————2-Methylphenol_________108-60-1—-—---bii (2-Chloroicopropyl) ether106-44-5——————4-Methylphenol________ '621-64-7—————-N-Nitro»o-di-n-propylaaine67-72-1———————Hexachloroe thane_________S8-95-3——————Nitrobenzene ________78-59-1-------Icophorone "~~~~"̂ ~~——•———88-75-5———————2-Nitrephenol • ~105-67-9——————2.4-Di-ethylphenel65-85-0———————Benzole acid_____________111-91-1—————bi«(2-Chloroethoxy)»ethane_120-83-2——————2.4-Dichlorophenol________120-82-1—————1.2,4-Trichlorobenzene____91-20-3——————Naphthalene____________106-47-*————4-Chlereaniline•7-68-3——————Hexachlerobutadiene59-50-7——————4-Chloro-3-»ethylphenol___91-57-6——————2-Methylnaphthalene__^_____77-47-4——————Hexaehlerecyclopentadiene• 8-06-2———————2,4,6-Trichlorophenol_____95-95-4————~ 2,4,5-Trichlorophenol____91-58-7——————2-chloronephthalene______• •-74-4——————2-Nitroaniline__________131-11-3—————Di-ethylphthalate________208-96-8—————Acenaphthylene_________606-20-2—————2,6-Dinitrotoluene_________

FORM I SV-1

SEMIVOLATILE OROANICS ANALYSIS DATA SEZET

Lab Naae:Lab Sample I.D. __

Matrix: . ' "walvrSaapl* vol:

Level: (lov/aed)

Extraction: (SepF/Cont/Sonc)

CPC Cleanup: (Y/K)__ pH:_

_. Field Sanple Nunber_Lab Caapla XD:Lab File XD:

Data Received: .Data Extracted:,Data Analysed:

CAS NO. COMPOUHD

Dilution Factor:CONCENTRATION UNITS:(ug/L

99-09-2 ————— •83-32-9 ————— •51-28-5 ————— •100-02-7 ———— •132-64-9 -----121-14-2 ———— •84-66-2 ————— •7005-72-3 ——— •86-73-7 ————— •100-01-6 ———— •534-52-1 ———— •86-30-6 ————— •101-55-3—— ——118-74-1 ————87-86-5 ————— •85-01-8 ————— •120-12-7 ———— •84-74-2 ————— •206-44-0 ———— •129-00-0 ———— •85-68-7 ————— •91-94-1 ————— •56-55-3 ———— •218-01-9 ———— •117-81-7 ———— •117-84-0 ———— •205-99-2 ———— •207-08-9 ———— •50-32-8 ————— •193-39-S ———— •53-70-3 ————— •191-24-2 ———— •

(1) - Cannot be

— 3-Nitroaniline— Acenaphthene— 2,4-Dinltrophenol— 4-Nitrophenol

— 2 , 4-Dinitrotolu«ne— Diethylphthalate™4-Chlorophenyl-phenylether _— Fluorene— 4-Nitroaniline- — 4 , 6-Dinitro-2-»ethy Iphenol• — N-Nitro«odiphenylaalne (1)—— 4-Bro«oph«nyf-ph«nyl«th«r __— - Hexechlorebenzene

— Fhtnanthrene—Anthracene— Di-n-butylphthalate— Fluoranthene— Pyrene— Butylbenzylphthalate• — -3 . 3 ' -Dichlorobenzidine—Benzo (a) anthracene— Chryaene— bis(2-Ethylhexyl)phthalate— Di-n-octylphthalate— Benzo (b) f luoranthene— Benzo (k) f luoranthene• — Benzo(a)pyrane— Xndeno (1,2, 3-ed) pyrene ____— Dibenz (a, hj anthracene _____— Benzo (9 . h , i ) pery lene

separated fron Diphtnylanint

_ _ _L—

————

———

———

FORM I SV-2

SDOVOLATIIZ ORGAXXCS ANALYSIS DATA SHOTTBTTATIVZLY IDENTIFIED COKPOONDS

Lab Mane:

Matrix: water.Staple vol: _____ -mL

Level: (low/»ed) ____

t Moictura: not dec. d*e>_Extraction: (Sapr/Cont/Sone)

GPC Cleanup: (T/K)__ pH:_

jJujsber TICs found: ____

Field Sample number_XAb Saaple XD: _XAb rila XD: _

Data Received: _Date Zxtracted:_Date Analyzed: _

Dilution Factor:

CONCENTRATION UNITS:(ug/L

CAS HUMBER

1.2.3.4.5.6.7.a.9.

10.11.12.13.14.15.16.17.18.19.20.21.22.23.24.25.26.27.28.29.30.

COMPOUND NAME FT EST. CONC. C

FORM I SV-TIC

HATER CBOVOtATXLE SURROGATE RECOVERY

Lab NBBC:

| Field| SAMPLE HO.!•..., . ....... .

Oil02103104105106107108109110111112113114115116117118119 |20121122123124|251261271281291301

SI(MBZ) f

62(FBP) I

S3(TPH)I

64(PHL)I

«5(2FP)I

S6(TBP)|

OTHER TOTIOUT]

——

——

——

QC LIMITSSI (NBZ) - Nitrobeniene-d5 (35-114)S2 (FBP) • 2-Fluorobiphenyl (43-116)S3 (TPH) • Terphenyl-dl4 (33-141)S4 (PHL) • Phenol-d6 (10-94)S5 (2FP) - 2-Fluorophenol (21-100)S6 (TBP) • 2,4,6-Tribro»oph«nol (10-123)

I Column to be used to flag recovery v«lu«»* Values eutcid* of contract required QC limits0 Surrogates diluted out

page _ of _FORM II SV-1

WATER SEMIVOIATIU MATRIX SPIKE/MATRIX SPIKZ DUPLICATE RECOVERY

X«b Haae:

Lab Sample I.D.Matrix Spike - EPA Sample No.:

Field Sanple Number_

COMPOUND

Phenol2-Chlorophenol1,4-DichlorobenzeneN-Nitroso-di-n-prop. (1)1 , 2 , 4-Trichlorobeniene4-Chloro-3-aethylphenoTAcenaphthene4-Nitrophenol2 . 4-DinitrotoluenePentachlorophenolpyrene

COMPOUND

Phenol2-Chlorophenol1,4-DichlorobenzeneM-Nitroco-di-n-prop . < 1 )1 , 2 ,4-Trichlorobenien*4-Chloro-3-aethylphenoTAcenaphthene4-Nitrophenol2 . 4-DinitrotoluenePentachlorophenolPyrene

6PJKEADDED(U?/L)

SPIKEADDED(ug/L)

CAMPLECONCZNTRATIOH

(ug/L)

MSDCONCENTRATION

(ug/L)

MSCONCENTRATION

(ug/L)

MSD%

RTC 1%

RPD 1

MS 1 QC |* I LIMITS |

REC l| REC. |

112- (91127-1231136- 971141-1161139- 961123- 971146-1181110- 801124- 9611 9-1031126-12711 1

1CC LIMITS jRPD | R£C. |

...... | ...... |42 |12- 89|40 (27-123128 |36- 97|38 141-116]28 139- 98)42 |23- 97 |31 |46-118|50 |10- 80|38 |24- 96|50 I 9-103|31 |26-127|

1 1

(1) N-Nitro«o-di-n-propyl»nine

t Column to be uced to flag recovery and RPD values with an actericX• Values outside of QC Halts

RPD:____ out ofSpike Recovery:__COMMENTS: _____

__ outside Haltsout of ____ outside Halts

roRM III 8V-1

SDUVOLATILE KETHOD BLANK SUMMARY

Lab Naae:

Lab File ID: _

Date Extracted:

Date Analysed:

Matrix: . water;

In»trua«nt ID:

Lab Sample ID:

Extraction:(Sepr/Cont/Sonc)Ti»e Analysed: __Level:(low/Bed) __

THIS KETHOD BLANK APPLIES TO THE FOLLOWING SAMPLES, US AND USD:

1 Fieldj SAMPLE HO.

Oil02103104105106107|081091101an1211311411511*117|18119120121122123124 I2SI261271281291301

LABSAMPLE ID

-

LABFILE ID

_.

•.

DATEANALYZED

.

COMMENTS:

page _ of _FORM IV SV

8ZHIVOLATIIZ ORGANIC CC/MS TONING AND KASSCALIBRATION - DECAnBOROTRIPHENYLPHOSPHINE (DTTPP)

Lab Maae:

Lab File ID:Instrument ID:

BFTPP Injection Bete i.DFTPP Injection Ti»e:_

»/•5168C970

127197198199375365441442443

ION ABUNDANCE CRITERIA

30.0 - CO.0% of »as« 198Less than 2.0* el M» 69Mass 69 relative abundanceLess than 2.0% ef MM «940.0 - 60. 0» of ••(> 198Less than 1.0% ef Base 198Bax P«ak. 100% relative afcunianc*S.O to 9.0% of aasc 19810.0 - 30.0% of macs 198Gr««t«r than 1.00% of matt 198Present, tout less than >ass 443Greater than 40.0% of «asc 19817.0 - 23.0% Of »ass 442

I 4 RZIATIVr |ABCXDANCE |

1( )ll

1( )ll

11111111

( )2I1

1-Value is %aass 69 2-V«lu« is % »ass 442THIS TUNE APPLIES TO THE FOLLOWING SAMPLES. MS, USD, BLANKS, AND STANDARDS:

1 FieldI SAMPLE NO.

Oil021031041051061071081091101111121131141151161171181191201211221

LABSAMPLE ID

———————— •—— •

LABFILE ID

_

.

.

DATEANALYZED

.

TIMEANALYZED

.

page _ of _FORM V SV

CZXIVOIATILZ ORCANICS IHITIXL CALIBRATION OATA

Lab Hue:

Instrument ID:Kin 55? for CKC(I) • 0.050

Calibration D»t«(»):_Has %RSD for CCC(») . 30.0%

(LAD FILE ID:(MtrtO -_____I.

RW120-"XRF50 •mn<o-

COKPOUHD (KXT20 IXXrSO (KKFtO SKT_^__________|bi«(2-Chloro«thyl)«th«r

|2-Chloroph«nol_jl,3-Dichlorob«nzen«j1,4-Dichlorob«nz*n«~jBenzyl «lcohol_jl,2-Dichlorob«nz«ne|2-M«thylph«nol_jbis(2-Chloroicopropyl)tthtr|4-M«thylph«nolJH-Hitro»o-di-n-propylaain«_(Hexachlorocthan*__ ""(Nltrobcnzaii*______|I»ophoron«Ia-Mitroph«nol ~12,4-Di»«thylph«nol_|Benzole acid_|bl*(2-Chlorocthoxy)B«tbana

~|1,a,4-Trichlorob«nsana(Naphthalana|4-Chlorcanilin*|H«x»chlorobut»dl«n«14-Chlore-3-«*thylphanoiI2-Methyln»phth»l«n«_(Haxachlorocyclopantaj 2.4,6-Trichloroph«nol.j 2,4,5-Trichloroph*noljj 2-ChloronaphthalWM|2-Nitroanilin«IDi»«thyIphtbalatajAcanaphthyl«n«12,e-Dinitrotolu«n«|3-Nitroanilin«|Ac«n»phthana12.4-Dinltroph«nol|4-Nitropb«nol

USD

ram vx rv-i

cexivoiATXu ORCJuncs ZMITZAL OUIBRATIOH DATA

Lab Ham*:

In«tru»«nt ID: Calibration Dat«(a)iERF for spcc(f) » o.oso •ax %RSD for ccc(») .

|1AB fJLI ID:(RKFSO -_____I___________I

|Dibcnzofuran_

KWSO •~

COMPOUND IXRT20 intrso |Mtrao |RRri20|Rwi«o| RSD

j 2,4-Dinltrotolu«n«(Dicthylphthalat* ~14-Chloroph«nyl-pb«nyl«tb«r_JFluortn* ~j 4-Nitro«nilin«__________14,6-Dinitro-2-IethyIphenoI~|N-Hitrocodiph*nylaAin* (1)~j 4-Brcaoph«nyl-ph«nyl«th«r ~|Hcxaehlorob«nz*n*_j Fcntachleroph*nol~| Phcnanthran*___~|Anthrac«n*_IDi-n-butylphthalat«_j Fluorantban*____~1Pyr«n«_|Butylb«nzylphthalat«13,3 '-Dlchlorob«nsidin«_jB«nzo(alanthraean«(Chryccn*Jbic(2-Ethylh«xyl}phthal«t«|Di-n-octylphthalat»_ ~|Bcnzo(b)tluor»nth«n«_|B«nzo(k)fluor»nth«n«~|B«nzo(a)pyran«|Indeno(1,2,3-cd)pyr«n«_IDibanz(a,h)anthraean*IBanzotg.h.ijparylana

|Nitrob«nz«n«-d3_______12-Flu orob iphanvl|T«rph«nyl-dl4_______|Ph«nol-d6j 2-riuorophanol ~12,4,«-Tribro»oph«nol_

(1) Cannot b* ••paratad from Diphanylaain*

FORM VI SV-2

•BflVOXATILE CONTINUING CALIBRATION CRZCX

Lab Name:

Zn*truB«nt ZD: Calibration Oat«:Lab Fil« ZD: Znit. Cftlib. Dat«(»)t_Min ftRTSO for CPCCd) * 0.050 Max %D for CCC(») • 25.0%

II COMPOUND

| Phenol___________jbiB(2-Chloro«thyl)«th«r_I2-Chloropb«nol_11,3-Dichlorob«nzen«_|l,4-Dichlorob«ni«j>«~|B«nzyl alcoholj1,2-Dichlorob«nt«n«|2-M«thylph«nol_|bi«(2-Chloroi«opropyl)«th«r|4-M«thylph«nol|H-Nitro»o-di-n-propyIa»in«_|H«xaehloro«than«__ ~j Hitrobentcn*_____jiBophoron*______j 2-Kitrophanol ~~j 2,4-Di««thylph«nol_jBenzole acid_I bic (2-Chloro«thoxy) _«thaj)«|2,4-Dlchloroph«Jiol___ ~11,2,4-Tr1chlorob«nz an«|Naphthal«n«|4-Chloroanllin«14-Chloro-3-attthylpb«noI|2-M«thvlnaphthal«na|H«xachloroeyclop«ntadl*na_|2,4,6-Trichloroph*nel___12.4.5-Trichlorophanel12-Chloronaphthalan*_|2-Nitroanilln«_____|Di»«thylphth»lat«_|Ac«naphtbyl«n«_____j 2,6-Dinitrptolu«n«|3-Nitroanilin«_JAccnaphthcn*__ja,4-Dinltrophanol|4-Nitroph«nolI_______

|RRT50 %D

FORM VII SV-1

SB4XVOUTILE OOHTIKUZHC CALIBRATION CHECK

Lab Na*«:

Instrument ID: Callbr»tion Dtte: .*IJM:Lab File ID: _______Kin ItXTSO for SPCC(I) - 0.050

. Init. Calib. Dete(«)t_tux %D tor ccc(») - 25.o*

I COMPOUND

|Dibentofurtn_|2,4-Dinitrotoluene|Di«thylphth«l«t« "|<-Chloroph«nyl-ph«nyl«th«r_jFluor*n* ~l 4 - H i t r o a n i l i n « _ _ _14,6-Dinitro-2-»«thylphtnol|N-Kitro>cx3iphtnyla>in« (1)~I4-Bro»oph«nyl-ph«nyl«thtr_3|Htxachlorob«nz«n«I P«nt»ehloroph«nol]| Phen»nthr«n«___'_|Anthr»c«n»IDi-n-butyiphth«l»t«_| Fluor»nth»n«_____~|Pyr«n«j Butylbenzylphthalatej 3,3 '-DichlorobenzidineIBcnzo(a)anthracene__~j ChryteneJDl-n-octylphthalata__|Benzo(b)fluoranthene__IBenzo(k)fluoranthene__|B*nzo(a)pyreneIXndeno(1,2,3-ed)pyrenejDibenz(a,h)anthracenetBenze(g.h.r|Nltrobenxene-d5I2-Fluoroblphenyl|Terphenyl-dl4__IPhenol-46|a-rluoroohanol(2,4,t-Tribro»oph«nolI___________________(1) Cannot b« Beparated frm Diphanylaalne

%D

FORM VII CV-2

•ZMZVOIATIU INTERNAL STAHnARD ARIA SUMMARY

Lab Naaa:

Lab Ml* XD (Standard):

XnstruMJit ID: _____Data Analycad:_

Analysed:.

12 BOOR CTD|

ISl(DCB) |AREA l|

OFFER 1XXXTI

LOWER LIMIT |.•MM»»BMMMBM

Field SAMPLEMO.

-021.031.041.051.06|.071.0« I.09|.10).«L121.431.141.151.1«LI'l.HI-IS I.201.211.

ZS2(NtT) |AREA l| XT

IS 3 (ANT) |AREA l| RT

XS1 (DCB) • l,4-Dichlorob«nl«n«-d4IS2 (HPT) • K*phthal*n«-dl2S3 (AKT) • Ac*n«phth«n*-dlO

OFFER LIMIT • + 100*ef internal Btandard area.LOWER LIMIT - - 50*ef internal •tandard area.

f Coluxn u>»d to flag lnt«rn»l atandard araa valu*s with an actcrlck

FORM VIII SV-1

MNXVOIATILE INTERNAL ITAXnARD AREA CDMUXT

Lab Xaaa:

Lab Flla ID (Standard) I

Instrument ZD: _____Data Analysed:

Analr»*d:

II 12 HOUR CTD

CTPER LIMIT

| LOWER LIMIT

[Field SAMPLEI »0.

02|03104|05|06|07|08|09|10 1"I

HI

17 Il«l19120|211

IS4(PHN) |AREA || XT

XCS(CRY) |AREA l| XT

ZS4 (PRN) - Ph«n»nthr«n«-dlOZSS (CRY) • Cbryaan«-dl2ZS6 (PRY) - Parylana-412

XS6(PRY) |AREA || XT

VPPZR LIMIT • «• lOOtof intarnal standard araa.LOWER LIMIT - - SOtof internal standard area.

I Col van u»»d to flag intarnal •tandard araa value* with an aitiricX

paga _ ef _FORM Till CT-2


FOR

THE ANALYSIS OF PESTICIDES/PCBs IN WATER WITH LOW DETECTION LIMITS

BY COMPUCHEM

Prepared July 6,1988Revised January 1989

Quality Assurance Notice

CompuChem follows the attached Pesticide/PCB SOP with modification to detection limits for4,4-DDE, Alpha-chlordane, Gamma-chlordane and methyloxychlor. CompuChem will reach.05 ug/I for alpha, and gamma chlordane and .01 ug/1 for 4,4-DDE. At present, we are unableto reach the .02 ug/1 detection limit for methoxychlor. We are, however undergoing detectionlimit studies which includes methoxychlor. We will attempt to reach the required detectionlimits for methoxychlor however, if samples are received in house prior to our ability to reachthe detection limit, we will contact Region V QAS at that time to resolve an acceptabledetection limit for methoxychlor.

[jhr-602-48]


FOR

THE ANALYSIS OF PESTICIDES AND PCBS IN DRINKING WATERS

1.0 INTRODUCTION

1.1 This standard operating procedure describe the detailedanalytical procedure for the determination of organo-chlorine pesticides and polychlorinated biphenyl (PCBs)listed in Table 1 in private well water, domestic welland municipal water samples.

1.2 This is a gas chromatography with electron capturedetection (GC-EC). This method also describes analyticalconditions for a second gas chromatographic column thatshall be used to confirm measurements made with theprimary column.

1.3 The method detection limits (MDLs) for each parameter islisted in Table 1.

1.4 This method is restricted to use by or under thesupervision of analysts experienced in the use of a gaschromatograph and in the interpretation of gas chromato-grams. Each analyst must demonstrate the ability togenerate acceptable results with this method using theprocedure described in Section


2.1 A 1-liter sample is extracted with methylene chlorideusing a separatory funnel. The methylene chlorideextract is dried with anhydrous sodium sulfate andexchanged to hexane during the concentration to a volumeof 1 ml. The extract is separated by gas chromatographyand the parameters are then measured with an electroncapture detector (ECD).

2.2 This method provides a florisil column cleanup procedureand an elemental sulfur removal procedure to aid in theelimination of interference that may be encountered.

TABLE 1

TARGET COMPOUND LIST (TCL) AND QUANTITATION LIMITS (QL)

(For Residential Well Water Samples)

PesticLdes/PCBs CAS Number Ouantitation Limits (ug/L)

alpha-BHCBeta-BHCdelta- BHCGamma-BHC (Lindane)Heptachlor

AldrinHeptachlor epoxideEndosulfan IDieldrin4, 4 '-DDE

EndrinEndosulfan II4,4' -ODDEndosulfan Sulfate4,4'-DDT

MethoxychlorEndrin Ketonealpha-chlordanegamma-chlordaneToxaphene

Aroclor-1016Aroclor-1221Aroclor-1232Aroclor-1242Aroclor 1248

Aroclor-1254Aroclor-1260

319-84-6319-85-7319-86-858-89-976-44-8

309-00-21024-57-3

959-98-860-57-172-55-9

72-20-833213-65-9

72-54-81031-07-8

50-29-3

72-43-553494-70-5

5103-71-95103-74-28001-35-2

12674-11-211104-28-211141-16-553469-21-912672-29-6

11097-69-111096-82-5

0.0100.0050.0050.0050.030

0.0050.0050.0100.0100.005

0.0100.0100.0200.1000.020

0.0200.0300.0200.0200.250

0.1000.1000.1000.1000.100

0.1000.100

3.0 INTERFERENCES

3.1 Method interferences may be caused by contaminants insolvents, reagents, glassware, and other sampleprocessing hardware that lead to discrete artifactsand/or elevated baselines in gas chromatograms. All ofthese materials must be routinely demonstrated to befree from interferences under the conditions of theanalysis by running laboratory reagent blanks(Section 8.2). The use of high purity reagents andsolvents help to minimize interference problem.

3.2 Glassware must be scrupulously cleaned. Clean allglassware as soon as possible after use by rinsingwith the last solvent used in it. Solvent rinsingshould be followed by detergent washing with hot water,and rinses with tap water The glassware shall then bedrained dry, and heated in a muffle furnace at 400°Cfor 15 to 30 minutes.

3.3 Interferences by phthalate esters can pose a majorproblem in pesticide analysis when using the electroncapture detector. These compounds generally appearin the chromatogram as large late eluting peaks,especially in the 15 and 50% fractions from florisil.Interferences from phthalates can best be minimized byavoiding the use of plastics in the laboratory.Exhaustive cleanup of reagents and glassware may berequired to elimiate background phthalate contamination.

3.4 Matrix interferences may be caused by by contaminantsthat are co-extracted from the sample. The cleanupprocedure in Section 9.4 shall be used to overcomemany of these interferences.


4.1 The toxicity or carcinogenicity of each reagent usedin this method has not been precisely defined; however,each chemical compound should be treated as a potentialhealth hazard. Exposure to the chemicals therefore mustbe reduced to the lowest possibel level by whatevermeans available. The laboratory is responsible formaintaining a current awareness file of OSHA regulationsregarding the safe handling of the chemicals specifiedin this method. A reference file of material datahandling sheets shall also be made available to all

personnel involved in the chemical analysis.

4.2 The following parameters covered by this method havebeen tentatively classified as known or suspected, humanor mammalian carcinogens: 4,4'-DDT, 4,4'-DDD, the BHCs,and the PCBs. Primary standards of these toxic compoundsshould be prepared in a hood. A NIOSH/MESA approved toxicgas respirator should be worn when the analyst handleshigh concentrations of these toxic compounds.

5.0 APPARATUS AND MATERIALS

5.1 Sampling Equipment

5.1.1 Grab sample bottle - 1-liter amber bottle,fritted with a screw cap lined with Teflon. Thebottle and cap liner must be washed, rinsed withacetone or methylene chloride, and dried beforethey are shipped to field to minimizecontamination.

5.2 Glasswares

5.2.1 Separatory Funnel - 2-liters with Teflon stopcock.

5.2.2 Drying column - Chromatographic column,approximately 406 mm long x 19 mm ID., withcoarse frit filter disc.

5.2.3 Chromatographic Column - 400 mm long x 22 mm ID,with Teflon stopcock and corse frit filter disc.

5.2.4 Concentrator tube, Kuderna-Danish - 10-ml,graduated. Ground glass stopper is used toprevent evaporation of extracts.

5.2.5 Evaporative Flask, Kuderna-Danish - 500-ml.Attached to concentrator tube with springs.

5.2.6 Snyder column, Kuderna/Danish - Three ballsmacro.

5.2.7 Vials - 10 to 15 ml amber glass, with Teflon-lined screw cap.

5.3 Boiling chips - approximately 10/40 mesh. Heat to400°C for 30 minutes or soxhlet extract with

methylene chloride.

5.4 Water Bath - Heated, with concentric ring cover,capable of temperature control (+2°C). The bathshall be used in a hood.

5.5 Balance - Analytical, capable of accurately wieghing0.0001 g.

5.6 Gas Chromatograph - an analytical system completewith gas Chromatograph suitable for on-column injectionand all required accessories including syringes,analytical columns, gases, detector, and strip chartrecorder. A data system is recommended for measuringpeak areas.

5.6.1 Quantitation and/or confirmation columns:

5.6.1.1 GC Column 1 - 1.8 m long x 4 mm ID glasspacked with 1.5% SP-2250/1.95% SP-2401 on Supelcoport(100/120 mesh) or equivalent.

5.6.1.2 GC Column 2 - 1.8 m long x 4 mm ID, glass,packed with 3% OV-1 onSupelcoport(100/120 mesh)or equivalent.

5.6.1.3 GC Column 3 - 1.8 m long x 4 mm ID, glass,packed with 5% OV-210 onGas Chrom Q (80/100 mesh) orequivalent.

5.6.2 Confirmation column ONLY :

Column - 30 m x 0.25 mm ID, 0.25 micron filmthickness, bonded-phase silicone coated,fused silica capillary column (J&WScientific DB-5 or DB-1701 or equivalent).

5.7 Detector - Electron Capture Detector.

6 .0 REAGENTS

6.1 Reagent Water - Water in which an interferent is not

observed at the MDL of the parameter of interest.

6.2 Sodium Hydroxide Solution (10 N) - Dissolve 40 g ofNaOH (ACS) in reagent water and dilute to 100 ml.

6.3 Sodium Thiosulfate - (ACS) Grannular.

6.4 Sulfuric Acid (1+1) - Slowly, add 50 ml of cone.H2S04 (ACS, sp. gr. 1.84) to 50 ml of reagent water.

6.5 Acetone, hexane, isooctane, methylene chloride -pesticide quality.

6.6 Ethyl Ether - Nanograde, redistilled in glassif necessary. Ethyl ether must be shown to be free ofperoxide before it is used.

6.7 Sodium Sulfate - (ACS) Grannular, Anhydrous. Purify byheating at 400°C for 4 hours in a shallow tray.

6.8 Alumina - neutral, super I woelm or equivalent. Prepareactivity III by adding 7% (V/W) reagent water to theSuper I neutral alumina. Tumble or shaXe in a wristaction shaker for a minimum od 2 hours or preferablyovernight. There shall be no lumps present. Store in atightly sealed glass container. A 25 cycle soxhletextraction of the alumina with methylene chloride isrequired if a solvent blank analyzed by the pesticidetechnique indicate any interferences for the compoundsof interest.

6.8.1 Alumina Equivalency Check. Test the alumina byadding the BNA surrogate in 1:1 acetone/hexaneto the alumina and follow the procedure inSection 7.0. The tribromophenol shall not bedetected by GC/EC if the alumina and itsactivation are acceptable. Also check recoveryof all single pesticides following the sampleprocedure. The percent recovery for all singlepesticide must be greater than 80%, except forendosulfan sulfate which must be equal to orgreater than 60% and endrin aldehyde which isnot recovered.

6.9 Mercury - Triple distilled.

6.10 Copper powder - Activated.

6.11 Stock Standard solutions (1.00 ug/ui) - Stock standardsolution can be prepared from pure standard materialsor purchased as certified solutions.

6.12 Pesticide surrogate standard spiking solution -

6.12.1 The surrogate standrad is added to all samplesand calibration standard solutions; the compoundspecified for this purpose is dibutylchlorendate.

6.12.2 Prepare a surrogate stndard spiking solutionat a concentraion of 0.2 ug/1.00 mL acetone.Store the spiking solutions at 4°C (+2°C)in Teflon-sealed containers. The solutionsshall be checked frequently for stability.These solutions must be replaced after

.12 months, or sooner, if comparison withquality control check samples indicates aproblem.

6.13 Pesticide Matrix standard spiking solution -

Prepare a spiking solution of acetone or methanol thatcontains the following pesticides in the concentrationspecified:

Pesticide ug/1.0 mL

Lindane 0.04Heptachlor 0.04Aldrin 0.04Dieldrin 0.10Endrin 0.104,4'-DDT 0.10

Matrix spikes are also to serve as duplicates by spikingtwo 1-liter portions from the one sample chosen forspiking.

7.0 CALIBRATION

7.1 Establish gas chromatographic operating conditionsequivqlent to those given in Table 2.The gas chromato-graphic system must be calibrated using the externalstandard technique.

7.2 External Standard Calibration Procedure:

7.2.1 Prepare calibration standards at a minimum ofthree concentration level for each parameter ofinterest by adding volumes of one or more stockstandard solutions to a volumetric flask anddiluting to volume with isooctane. One of theexternal standards should be at a concentrationnear, but above the MDL (Table 1), and the otherconcentrations should correspond to the expectedrange of concentrations found in real samples orshall define the working range of the detector.

7.2.2 Using injection of 2 to 5 ul, analyze eachcalibration standard according to Section 10.1and tabulate peak height or peak ares responsesagainst the mass injected. The results are usedto prepare a calibraiton curve for each compound.

8.0 QUALITY ASSURANCE/QUALITY CONTROL REQUIREMENTS

8.1 Determination of Retention Time Window

Before performing any sample analysis, the laboratoryshall determine the retention time window for eachpesticides/PCB target compound listed in Table 1 andsurrogate spike compound (Dibutylch;lorendate). Theretention time windows are used to make tentativeidentification of pesticide/PCBs during the sampleanalysis.

8.1.1 Prior to eatablishing the retention timewindows, the GC operating conditions (oventemperature and flow rate) shall be adjustedsuch that 4,4'-DDT has a retention time of>12 minutes on packed GC columns except onOV-1 or OV-101 columns.

8.1.2 The retention time windows shall be establishedas follows:

8.1.2.1 At the beginning of the project andeach time a new GC column is installed,make three injections of all singlecomponent pesticides mixtures, multi-response pesticides, and PCBsthroughout the course of 72-hour period.The concentration of each pesticides/PCBshall be sufficient to provide aresponse that is approximately halfscale. The three injections of eachcompound shall be made at approximatelyequal intervals during 72-hour period(i.e., each compound shall be injectednear the beginning,near the middle, andnear the end of the 72-hour periond).

8.1.2.2 Verify the retention time shift fordibutylchlorendate in each standard.The retention time shift between theinitial and subsequent standards shallbe less than 2.0% difference for packedcolumns, less than 1.5% for wide borecapillary columns (ID less than 0.32mm).If this criteria is not met, continueinjecting replicate standards to meetthis criteria.

8.1.2.3 Calculate the standard deviation of thethree absolute retention times for eachsingle component pesticide. For multi-response pesticides or PCBs, chooseone major peak from the envelope andcalculate the standard deviation of thethree retention time for that peak.

J.I.3 The standard deviation calculated in 8.1.2.3shall be used to determine the retention timewindows for a particular 72-hour sequence.Apply plus or minus three times the standarddeviations in 8.1.2.3 to the retention time ofeach pesticide/PCB for the first analysis of thepesticide/PCB standard in a given 72-houranalytical sequence. This range of retentiontimes defines the retention time window forthe compound of interest for that 72-hoursequence.

8.2 Analysis of Method Blank

8.2.1 A method blank is a volume of deionized,distilled laboratory water for water samplescarried through the entire analytical scheme(extraction, concentration, and analysis). Thevolume of method blank must be approximatelyequal to the sample volumes being processed.

8.2.2 Method blank analysis shall be analyzed at thefrequency of one per every 20 samples analyzed.

8.2.3 The method blank must contain less than orequal to the quantitation limits of any samplepesticide/PCB target compounds. If thelaboratory method blank exceeds these criteria,the laboratory shall investigate and appropriatecorrective measures must be taken and documentbefore further sample analysis proceeds.

8.3 Surrogate Spike Recovery

All standards, samples, blanks, matrix spike andmatrix spike duplicate samples will be spikedwith the surrogate spike compound (Dibutylchlorendate);and the spike amount and the recovery of surrogatespike compound shall meet the following requirements:

8.3.1 The Surrogate spiking standard compound shallbe spiked into the samples, blanks and patrixspike and matrix spike duplicates beforeextration at a. concentration of 0.2 ug/L(or 0.2 ppb).

8.3.2 The surrogate standard recovery shall be in the

range of 24-154%.

8.4 Matrix Spike/Matrix Spike Duplicate Analysis

8.4.1 Matrix spike / matrix spike duplicates shallbe prepared and analyzed at a frequency of oneper group of 20 or fewer field samples.

8.4.2 The matrix spiking standard solution shallcontain those compounds specified inSection 6.13 at a concentration of 0.1 and0.2 ug/mL respectively.

8.4.3 The matrix spiking standard solution shall beadded to sample aliquots prior to theextractions.

8.4.4 Sample requring optiomal dilution and choosenas the matrix spike/matrix spike duplicatesamples must be analyzed at the same dilutionas the original unspiked samples. Calculatethe matrix spike recovery and the relativepercent difference (RPD) as follows:

SSR - SRMatrix spike Percent Recovery = ——————— x 100

SA

Where:SSR = Spiked sample results.

SR = Sample results.

SA = Spiked added from Spike Mix.

Relative Percent DI - D2Difference (RPD) = —————————————— x 100

(Dx + D2)/2

Where:DI = First sample value.

D£ = Second sample value (duplicate).

8.4.5 The matrix spike/matrix spike duplicatesrecovery shall fall within the following ranges:

Fraction Matrix Spike Compound ^Recovery

Pesticide Lindane 56-123Pesticide Heptachlor 40-131Pesticide Aldrin 40-120Pesticide Dieldrin 52-126Pesticide Endrin 56-121Pesticid 4,4'-DDT 38-127

8.5 External Standard Quantitation method must be used toquantitate all pesticide/PCBs before performing anysample analysis, the laboratory shall determine theretention time window for each pesticide/PCB targetcompounds listed in Table 1.

9.0 SAMPLE PREPARATION

9.1 Sample Collection, Preservation, and Handling

9.1.1 Grab samples must be collected in glasscontainers.

9.1.2 All samples must be iced or refrigerated at4°C. If samples will not be extracted within72 hours of collection, the sample shall beadjusted to a pH of 5.0-9.0 with sodiumhydroxide or sulfuric acid. If aldrin is to bedetermined, add sodium thiosulfate whenresidual chlorine is present.

9.1.3 All sample must be extracted within 5 days ofcollection and completely analyzed within40 days of extraction.

9.2 Sample Extraction - Separatory Funnel

9.2.1 Using a 1-liter graduated cylinde, measureout a 1-liter sample aliquot and place it intoa 2-liter separatory funnel. Check the pH ofthe sample with wide range pH paper and adjustto between pH 5 and 9 with ION sodium hydroxideand/or 1:1 sulfuric acid solution.(NOTE: Recovery of dibutylchlorendate will be

low if pH is outside this range. Alpha-BHC,Gamma-BBC, Endosulfan I and II, and Endrin aresubject to decomposition under alkalineconditions, and therefore may not be detectedif the pH is above 9.) Pipet i.o ml ofsurrogate standard spiking solution into theseparatory funnel and mix well. Add 1.0 ml ofpesticide matrix spiking solution to each oftwo 1-liter portions from the sample selectedfor spiking.

9.2.2 Add 60 ml methylene chloride to the separatoryfunnel and extract the sample by shaking thefunnel for two minutes, with periodic ventingto release excess pressure. Allow the organiclayer to separate from the water phase fora minimum of 10 minutes. If the emulsioninterface between layers is more thanone-third the volume of the solvent layer, theanalyst must employ mechanical techniques tocomplete the phase separation. The optiumtechnique depends upon the sample, and mayinclude: stirring, filtration of the emulsionthrough glass wool, centrifugation, or otherphysical means. Drain methylene chloride intoa 250 ml Erlenmeyer flask.

9.2.3 Add a second 60 ml volume of methylene chlorideto the sample bottle and repeat the extractionprocedure a second time, combining the extractsin the Erlenmeyer flask. Perform a thirdextraction in the same manner.

9.2.4 Assemble a Kuderna-Danish (K-D) concentratorby attaching a 10-ml concentrator tube toa 500-ml evaporator flask. Other concentrationdevices or techniques may be used in place ofthe K-D if equivalency is demonstrated forall pesticides.

9.2.5 Pour the combined extract through a dryingcolumn containing about 10 cm of anhydrousgranular sodium sulfate, and collect theextract in the K-D concentrator. Rinse theErlenmeyer flask and column with 20 to 30 mlof methylene chloride to complete thequantitative transfer.

9.2.6 Add one or two clean boiling chips to theevaporator flask and attach a three-ball snydercolumn. Pre-wet the snyder column by addingabout 1 ml of methylene chloride to the top.Place the K-D apparatus on a hot water bath(80 to 90°C) so that the concentrator tubeis partially immersed in the hot water and theentire lower rounded surface of the flaskis bathed with the vapor. Adjust the verticalposition of the apparatus and the watertemperature as required to complete theconcentration in 10 to 15 minutes. At theproper rate of distillation, the balls of thecolumn will actively chatter but the chamberswill not flooded with condensed solvent.When the apparent volume of liquid reaches 1 ml,remove the K-D apparatus. Allow it to drain andcool for at least 10 minutes.

9.2.7 Momentarily remove the Snyder column, add 50 mlof hexane and a new boiling chip and re-attachthe Snyder column. Pre-wet the column by addingabout 1 ml of hexane to the top. Concentrate thesolvent extract as before. The elapsed time ofconcentration should be 5 to 10 minutes. When theapparent volume of liquid reaches 1 ml, removethe K-D apparatus and allow it to drain and coolat least 10 minutes.

9.2.8 Remove the snyder column, rinse the flask andits lower joint into the concentrator tube with1 to 2 ml of hexane. If sulfur crystal are aproblem, proceed to paragraph 9.4.2; otherwisecontinue to paragraph 9.2.9.

9.2.9 Nitrogen Slowdown Technique

Place the concentrator tube in a warm water bath(35°C) and evaporate the solvent volume to0.5 ml using a gentle stream of clean, drynitrogen (filtered through a column of activatedcarbon). CAUTION: New plastic tubing must notbe used between the carbon trap and the sample,as it may introduce interference. The internalwall of the tube must be rinsed down severaltimes with hexane during the operation and thefinal volume brought to 0.5 ml. During

evaporation, the tube solvent level must bekept below the water level of the bath. Theextract must be never be allowed to become dry.

9.2.10 Dilute the extract to 1 ml with acetone andproceed to Alumina Column Cleanup.

9.3 Sample Extraction - Continuous Liquid-Liquid Extractor

9.3.1 When experience with a sample from a givensource indicate that a serious emulsion problemwill result, or if an emulsion is encounteredin 9.2.2 using a separatory funnel,a continuous extractor shall be used.

9.3.2 Using a 1-liter graduated cylinder, measureout a 1-liter sample aliquot and place it intothe continuous extractor. Pipet 1.0 ml ofsurrogate standard spiking solution into thecontinuous extractor and mix well. Check thepH of the sample with wide range pH paper andadjust to between pH 5 and 9 with 10 N sodiumhydroxide and/or 1:1 sulfuric acid solution.

9.3.3 Add 500 ml of methylene chloride to thedistilling flask. Add sufficient reagent waterto ensure proper operation and extract for18 hours. Allow to cool, then detach theboiling flask and dry. Concentrate the extractas in 9.2.4 through 9.2.10 .

9.4 Cleanup and Separation

9.4.1 Alumina Column Cleanup

9.4.1.1 Add 3 g of activity III neutralalumina to the 10-ml chromato-graphic.column. Tap the column tosettle the alumina. Do not pre-wetthe alumina.

9.4.1.2 Transfer the 1 ml of hexane/acetoneextract from 9.2.10 to the top ofthe alumina using a disposable Pasteurpipet. Collect the eluate in a clean10-ml concentrator tube.

9.4.1.3 Add l ml of hexane to the originalextract concentrator tube to rinseit. Transfer these rinsings to thealumina column. Elute the column withan additional 9 ml of hexane. Do notallow the column to go dry during theaddition and elution of the sample.

9.4.1.4 Adjust the extract to a final volumeof 1 ml using hexane.

9.4.1.5 The pesticide/PCB fractionis ready foranalysis. Proceed to Section 10.0.Store the extract at 4°C (+2°C)in the dark in Teflon sealed containersuntil analyses are performed.

9.4.2 Optional Sulfur Cleanup

9.4.2.1 Concentrate the hexane extract fromSection 9.2.8 to 1 ml.

9.4.2.2 Transfer the 1 ml to a 50 ml clearglass bottle or vial with a Teflon-lined screw cap. Rinse theconcentrator tube with 1 ml of hexane,adding the rinsings to the 50 ml bottle.

9.4.2.3 Add 1 ml TBA-sulfite reagent and 2 mlof 2-propanol,cap the bottle, andshake for at least 1 minutes. If thesample is colorless or if the initialcolor is unchanged, and if clearcrystal (precipitated sodium sulfite)are observed, sufficient sodium sulfiteis present. If the precipitated sodiumsulfite disappears, add morecrystalline sodium sulfite inapproximately 100 mg portions until asolid residue remains after repestedshaking.

9.4.2.4 Add 5 ml of distilled water and shakefor at least 1 minute. Allow the sampleto stand 5-10 minutes. Transfer thehexane layer (top) to a concentratorampul and go back to Section 9.2.9 .

10.0 SAMPLE ANALYSIS

10.1 PRIMARY ANALYSIS (PRIMARY GC COLUMN. GC/EC)

Samples are analyzed according to the sequencedescribed in Figure 1. Quantitation may be performedon primary or confirmation analysis.

Adjust oven temperature and carrier gas flow rates sothat the retention time for 4,4'-DDT is equal to orgreater than 12 minutes. The operating conditions forthe gas chromatographic separation shall produce peakresolutions of 25% or greater. The percent resolutionis calculated by dividing the height of the valley bythe peak height of the smaller peak being resolved,multiplied by 100. This criteria shall be consideredwhen determining whether to quantitate on the primarycolumn analysis of the confirmation (secondardycolumn) analysis. When this criteri can not be met,quantiation is adversely affected because of thedifficulty in determining where to establish thebaseline.

Inject 2 to 5 ul of the sample or standard extractsusing the solvent-flush technique or auto sampler.Record the volume injected to the nearest 0.05 ul andthe total extract volume. NOTE: Dibutylchlorendaterecovery may bbe calculated from a capillary orpacked column GC/EC meeting all QC requirements forquantitation. However, matrix spike duplicates mustbe quantitated on a packed column.

10.1.1 Inject Individual Standard Mix A and B and allmulti-response pesticides/PCBs at the beginningof each 72 hours sequence. To establish theRT window within each 72 hours sequence for thepesticides/PCB of interest, use the absolute RTfrom the above chromatograms as the mid-point,and + three times the standard deviationcalculated for each compound. IndividualStandard A and B are analyzed alternately,and intermittenly throughout the analysis asin Figure 1. Any pesticide outside of itsestablished retention time window requiresimmediate investigation and correction beforecontinuing the analysis. The laboratory mustreanalyze all affected samples.

FIGURE 1

THE 72 HOURS SEQUENCE FOR PESTICIDE/PCB ANALYSIS

1. Evaluation Standard Mix A2. Evaluation Standard Mix B3. Evaluation Standard Mix C4. Individual Standard Mix A*5. Individual Standard Mix B*6. Toxaphene7. Aroclors 1016/12608. Aroclor 1221**9. Aroclor 1232**

10. Aroclor 124211. Aroclor 124812. Aroclor 125413. 5 Samples14. Evaluation Standard Mix B15 5 Samples16 Evaluation Standard Mix A or B17. 5 Samples18. Evaluation Standard Mix B19. 5 Samples20. Individual Standard Mix A or B

(Whichever not run in step 16)21. 5 Samples22. Repeat the Above sequence starting with

Evaluation Standard B (Step 14 above23. Pesticide/PCB analysis sequence must end

with individual Standard Mix A and Bregardless of number of samples analyzed.

* These may be combined into one mixture.

** Aroclor 1221 and 1232 must be analyzed one eachinstrument and each cloumn at a minimum of onceper month. Copies of these chromatogramsmust be submitted for sample analyses performedduring the applicable month.

10.1.2 Sample analysis of extracts from section 9.0(Sample preparation) can begin ONLY whenlinearity and degradation QA/QC requirementsspecified in Section 8.0 have been met.

NOTE: The 10% RSD linearity criteria is onlyrequired on the column)s) being usedfor pesticides/PCBs quantitation.If a column is used for surrogatequantitation only, the 10% RSD isrequired only for dibutylchlorendate.

Analyze samples in groups of no more than5 samples. After the analysis of the firstgroup of up to 5 samples, analyze EvaluationStandard Mix B. Analyze another group of upto 5 samples, followed by the analysis ofIndividual Mix A or B. Subsequent groupsof up to 5 samples may be analyzed byrepeating this sequence. Alternately analyzingEvaluation Standard Mix B and Individual Mix Aor B between the groups as shown in Figure 1.The pesticide/PCB analytical sequence must endwith individual Mix A and B regardless of thenumber of samples analyzed (Figure 1).

If a multiresponse pesticide/PCB is detectedin either of the preceeding groups of5 samples, the appropriate multiresponsepesticide/PCB may be substituted forIndividual Mix A or B.

If the samples are split between 2 or moreinstruments, the complete set of standardsmust be analyzed on each instrument with thesame 72-hour requirements. All standard mustanalyzed prior to the samples to avoid theeffects of poor chromatography caused by theunsuspected injection of a highlyconcentrated sample.

10.1.3 If one or more of the criteria have beenviolated during the 72-hour sequence, stopthe run and take corrective action. Aftercorrective action has been taken, the 72-hoursequence may be restarted as follows:

10.1.3.1 If a standard violated the criteria.

restart the sequence with thatstandard, determine that the criteriahave been met, and continue withsample analyses according to Figure 1.

10.1.3.2 If a sample violated the criteria,restart the sequence with thestandard that would have followedthat group of samples, determinethat the criteria have been met,and continue with sample analysesaccording to Figure 1.

10.1.4 If it is determined after the 72-hoursequence that one or more of the criteriahave been violated, proceed as follows:

10.1.4.1 If a standard violated the criteria,all samples analyzed after thatstandard must be reanalyzed a spartof a new 72-hour sequence.

10.1.4.2 If a subsequent standard in theoriginal sequence met all thecriteria, then only those samplesanalyzed between the standard thatdid not meet the criteria and thestandard that did meet the criteriamust be reanalyzed as part of anew 72-hour sequence.

10.1.4.3 If only samples violated the criteria,then those samples must be reanalyzedas part of a new sequence.

10.1.5 Sample must also be repested if the degradationof DDT and/or endrin exceeds 20.0% respectivelyon the intermittent analysis of EvaluationStandard Mix B.

10.2 CONFIRMATION ANALYSIS (SECONDARY COLUMN. GC/EC)

10.2.1 Confirmation analysis is to confirm thepresence of compounds tentatively identifiedin the primary analysis (10.1). Thereforethe only standards that are required are theEvaluation Standard Mixes (to check linearity

and degradation criteria) and standards of allcompounds to be confirmed. The 72 hours sequenceshown in Figure 1 is therefore modified to fitsuch case. Quantitation may be performed onthe cinfirmation analysis. NOTE: If toxapheneor DDT is to be quantitated, additionallinearity requirements are specifiedin 10.1.2

10.2.2 The peak resolution criteria of 25% or greaterbetween peaks shall be observed when determiningwhether to quantitate on the confirmationanalysis (See 10.1). If a fused silicacapillary column (FSCC) is used, the peakresolution criteria shall be checked for thefollowing pesticide pairs: a) Beta-BHC andDelta-BHC; b) Dieldrin and 4,4'-DDT;c) 4,4'-DDD and Endrin Aldehyde; d) Endosulfansulfate and 4,4'-DDT.

10.2.3 All QC requirements specified for primary GCcolumn analyiss shall be observed.

10.2.4 Begin the confirmation analysis GC sequencewith the three concentration levels ofEvaluation Standard Mixes A, B, and C. Theexception to this occurs when toxaphene and/orDDT series are to be confirmed and quantitated.There are four combinations of pesticides thatcould occur, therefore the following sequencemust be followed depending on the situation:

10.2.4.1 Toxaphene Only -

Begin the sequence with EvaluationStandard Mix B to check degradation,followed by three concentrationlevels of toxaphene. Check linearityby calculating the %RSD.If %RSD <10.0%,then use the Equation 1 for calculation.If %RSD > 10.0%, then plot a standardcurve and determine the nanogram foreach sample in that set from the curve.

10.2.4.2 DDT, DDE, DDD Only -

Begin the sequence with EvaluationStandard Mix B. Then inject three

concentration levels of a standardcontaining DDE, DDD, and DOT.Calculate linearity and follow therequirements specified in 10.2.4.1.for each compound to be quantitated.

10.2.4.3 DDT Series and Toxaphene -

Begin the sequence with EvaluationStandard Mix B. Then inject threeconcentration levels of toxaphene andanother three levels of the DDT series.Calculate linearity and follow therequirements specified in 10.2.4.1 foreach compound to be quantitated.

10.2.4.4 Other Pesticides/PCBs Plus DDT Seriesand/Or Toxaphene

Begin the sequence with EvaluationStandard Mixes A, B, and C. Calculatelinearity of the four compounds in theEvaluation Standard Mixes. If DDTand/or one or more of the othercompounds have RSD > 10.0% and/ordegradation exceed the criteria,corrective action shall be performedbefore repesting the above chromato-graphy evaluation.

If only DDT exceed the linearity anaone or more of the DDT series is to bequantitated, follow the procedure forDDT,DDE, and DDD only in 10.2.4.2.

If none of the DDT series is to bequantitated and DDT exceed the 10%RSDcriteria, simply report the %RSD on theproper form. Anytime toxaphene is tobe quantitated, procedure in 10.2.4.1shall be used.

10.2.5 After the linearity sstandards required in10.2.4 are injected, continue the confirmationanalysis injection sequence with all compoundstentatively identified during the primary GCcolumn analysis to establish the daily retentiontime windows during primary analysis. Analyze

all confirmation standards for a case or set atthe beginning, at intervals of every 5 samples,and at the end. Any pesticide outside theretention time window requires immediateinvestigation and correction before continuethe analysis. The laboratory shall reanalyzeall samples between the standard that exceedsthe criteria and a subsequent standard thatmeet the criteria.

10.2.6 Begin injection of samples. Analyze group of5 samples with a standard pertaining to thesample after each group (Evaluation StandardMix B is required after the first 5 samples,and every 10 samples thereafter).The alternating standard calibration factorsmust be within 15.0%of each other ifquantitation is performed. Deviation greaterthan 15% requires the laboratory to repeatthe samples analyzed between the standradthat exceeds the criteria and a subsequentstandard that meet the criteria. The 15%criteria only pertains to compounds beingquantitated.

10.2.6.1 If more than one standard isrequired to confirm all compoundsidentified in the primary analysis,includes a alternate standard aftereach 10 samples.

10.2.6.2 Samples shall also be repested ifthe degradation of either DDTand/or endrin exceed 20% on theintermitten Evaluation StandardMix B.

10.2.6.3 If the sample s are splitted between2 or more instruments, all standardsand blanks pertaining to those samplesmust be analyzed on each instruments.

10.2.7 Inject the method blank (extract with each setof 20 samples) on every GC and GC columns onwhich the samples are analyzed.

10.2.8 If quantitation is performed on the confirmation

analysis, follow the instruction in Section 10.1regarding dilution of extracts and reportingresults.

11.0 CALCULATION

11.1 Determine the concentrationof individual compoundsin the sample.

11.1.1 If the external standard calibration procedureused, calculate the amount of material injectedfrom the peak response using the calibrationcurve or calibration factor determined inSection 7.2.2. The concentration in the samplecan be calculated from the following equation:

(A) (Vt)Concentration (ug/L) = ——————————

(Vi) (Vs)

Where:

A = Amount of material injected (ng).

Vi = Volume of extract injected (ul).

V-t = Volume of total extract (ul)

Vs = Volume of water sample extacted (ml)

12.0 DATA REPORTING REQUIREMENT

12.1 All reports and documentations shall be legible,single-sided, and clearly labelled and paginated.

12.2 The sample data package shall be consecutivelypaginated, and shall include cover pages, sampledata, raw data.

12.2.1 Cover pages for the data package,including the project name, laboratoryname, field sample number cross-referencedwith laboratory ID number, commentsdescribing in details any problemsencountered in processing the samples,

and the validation and signature by thelaboratory manager.

12.2.2 Sample Data

Sample data shall be reported using theOrganic Analysis Data Reporting Forms(Attachment I) for all samples, arrangingin increasing alphanumeric sample numberorder, followed by the QC analysis data,quarterly verification of instrumentparameter forms, raw dataincluding copiesof the sample custody records and samplepreparation logs.

12.2.2.1 FORM I (Pesticides OrganicAnalysis Data Sheet)

12.2.2.2 FORM II (Pesticides SurrogateRecovery)

12.2.2.3 FORM III (Pesticides MatrixSpike/Matrix Spike Duplicate(MS/MSD) Recovery)

12.2.2.4 FORM IV (Pesticides MethodBlank)

12.2.2.5 FORM VIII A (PesticidesEvaluation Standard Summary)

12.2.2.6 FORM VIII B ( Evaluation ofRetention Time Shift forDibutylchlorendate)

12.2.2.7 FORM IX ( Pesticides/PCBsStandard Summary)

12.2.2.8 FORM X (Pesticides/PCBsIdentification)

12.2.2.10 RAW DATA

Raw data shall include allinstrument printouts used forthe sample results, includingthose readout that fall below

the method detection limits,and copies of GC chromatograms.Raw data must be labelled withproject name, field samplenumber, time and date of eachanalysis, instrument used.

13.0 REFERENCES

13.1 "Determination of pesticides and PCBs in industrial,and municipal Wastewaters." EPA-600/4-82-023,U.S.Environmental Protection Agency, EnvironmentalMonitoring and Support Laboratory, Cincinnati, Ohio,45268,June, 1982.

13.2 40 CFR Partl36, Appendix B.

PESTICIDE ORCANICS ANALYSIS DATA SHEET

Lab Mane:

Matrix:

SazplaLav.l:

wat«r

vol: •L

Extraction: (S«pF/Cont/Sonc)

GPC Cleanup: (Y/N)__ pH:_

Field Sample Huober_Lab Sazpla ID:

Lab Fila XD:

Data RacaivacJ:

Data Extracted:_

Data Analyzad:

CAS NO. COHPODND

Dilution Factor:

CONCENTRATION TJNITS:(ug/L

I| 319-84-6—————alpha-BHC_______

319-85-7——————b«ta-BHC_________319-86-8—————delta-BHC_______58-89-9———————gaona-BHC (Lindan«)76-44-8———————H«ptachlor_______~_309-00-2——————Aldrin_______ .1024-57-3—————Heptachlor «poxide_959-98-8——————Endo»ultan I______60-57-1———————Dlcldrin_________72-55-9 ——————— 4,4'-DDE________72-20-8———————Endrin___________33213-65-9————Endoiullan II_____72-54-8———————4 ,4 '-ODD_________1031-07-*——•——Endoculfan «ulf«t*_50-29-3————————4,4 '-DOT______•72-43-5——————M«thoxychlor______53494-70-5————Endrin ktton«_____5103-71-9—————alpha-Chlordan*___5103-74-2—————gamaa-Chlordane___8001-35-2—————Toxaph«n«_______12674-11-2————Aroclor-1016_____11104-28-2—————Aroclor-1221______11141-16-5————Aroelor-1232_____53469-21-9—————Aroclor-1242______12672-29-6—————Aroclor-1248______11097-69-1—————Aroclor-1254______11096-82-5————Aroelor-1260_____

FORM I PEST

Lab Maae:

WATER PESTICIDE SURROGATE RECOVERY

1 rieiaI SAMPLE NO.|. —— m ———— __

Oil02103104|05106|071081091101HI12113114115116|1711811912012112212312412512CI271281291301

5BC) • Dibutylch

61(DBC)I

Lorenda

OTHER

te

HOVISORVBC LIMITS(24-154)

f Colusn used to flag recovery values

• Values outside of QC Halts

D Surrogates diluted out

page _ of _FORM II PEST-1

WATER PESTICIDE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVER*

Lab Naaa:Lab Sample I.D. _. Field Sample mmber_

Matrix Spike - EPA Saaple Mo.:

COMPOUND

qaana-BHC (Lindane)HeptachlorAldrinDieldrinEndrin4, 4 '-DOT

SPIKEADDED(ug/D

SAMPLECONCENTRATIOK

(ug/L)KS

CONCENTRATION(ug/L)

MS | QC |% | LOUTS |

RZC || RZC. |

156-1231140-1311140-1201152-1261156-1211138-12711 1

COMPOUND

gamna-BHC (Lindane)HeptachlorAldrinDieldrinEnd r in4,4'-DDT

SPIKEADDED(ug/L)

KSDCONCENTRATION

(ug/L)MSD*

REC «%

RPD t

1CC LIMITS |XfD | REC. |

15 |56-123|20 |40-131|22 |40-120|18 |52-126|£1 4 56-121 |27 |38-127|

1 I

t Column to be used to flag recovery and RPD values with an asterisk

* Values outside of QC liaits

RPD:____ out of ____ outside linitsSpike Recovery:^____ out of _____ outside linits

COMMENTS:

FORM III PEST-1

PESTICIDE XETHOD BLANK SUMMARY

Lab N«n«:

Lab Saaple ZD: __

Matrix: ifater.Oat* Extracted:

Oat* Analyzed (1):

Ti»« Analyzed (1):'

Instrument ZD (1):

CC Coluan ZD (1):

Lab File ZD: ________

level:(lev/»*d) ___Extraction: (C*pF/Cont/Sonc)_

Oat* Analyzed (2): ____

Ti»* Analysed (2): ____

Zn«tru»ent ZD (2): ___CC Column ZD (2):

THIS METHOD BLANK APPLIES TO THE FOLLOWING SAMPLES, MS AND MSD:

1 FieldI SAMPLE NO.1— —— ——— ——

Oil021031041051061071081091101111121131141151161171181191201211221231241251261

LABSAMPLE ID

DATE | DATEANALYZED 1| ANALYZED 2

.

COMMENTS:

page _ of _FORM ZV PEST

PESTICIDE EVALUATION STAHDARDS SUMMARY

Lab HIM:

Instrument ID: CC Colon ID:

Dates of Analyses:_ to

Evaluation Cbeck for Linearity

PESTICIDE

AldrinEndrin4,4* -DOTDEC

CALIBRATIOMFACTOR

TVAL XIX A

CALIBRATIOMFACTOR

ZVAL MIX B

CALIBRATIONFACTOR

EVAL MX C

%RSD(</•10.0*)

(1)

(1) If > 10.0% RSD, plot a standard curv« and determine tht n<jfor each sample in that sat from the curva.

Evaluation Chack for 4,«'-DDT/Endrin Braakdovn(p«rcant braaXdovn expressed as total degradation)

I"\t

oil02|03 |04 |05|06|07|08|09 |10|"I12|13 I141

INITIALEVAL MIXEVAL MIXEVAX, MIXEVAL MIXEVAL MIXEVAL MIXEVAL MIXEVAL MIXEVAL MIXEVAL MIXEVAL MIXEVAL MIXEVAL MIXEVAL MIX

DATEAKALYZED

TIKEANALYZED

ENDRIN |4,4'-DOT|COMBINED|(2)

(2) See For* instructions.

FORM VIII PEST-1

PESTICIDE EVALUATION STANDARDS SOTOtARYEvaluation of Jlatantion Tla« Shift for Dibutylcfalorandata

lab K»»«:

Instrument ID:_ CC Coluan 10:

Dates of Analyses:_ to

I Field| SAMPLE MO.

Oil021031041051061071081091101111121131141151161171181191201211221231241251261271281291301311321331341351361371381

IAB SAK?LEID

BATEANALYZED

-

.

TIMEANALYZED

%D *

• Values outside of QC limit* (2.0% for paek*d eeluans,0.3% for capillary column*)

P»ge _ of _VIII PEST-2

PESTICIDE/KB STANDARDS RMKUtY

Lai Kaae:

Instrument ID: CC Colon ID:DATE(S) OFANALYSISTI«(S) OFANALYSIS

"FROM:TO:"

FROM:"TO:"

DATE Or ANALYSISTIXZ Or ANALYSISEPA SAMPLE NO.(STANDARD)

COMPOUND1

I

lalpha-BHC|b«ta-BHC ~ldelta-BHC_Igamna-BHC_JKeptachlorlAldrin(Kept, epoxideJEndosulfan IIDieldrin_|4,4'-DDE__|Endrin___JEndosulfan|4,4'-DDD____.JEndo. culfate|4,4'-DDT____|Methoxychlor_IEndrin XetoneI a. Chlordanejg. ChlordaneI Toxaphene___JAroclor-1016lAroclor-1221"lAroclor-1232~(Aroclor-1242~|Aroclor-1248~|Aroclor-1254~(Aroclor-1260~

KT ICALIBKATIONFACTOR

KTI I I| CALIBRATION | QHT1 %D

FACTOR |Y/X|

Under QNT Y/H: enter Y if quantitation was performed, N if not performed.%D «ust be less than or equal to 15.0% for quantitation, and less thanor equal to 20.0% (or confirmation.Note: Determining that no compounds were found above the CRQL is • form ofquantitation, end therefore at least one column must meet the 15.0* criteria.For aulticomponent analytes, the single largest peak that is characteristicof the component should be used to establish retention time and «D.Identification of such analytes is based primarily on pattern recognition.

page _ of _FORM IX PEST

PESTICIDE/KB IDENTIFICATION

*»»«:_

CC Column XD (1):Xn»tru»«nt XD (1):Lab Caapl* XD: ___

X*b ril« XD:

CC Column XD (2):

instrument XD (2):

(only if cehfir»«<S by CC/MS)

FESTICIDE/PCB KZTENTION TIME RT WIMDOWOF STANDARD

TO

QOXNT? CC/MS?(V/N)

01

02

FORM X

APPENDIX E-9

ANALYSIS OF LANDFILL GAS FOR VOCs (ENSECO)


RMT SOPSECTION NO. 2.07REVISION NO. 2DATE: June 1990PAGE 1 OF 4

INSTRUMENT TYPE: Total Organic Carbon (TOC) Analyzer

MANUFACTURER: Rosemount Analytical, Dohrmann Division

MODEL: DC-80

LABORATORY NO.:

SERIAL NO.: DC-80 Electronics ModuleDC-80 Reaction ModuleASM-1 Auto Sampler ModulePRG-1 Purgeables ModuleDC-80 Sludge/Sediment SamplerPrinter

PROCEDURE:

Serial No. HD 1264Serial No. HD 1291Serial No. HD 1165Serial No. NoneSerial No. NoneSerial No. None

The DC-80 TOC Analyzer can be configured several ways. This procedurewill explain the configuration for the analysis of waters (WTOC) and soils(STOC) and will be dealt with in separate sections.

I. Waters TOC (WTOC) configuration

A. Routine Operation

1. Turn on 02 purge gas tank and adjust line pressure to 30psi.

2. Turn power switch of ASM-1 autosampler on and verifythat "Manual" switch is lit.

3. Turn on Power switch of DC-80 Reaction Module and verifythat "Pump" and "Lamp" switches are activated.

4. Turn on Power to DC-80 Electronics Module.

5. Power of Horiba PIR-2000 detector is always left in the"ON" position.

6. Connect junction between manifold ports #4 and #5located on the right side of the DC-80 Reaction Module.Verify purge gas is bubbling through the reactionvessel.


7. Put pump fingers in place on peristaltic pump on rightside of DC-80 Reaction Module. Verify that waste linesfeed into proper container and oxidant reservoir isfilled.

8. Place function switch on front panel of ElectronicsModule to "TOO" mode.

9. Place detector function switch on front panel ofElectronics Module to "Det" setting. Allow baselinereading to stabilize to historical value, typically0.0100 - 0.0200.

10. Set 3 function range switch to 1 mL for low levelanalyses or 200 ^L for high level analyses.

11. Calibrate with appropriate standard based on rangeselected.

B. Shutdown

1. Remove junction between ports #4 and #5.

2. Turn off purge gas flow.

3. Turn off power switch on front panel of the ElectronicsModule.

4. Turn off power switch on front panel of the ReactionModule.

5. Turn off power switch on ASM-1 autosampler module.

6. Release tension on peristaltic pump fingers.

II. Soils TOG (STOC) Configuration

A. Routine Operation

1. Turn on Oj purge gas tank and verify line pressure of 30psi.

2. Connect lines from PRG-1 purgeables module labeled "4"and "5" to ports "4" and "5," respectively on the rightside of the DC-80 Reaction Module. Verify gas flow byobserving bubbling in reaction vessel.


3. Turn on power switch labeled "Furnace" on PRG-1 module.

4. Turn "Power" of ASM-1 autosampler module on. Verifythat "Manual" switch is lit.

5. Turn "Power" switch of DC-80 reaction module on. Turnoff switches labeled "Pump" and "Lamp."

6. Turn on "Power" switch of DC-80 Electronics Module.

7. Set function switch to "TOX."

8. Set injection volume control to "40 til* setting.

9. Allow furnace to heat up (- 30 minutes) and baselinevalue to stabilize to historical value, typically 0.0100- 0.0200.

10. Calibrate and operate as described in analytical methodfor soils TOG. (See RMT Method, Section No. 2.44.)

B. Shutdown

1. Disconnect lines to ports #4 and #5.

2. Turn off purge gas.

3. Turn off power switches on DC-80 Electronics Module,(leave power to Horiba PIR-2000 on at all times), DC-80Reaction Module, ASM-1 Autosampler Module and PRG-1Furnace Module.

Ill. Routine/Preventative Maintenance

A. Septum ReplacementReplace the injection septum every 100 injections or at anytime leakage is obvious.

B. Reagent ReplenishmentCheck daily.

C. Sparge/Carrier Gas ReplenishmentCheck once a week.


D. Tin ScrubberCheck daily. Color will change as it is used. Repack the tubewhen one-half of the tin is exhausted. Use 20 mesh granulartin.

E. Pump Tube ReplacementReplace every two weeks if instrument is operated continuously.Release pressure fingers when not in use. Plug reagent linesbefore releasing.

F. Printer TapeCheck every two or three days. Always check before anunattended automated run.

G. Infra-red ZeroCheck once or twice a day to see that zero reading is around0.0100 on the digital readout when the detector/ppm switch isin the detector position. It should always be ABOVE zero. Areading of 0.0100 on the DVM is reasonable.

H. Infra-red SpanThe IR span should not need any routine resetting.

REVIEWED BY: (-***_, ~L- "l-4-GrrJ**&-________ Cp I IEric L. Thomas DateSupervisorInorganic Section

APPROVED BV:

____Mark S. Wirtz 7\ DateQuality Control CooWlnator

(, ' </• 9£>R. Alan Dough ty*" I (s DateLaboratory Director

LABORATORIESRMT METHODSECTION NO. 2.44REVISION NO. 1DATE: April 1990PAGE 1 OF 5

ANALYTICAL METHOD

TITLE: Total Organic Carbon Analysis

DEPARTMENT: Inorganic - Wet Chemistry

APPLICATION: Water and wastevater for nonpurgeable organic carbon

REFERENCE: EPA 600 4-79-020, Revised March 1983, Method 415.2EPA Manual SW-846, 3rd Edition, Method 9060Standard Methods for the Examination of Water and

Uastewater. 17th Edition, 1989, Method 5310CDohrmann DC-80 TOC Systems Manual, Edition 6, January 1984

PROCEDURE SUMMARY:

This procedure uses the persulfate ultraviolet oxidation method. It isa rapid and precise method for the measurement of trace levels oforganic carbon in water. Organic carbon is oxidized to C02 bypersulfate in the presence of ultraviolet light. The C02 produced ismeasured directly by an infrared analyzer.

REVIEWED BY : CA*-Eric L. ThomasSupervisorInorganic Section

Date

APPROVED BY:

Quality Control CoordinateDate

R. Alan Doughty ^fLaboratory Director

Date

RMT METHODSECTION NO. 2.44REVISION NO. 1DATE: April 1990PACE 2 OF 5

SAMPLE HANDLING & PRESERVATION:

The sample is preserved at the time of sampling by acidifying to pH < 2with sulfuric acid (H2S04) . The sample is refrigerated in a glassbottle. Hold time for the preserved sample is 28 days.

INTERFERENCES:

The presence of chloride in high concentrations (> 0.10%) interfereswith the rate of oxidation. The tailing which results may fall outsideof the 8 minute analysis window. The reagent can be slightly modifiedby adding mercuric chloride and mercuric nitrate. The chloride thencomplexes with the mercury which in turn allows the carbon to oxidize ata normal rate. The procedure can be found on page 7-1 of the systemsmanual.

Highly suspended solids can also give variable results. However, it isimperative that the sample be suspended evenly if total organic carbonis being measured. Settling should not occur before injection.Particles may clog the autosampler tubing. Therefore, samples withsuspended matter must be manually injected.

APPARATUS:

Dohrmann DC 80 Total Organic Carbon Analyzer18 x 150 mm test tubesSyringes: 50 tiL, 100 - 250 iiL, 1 mLVolumetric flasks: 100 mL, 200 mL, 1000 mL

REAGENTS:

Deionized (D.I.) waterPotassium persulfateNicric acid (HN03)Mercuric chloride (HgCl)Potassium hydrogen phthalate (KHP)Mercuric nitrate, monohydrate (Hg2N03 • H20)

Prepare Potassium Persulfate Solution

Dissolve 40 grams potassium persulfate in 1 liter of D.I.water.

Add 1 mL cone, nitric acid. Mix well. Store in cool darkplace. Shelf life is one month.

RMT METHODSECTION NO. 2.44REVISION NO. 1DATE: April 1990PAGE 3 OF 5

Prepare Potassium Persulfate-Mercuric Salt Solution

Dissolve 8.2 grams HgCl and 9.6 grams Hg2N03 • H20 in 400 mL D.I.water.

Add 20 grams potassium persulfate and 5 mL cone, nitric acid. Mixwell and bring to 1 liter with D.I. water.

Prepare Standard (ppm as Carbon), 2000 ppm

Dissolve 425 mg KHP in 100 mL D.I. water. Add 0.1 mL cone. HN03.Store in an amber bottle and refrigerate. Shelf life is onemonth.

Prepare Standard (ppm as Carbon), 400 ppm

Dilute 20.0 mL 2000 ppm Standard to 100 mL in a volumetric flask.Store in an amber bottle and refrigerate. Shelf life is onemonth.

Prepare Standard (ppra as Carbon), 10 ppm

Dilute 1.0 mL 2000 ppm Standard to 200 mL in a volumetric flask.Store in amber bottle, refrigerate. Shelf life is one month.

PROCEDURE:

1. Start-up instrument. (See RMT SOP, Section No. 2.07.)

2. Calibrate the instrument. The instrument is calibrated with a onepoint standard. Uhen the CAL light is off, the instrument has nocalibration in its memory. To calibrate:

a. Inject a standard,b. Push START.c. When READY light comes on, push CAL. CAL light should

now be on.

When CAL light is on, the instrument is already storing acalibration. In most cases an update of the existing calibrationis sufficient. Follow the same calibration steps to update acalibration. The CAL light should remain on the entire time.

In order to erase an existing calibration from memory, simply holdCAL in for at least 1 second. The CAL light will go off.


Select a calibration standard from the following ranges:

Sample Cone. Volume Injected (uL> Calibration Std.0.1 - 20 ppra 1000 10 ppm KHP10 - BOO ppra 200 400 ppm KHP100 - 4000 ppra 40 2000 ppm KHP

When selecting a range, make sure the selector knob on the frontpanel is in the correct position.

3. Sample is prepared for injection. Sample is shaken vigorously andpoured into a labeled test tube. (All sediment must be suspendedevenly.)

4. Sample is sparged for 10 minutes with oxygen. A syringe is usedto agitate the sample to insure uniform suspension of solids.The syringe is then filled to sample volume.

5. Sample is injected and START is pushed. When the sample has beenprocessed, the READY light will come on and the integratedconcentration will be sent to the printer. This indicates thatthe instrument is ready for the next injection.

6. Shut down instrument. (See RHT SOP, Section No. 2.07.)

Quality Control

A Method Blank and calibration standard are run each day to verifycalibration. Recalibration (or updating an existing calibration) isnecessary if standards vary by more than 10% from calibration. A checkstandard is run after every 10 samples to monitor system stability.

Initial Calibration Verification (ICV)The ICV must be run immediately after calibration and meet currentcontol limits.

Initial Calibration Blank (ICB)The ICB must be analyzed after the ICV and be less than theinstrument detection limit (IDL).

Laboratory Control Sample (LCS)An LCS consisting of known concentration must be prepared andanalyzed for each matrix type and meet current control limits.

Continuing Calibration Verification (CCV)The CCV is analyzed after every 10 analytical samples and meetcurrent control limits.


Continuing Calibracion Blank (CCB)The CCB is analyzed after every CCV and be less than the IDL.

Spike (10 ppra)A spike must be performed on each group of samples of a similarmatrix type with a frequency of 10%.

DuplicateA duplicate must be analyzed on each group of samples of a similarmatrix type with a frequency of 10%.

Calculations

Spike:

% Recovery - SSR-SR SSR - Spiked Sample ResultSA SR - Sample Result

SA - Spike Added

Duplicate:

If the sample value and/or the duplicate value is less than 5 times theinstrument detection limit (IDL), use absolute difference.

|Sample-Duplicate| - Absolute Difference

If both the sample value and the duplicate value are equal to or greaterthan 5 times the IDL, use relative percent difference (RPD).

RPD - S-D x 100 S - Original Sample Value(S+DJ/2 D - Duplicate Sample Value

LABORATORIESAppendix

APPLICATION: To analyze soil, sludge, and solid waste for organic carbon.

REFERENCE: ASTH Method D4129-82, 1982.Dohrmann DC-80 TOC Systems Manual, ed. 6, January 1984.

SAMPLE HANDLING AND PRESERVATION:

The sample is not preserved, but is refrigerated in a glassbottle.

APPARATUS:

Dohrmann DC 80 Total Organic Carbon Analyzer with Sludge nml SedimentSample Accessory

ForcepsWatch Glass50 uL SyringeSmall SpatulaPlatinum Boat

PROCEDURE:

1. Start up:

Three POWER 's are turn on — right to lefc. Furnace is turned on.Gas supply is turned up to 30 psi oxygen. The furnace must be allowedto warm up for approximately one hour. During this time, the two tubesfrom the furnace should be immersed in water, ph - 10, to absorb anyNOX that may be formed. The furnace is ready when the tube near thesample inlet is glowing. When the baseline is stabilized around 0.0100,the instrument is ready for the first injection. The PUMP and LAMPdo not have to be turned on.

The teflon loop is removed form inlets 4 and 5 on the reaction module andlines 4 and 5 from the furnace are attached in its place.

2. Boat preparation:

The platinum boat is lined with quartz wool. The boat is introduced intothe furnace and allowed to "bake-out".

3. The instrument is calibrated using 2000 ppm KIIP standard. The standard isinjected into the boat through a septa in the sample port.

4. Sample preparation:

Sample is mixed until homogeneous.Transfer approximately 5 grams of sample into a porcelain dish. Add 5tsulfuric acid dropwise, while mixing, until effervescence is no lonp.ervisible. Dry in nn oven at 105"C until constant dry weight is obtained.

LABORATORIES

Sample is weight into a lined platinum boat. (Sample si/.o iiuis t be keptbetween 10 and 100 mg.)Sample is placed in the saddle and the injection port is closed. Sampleis allowed to stand outside of furnace for about 2 minutes Co stabilizethe systcm.Note: When calibrating, the boat Is immediately introduced into the furnace;.

5. START is pushed and sample in introduced into the furnace. When thesample has been processed, the READY light will come on and the integratedconcentration will be sent to the printer. Thlfl indicates that the ins cm*ment is ready for the next sample.

6. Instrument shut down:

Three POWER 's are turned off—left to right. Gas supply is turned off.The reagent supply Cube, the two waste exit tubes, and lines A and 5 arcdisconnected to prevent syphoning.

APPENDIX F

RMT STANDARD OPERATING PROCEDURE FOR THE ANALYSIS OF TOTAL ORGANIC CARBON

STANDARDOPERATINGPROCEDURE

Subject or Title: Page 1 of 22The Determination of Volatile Organics (VOCS)

in Ambient Air by GC/MS - Scan Mode

SOP NO: Revision No.: 2.0 Effective Date:CRL-LM-7001 March 1, 1990

Supercedea: Revision 1.0

1. Scope and Application

1.1 Analytes (See Table 1)

1.2 Detection limit (See Table 1)

1.3 Applicable matrices - air

1.4 Dynamic range (See Table 1)

1.5 Approximate analytical time

4 min. - cool down of cryo trap2 min. - flush of inlet system on trap10 min. - collection of 500 mL sample on trap2 min. - flush of inlet system with internal std.2 min. - collection of 100 mL of internal std on trap2 min. - flush of trap with HP Helium32 min. - GC run time

When running multiple samples, steps can be overlappedto reduce run time to 40 min.

Prepared by: Steve Harris

QA Officer Approval:

STANDARD; OPERATING

PROCEDURE

Page 2 of 22The Determination oi Volatile Organica (VOCa)

SOP

in Ambient Air by

NO:

OC/MS -

Revision

Scan Mode

. No. : 2.0CRL-LM-7001

TABLE 1. VOC Target Compounds

Effective Date:March 1, 1990

Detection Limits Dynamic

2)3)4)

5)6)7)B)9)

10)11)

12)14)15)16)17)18)19)20)21)22)23)24)25)26)27)28)29)30)31)32)33)34)35)36)37)38)39)40)41)

Compound

Dichlorodifluoromethane (Freon 12)Chloromo thane1, 2-Dichloro-l, 1,2,2-

tetraf luoroethane (Freon 114)Vinyl chlorideBromome thaneChloroethaneTrichlorofluoromethano (11)cie-l,2-DichloroetheneCarbon disulfide1,1,2-Trlchloro- 1,2,2-

trif luoroethane (Freon 113)AcetoneHethylene chloridetrans-1, 2-DichloroetheneHexane1 , 1-DichloroethaneVinyl Acetate1 , 1-Dichloroethene2-ButanoneChloroform1,1, 1-Tr ichloroethanoCarbon tetrachlorideBenzene1, 2-DlchloroethaneTrichloroethene1 , 2-Dichloropropane1, 4-DioxaneBromodichloromethanecis-1 , 3-Dichloropropene4-Methy 1-2 -pent anoneToluenetrane-1, 3-Dichloropropene1, 1,2-TrichloroethaneTetrachloroethene2-HexanoneDibromochlorome thane1,2-Dibromoethane :ChlorobenzeneEthylbenzene1,4-and l,3-(p,m) Xylene

R.T.

1.492. 48

2.522.863.583.. 934.545.635.63

5.876.106.897.367.988.228.719.439.68

10.2710.2710.5311.0011.1912.4412.8713.3413.6814.6115.1415.1616.0016.3416.2817.1017.0617.0818.2818.7319.04

HDL (ppbv)

0.871.2

1.01.21.52.50.550.846.2

0.966.61.91.94.01.21.31.11.41.10.450.551.60.531.23.93.50.901.51.61.51.61.41.43.01.41.01.31.32.6

Range (ppbv)

0.87-3001.2-300

1.0-3001.2-3001.5-3002.5-3000.55-3000.84-3006.2-1200

0.96-3006.6-3001.9-3001.9-3004.0-3001.2-3001.3-3001.1-3001.4-3001.1-3000.45-300O. 55-3001.6-3000.53-3001.2-3003.9-3003.5-3000.90-3001.5-3001.6-3001.5-3001.6-3001.4-3001.4-3003.0-3001.4-3001.0-3001.3-3001.3-3002.6-600


PageTha Determination of Volatile Organica (VOCe)

in Ambient J.ir by CC/MS - Scan Mode

22

SOP NO:CRL-LM-7001

Revision No.: 2.0 Effective Date:March 1, 1990

TABLE 1. voc Target Compounds(Continued)

Detection LimitsR.T. MDL (ppbv)

19.91 1.120.02 3.520.37 1.021.99 1.921.90 1.022.31 2.022.48 1.323.37 1.523.04 1.724.13 2.224.97 2.429.28 3.629.93 2.4

DynamicRange

1.1-3003.5-3001.0-3001.9-3001.0-3002.0-3001.3-3001.5-3001.7-3002.2-3002.4-3003.6-3002.4-300

Compound

42) l,2-(ortho) Xylena43) Styrene44) Bromoform45) 1,1,2,2-Tetrachloroethane46) Benzyl chloride47) 4-Ethyltoluene48) 1,3,5-Trimethylbenzene49) 1,2,4-Trimethylbenzene50) 1,3-Dichlorobenzene51) 1,4-Dichlorobenzene52) 1,2-Dichlorobenzene53) 1,2,4-Trichlorobenzene54) Hexachlorobutadiene2. Summary of Method

2.1 A pressurized air sample is metered through a mass flow controlleronto a cryogenically cooled trap. After 500 mL of the sample hasbeen trapped, a valve is switched and the trap is heated to purge thetrap's contents onto the gas chromatography column. The targetcompounds are analyzed with a mass spectrometer operated in the scanmode.

3. Comments

3.1 Interferences

3.1.1 Gas regulators are cleaned by the manufacturer using Preon113, which is one of the target compounds. Before using ultrahigh purity (UHP) Nitrogen (Ni), Hydrocarbon (HC) free air,Internal Standard (I.S.), or a target compound standard mix,each regulator should be purged a minimum of three timefi withthe appropriate gas.

3.1.2 Contamination may occur in the sampling system if canistersare not properly cloaned prior to use. Canisters used tocollect source samples should not be used for the collection


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in Ambient Air by OC/MS - Scan Mode

S O P N O : " ~ ~ R e v i s i o n No.: 2 . 0 E f f e c t i v e Date:CRL-LM-7001 March 1, 1990

of ambient air samples until a blank analysis indicates that no targetcompounds are present above the MDL. All other sampling equipment includingpumps, flow controllers and filters must be thoroughly cleaned to ensure thatthe filling apparatus will not contaminate samples.

3.2 Helpful Hints

None

4. Safety Issues

4.1 In order to prevent contamination of the lab air by the samples, thevent line must be connected io the system outlet and the fume hoodmust be on.

4.2 While making standards, tho fume hood must be running. When finishedvalves must be closed and lines vented.

4.3 All compressed gas cylinders must be securely fastened to a bench orwall.

4.4 Normal precautions should be used in the handling of liquid nitrogen(LNi ) (do not touch transfer lines aa burns can result).

4.5 Sampling canisters should never be pressurized over 40 psig.

5. Sample Collection, Preservation, Containers and Holding Times

5.1 Samples should be collected in precleaned and batch analyzed SUMMApassivated canisters. A 7 n.icron filter should be placed on theinlet of the can to protect the valve from particulates. Canistersshould never be pressurized over 40 psig.

5.2 The absolute pressure of the canister must be recorded before andafter sample collection.

5.3 Samples must be kept at <25°C.

5.4 Sampled should be analyzed within 14 days of collection.

6. Apparatus and Materials

6.1 Gas chromatograph - capable of subambient temperature programming forthe oven and with the jet neparator option (Hewlett Packard 5890).

6.2 Maas—selective datector - equipped with computer and appropriatesoftware (Hewlett Packard 5i970Q with HP-1000 RTE-A data system).


Page 5 of _22_Tha Determination oi Volatile Organice (VOCa)

in Ambient Air by GC/MS - Soan Mode


6.3 Cryogenic trap with temperat ure control assembly (Nutech 8533).See Figure 1.

6.4 Electronic mass flow controller - for maintaining constant sampleflow (Unit Instruments)

6.5 Chromatographic grade stainless ateel tubing and stainless steelplumbing fittings.

6.6 Chromatographic column - 011-624 0.53 ID, 30 meter length (JfiiWScientific).

6.7 Stainless steel vacuum/presfire gauge capable of measuring from 30"of mercury (Hg) to 40 psig. (Span Instruments)

6.8 High precision vacuum gauge - for making daily standards. (Wallace &Tiernan Pennwalt)

6.9 Pressure regulators for carrier gaa and standards - 2 stage,stainless steel diagram.

6.10 SUMMA passivated canisters 6 L (Scientific InstrumentationSpecialists)

6.11 7 micron filters (Nupro), or equivalent.

7. Reagents and Standards

7.1 4-bromofluorobenzene, 50 ng/mL in methanol (for tuning of massspectrometer).

7.2 High purity helium for carrier gas.

7.3 Standards at a nominal concentration of 1 ppmv (CSa is not as stableand so the concentration is 5 ppmv). Standards are prepared in abalance gas of nitrogen and are analytically certified by thesupplier (Scott-Marrin and £cott Specialty). To facilitatecertification by vendor, the standards were divided into 5 cylinders.(See Tables 2-7.)

7.4 Internal standard mix of bromochloromethane, 1,4-difluorobenzene,and chlorobenzene-d5 at 1000 ug/ml each in methanol (Supelco).(See Table 6.)


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SOP NO:CRL-LM-7001


TABLE 4. Standard Cylinder No. CC72063

Component Concentration (v/v)

Vinyl Chloride1,1-Dichloroethene1,1-Dichloroethane2-Butanonecia-1,2-DichloroetheneBenzene4-Methyl-2-pentanone1,1,2-TrichloroethaneToluene2-HexanoneChlorobenzenem-Xyleneo-Xylene1,2-DichlorobenzeneAcetone1,4-Dichlorobenzene _Nitrogen Balance

1.1.1.1.1.1.1.1.1.1.1.1.1.1.0.1.

00080602070709060818OS1112259904

+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0+ 0

.05

.05

.05

.05

.05

.05

.05

.05

.05

.05

.05

.05

.05

.05

.05

.05

ppmppmppmppmppmppmppmppmppmppmppmpprappmppmppmppm

TABLE 5. Standard Cylinder No. CC12390


Freon-12Freon-114Freon-11Freon-113n-Hexane1,2-Dibromoethane4-Ethyltoluene1,3,5-TrimethyIbenzene1,2,4-TrimethylbenzeneNitrogen

015 + 0.05 ppm95 + 0.05 ppm

0.05 ppm0.05 ppm0.05 ppm0.05 ppm0.05 ppm0.05 ppm

00.940.991.020.99O.B90.95 _0.92 0.05 ppmBalance

TABLE 6. Internal Standard Liquid Mix

Component Concentration (ug/ml)

Bromochloromethane1,4-DifluorobenzeneChlorobenzene-d5

100010001000


———— Page 6 of _22_The Determination of Volatile OrganioB (VOCa)


SOP NO:CRL-LM-7001

Revision No.: 2.0

FIGURE 1. Nutech 3523 Flow Diagram

Effective Date:March 1, 1990

INJ. PORT I

TRAP CONCENTRATOR

LOAD

TRAP PURG

w/ VDST ANALYZER FLOW DIAGRAM (FRIINT VIEV)


Page 7The Determination Ci Volatile Organica (VOCe)

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SOP NO:CRL-LM-7001


TABLE 2. Cylinder No. CC72069

Component

ChloromethaneBromomethaneChloroethaneDichloromethanetrana-1,2-DichloroethyleneTrichloroethane1,2-Dichloroethane1,1,1-TrichloroethaneTetrnch.l nrnmoth'*»no1,2-Dichloropropanecie-1, 3-Dichloropropsr.etrans-1,3-dichloropirOp.iineDibromochloromethaneTetrachloroethyleneEthylbenzenep-XyleneStyrenc1,1,2,2-TetrachloroethaneBromodichloromethaneTrichloroetheneAcetonitrileNitrogen

Concentration (v/v)

0.981.000.961.081.081.071.100.991.011.081.031.201.131.141.201.201.251.241.080.821.00Balan

t- 0.05 ppm• 0.05 ppm• 0.05 ppm

0.05 ppm0.05 ppm0.05 ppm

r 0.05 ppm[ 0.05 ppm: 0.05 ppm•0.05 ppm

0.05 ppm: 0.06 ppm; 0.05 ppm" 0.05 ppm; 0.06 ppm• 0.06 ppm' 0.06 ppm

0.06 ppm• 0.05 ppm" 0.05 ppm

0.05 ppma

TABLE 3. Standard Cylinder No. CO72058


Carbon DisulfideNitrogen

4.86 + 0.1 ppmBalance


Page 9 ofThe Determination of Volatile OrganlcB (VOCfl)

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SOP NO: Revision No. : 2.0 Effective Date:CRL-LM-7001 March 1, 1990

TABLE 7. Standard Cylinder No. ALM 002636


Benzyl chloride 0.737 ppra1.3-Dichlorobenzene 0.768 ppm1.4-Dioxane O.B9S ppmHexachloro-1,3-butadiene 0.804 ppmBromoform 0.84 ppm1,2,4-Trichlorobenzene 0.898 ppmVinyl acetate 0.838 ppmNitrogen

8. Procedure

8.1 Sample Preparation

8.1.1 The pressure of the sample canister is checked and recorded byattaching a vacuum/pressure gauge to the top valve of thecanister (the gauge should be rinsed for few seconds with HCfree air by physically holding against the air outlet andflushing). The canister valve is opened briefly and thepressure is recorded. If the pressure IB less than 10 psig,pressurize the canister to 10 psig with HC free air.

8.1.2 If the canister pressure is increased, a dilution factor (DF)is calculated and recorded.

DFX.

Where: X« c absolute canister pressure absolute before dilution

Y« = absolute caniuter pressure absolute after dilution

8.2 Daily GC/MS Tuning

8.2.1 At the beginning of each day or prior to a calibration, theGC/MS system must be tuned to verify that acceptableperformance criteria are achieved. If any of the key ionsfail the abundance criteria listed in Table 8, the system mustbe retuned using 4-Bromofluorobenzene (BFB).


PageThe Determination of Volatile Organlca (VOCa)


22

SOP NO:CRL-LM-7001


8.2.2 For daily tuning, thei relaya on the Nutech controller(see Figure 1) should be in the right hand position, withthe cryo trap at 150°C (alternatively valves 2 and 6 couldbe placed in the left, hand position with the auxiliary Heflow set at 10 ml/min or greater). The GC program iainitiated by using the Datac command in file manager (FMGR).The GC program ia named "GCQFB1." This downloads theprogram from the data system to the GC. Once the oven haastabilized, the remote start light will turn on and thesystem ia ready for injection.

1 uL of a SO ng/uL, 4-bromofluorobenzene (BFB) standard iainjected into injection port 2 of the Nutech 8533 and theremote start button is activated.

TABLE 8. 4-Bromofluorobenzene Key Ions and Ion Abundance Criteria

Maaa Ion Abundance Criteria

SO759596

173174175176177

15 to 40% of mass 9530 to 60% of mass 95Base Peak, 100% Relative Abundance5 to 9% of mass 95<2% o:? mass 174>50% of mass 965 to 9% of mass 174>95% but <101% of mass 1745 to 9% of mass 176

8.2. 3 Once the tuning run ia complete (~ 8 minutes)t review a scanclose to the center of the BFB peak. If it looks cloee topassing, type in the command TRF, TUNVOA, data file. Thiswill start a program that will find a scan that will pass thetuning and print out the required information automatically.If the BFB tuning criteria cannot be met on 2-3 injections,retuning the instrument with PFTBA may be required.


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SOP NO:CRL-LM-7001

Revision No.: 2.0 Effective Date;March 1, 1990

TABLE 9. BFI) Tuning Method

Enter the name of the method file: GCBFB1

M E T H O D F I L E L I S T

Method file: CCBFB1

Temperature: Inj.P90.0

GC/DIP

Temp 1Time 1RateTemp 2Time 2

30.01.0

35.0100.0

15.0

GC type: 5890Column: Cap

r.ntfc250.0

LEVEL A

100.015.00.00.00.0

Oven equilibration Time .10 min

Run time: 6.00Scan Start time: 2.50Splitleee valve time: .80

Relay II:Relay 12:Triac »0:Triac »1:

ON

327.0327.0327.0327.0

0.00.00.00.00.0

OFF

327.0327.0327.0327.0

Run type: SCAN, GC, ElSplltlesa: Yes

Source0.0

0.00.0

ON

327.0327.0327.0327.0

OFF

327.0327.0327.0327.0

Scan Parameters: Mass Range 35 to 260Multiplier voltage: 2244 Number of A/D samples: 8CC Peak threshold: 20000 countsThreshold: 100 counts


PageThe Determination of Volatile Organica (VOCo)


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SOP NO:CRL-LM-7001


TABLE 10. Analytical Method

Enter the name of the method file: GCTO14

Method file: GCT014

M E T H O D F I L E L I S T

GC type: 5890Column: Cap

Temperature: Inj .P90.0

GC/DIP

Temp 1Time 1RateTemp 2Time 2

-SO.O2.0

70.0-20.0

0.0

Intfc::so.o

Oven equilibration Time

Run time: 32.10Scan start time: .10Splitleaa valve time: 0.00

LEVEL A

-20.00.05.0

127.020.0

.10 min

Relay 111Relay 12:Triac lOiTriac II:

ON

327.0327.0327.0327.0

127.020.00.00.00.0

OFF

327.0327.0327.0327.0

Run type: SCAN, GC, ElSplitleaai Yes

Source0.0

POST RUN

0.00.0

ON

327.0327.0327.0327.O

OF?

327.0327.0327.0327.0

Scan Parameters: Masa Range 35 to 260Multiplier voltage: 2244 Number of A/D samples: aGC Peak threehold: 20000 countsThreshold: 10 counta

8.3 Calibration

B.3.1 A atatic dilution of the stock standard gaa mixtures is madein a 6 liter canister. The high preciaion vacuum gauge iaflushed with HC free air and attached to the top valve of aclean, evacuated canister. After recording the absolutepressure/ 2 psi of each of the 5 standard mixtures ia added tothe caniater (each regulator and the tranafer line muat be


PageTho Determination of Volatile Organic* (VOCa)


SOP NO: Revision No.: 2.0 Effective Date;CRL-LM-7001 March 1, 1990

fluahed several times before transfer of standard to thecanister). Close the canister valves and replace the highprecision gauge with a vacuum/pressure gauge. Pressurize thecan with UC free air to 30 peig. This will yield a standardwith a nominal concentration of 44 ppbv for moat compounds(see Table 11) .

8.3.2 An initial 5 point curve is run in the linear workingrange of the system. The nominal concentration of the5 standards will ba 18 ppbv, 67 ppbv, 90 ppbv, 224 ppbvand 287 ppbv.

8.3.3 On a daily basis, a one point midrange standard (500 ml of44 ppbv) is run to verify the $ point curve. 90% of the fCtarget compounds must be within 30% of the B point curve, ^or a new c point muet. be run. The daily, one point checkstandard is used to calculate the concentration of thesamples.

8.3.4 After the calibration rune and the QA/QC sample runs, an HCfree air blank is run. This must be < the MDL for each targetcompound.

8.4 Analysis

8.4.1 The daily check standard and the QA/QC samples are analyzedthe same as samples. The HC free air blank is a system blankand differs only in that it is not transferred to a canister,but run directly from the cylinder regulator to the sampleinlet system,

8.4.2 The sample canister is connected to the sample inlet system.The Nutech controller should have valves 2 and 6 in the lefthand position, while valves 1 and 3-5 should be in the righthand position. The auxiliary He flow should be set at 40 ml/minute. The canister valve is opened and the pressurizedsample is allowed to flow through the mass flow controller(set at 50 ml/min) and out the vent line.

8.4.3 The cryogenic trap ie cooled to its lower set point of -170° C.When the cryo trap reaches -170° C, the Nutech valve |2 isswitched to the right hand position and a timer Is started.After 10 minutes (500 mL) valve 12 is switched back to theleft hand position. Thus 500 ml of blank, standard or sampleia concentrated on the cryo trap.


Page 14 of _ 22_The Determination of Volatile Organics (VOCs)

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SOP NO: " ~~ Revision No. : 2.0 Effective Date:CRL-LM-7001 March 1, 1990

Q.4.4 The valve on the sample canieter is closed and the remaining linepressure is allowed to drop to ambient. The 3-way valve is thenswitched to the internal standard canister and the I.S. canistervalve is opened and allowed to flush for at least 2 minutes. (Theinternal standard is made by injecting 20 ul of the liquid mix intoan evacuated canister and pressurizing to 30 psi(44.6 psia) . Valveis then switched to the right hand position and a timer is started.After 2 minutes, Valve 2 is switched back to the left hand positionThus 100 ml of 200 ppbv nominal Internal standard mix is injected othe cryotrap with each blank, standard or sample.

8.4.5 The GC is cooled to its' initial set point of -50*C by usingDatac in file manager. The name of the GC program is"GCTO14." This takes about 2.5 minutes. During this timevalves 2 and 6 remain in the left hand position, allowing Heto sweep the trap and remove most oxygen, nitrogen and otherpermanent gases .

8.4.6 When the GC has reached eguilibrtum the red remote start lightwill turn on. Switch valve 16 to the right hand position.Wait at least 10 seconds to allow flow through the trap toequilibrate. The blue "cool" button on the Nutech controllerand remote start button should be pressed simultaneously.This will heat the cryo trap to 150° C and start the GCprogram.

9 . Data Interpretation

9.1 ' Qualitative Analyses

9.1.1 those listed in Table 1} is identified

.should be obtained on the user's GC/MS within the same12 hours as the sample analysis. These standard reference

same GC relative retention time (RRT) as those of tnestandard component; and (2) correspondence of the samplecomponent and the standard component mass spectrum.


~" Page IS of _22The Determination of Volatile Organios (VOCa)

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SOP NO: Revision No.: 2.0 Eff&ctive Date:CRL-LM-7001 March 1, 1990

9.1.1.1 The sample component RRT must compare within+ 0.06 nm? units of the RRT of the standardcomponent. For reference, the standard must berun within the same 12 hours as the sample. Ifcoelution of interfering components prohibitsaccurate assignment of the sample component RRTfrom the total ion chromatogram, the RRT shouldbe assigned by using extracted ion currentprofiles for ione unique to the component ofinterest.

9.1.1.2 (1) All Ions present in the standard massspectra at a relative intensity greater than10% (most abundant ion in the spectrum equals100%) mutit be present in the sample spectrum.(2) The relative intensities of ionsspecifiod in (1) must agree within plus orminus 20% between the standard and samplespectra. (Example: For an ion with anabundance of 50% in the standard spectra,the correspondin sample abundance must bemust be between 30 and 70 percent.

9.1.2 For samples containing components not associated withthe calibration standards, a library search may bemade for the purpose of tentative identification. Thenecessity to perform this type of identification willbe determined by the type of analyses being conducted.Guidelines for making tentative identification are:

(1) Relative intensities of major ions in the referencespectrum (ions >10% of the most abundant ion) should bepresent in the sample spectrum.

(2) The relative intensities of the major ions shouldagree within + 20%. (Example: For an ion with anabundance of 50%.in the standard spectrum, thecorresponding sample ion abundance must be between 30and 70%) .

(3) Molecular ions present in the reference spectrumshould be present in the sample spectrum.


Page 16 of _22_The Determination of Volatile Organics (VOCa)

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SOP NO: Revision No.: 2.0 Effective DateiCRL-LM-7001 March 1, 1990

(4 ) Ions present in the sample spectrum but not inthe reference apectrum should be reviewed for possiblebackground contamination or presence of coelutingcompounds .

{ 5 ) lona present in the reference spectrum but not inthe sample spectrum f.hould be reviewed for possible

Computer generated library search routines should notuse normalization routines that would misrepresent thelibrary or unknown spectra when compared to each other.Only after visual comparison of sample with the nearestlibrary searches will the mass spectral interpretationspecialist assign a tentative Identification.

9.2 Quantitative Analysis:

When a compound has been identified, the quantification ofthat compound will be based on the integrated abundance fromthe EICP of the primary charateristic ion. Quantificationwill take place uaing the internal standard technique.


PageThe Determination or Volatile Organica (VOCe)



10. QA/QC Requirements

10.1 The mass spectrometer must meet the tuning criteria described inSection 8.2.

10.3 A laboratory control sample (LCS) must be analyzed after the checkstandard. This sample will consist of the target VOCs prepared in aseparate canister at a concentration that differs from that of thecheck standard. Five compounds will be used to assess control forthe LCS: methylene chloride, 1,1-dichloroethene, trichloroethene,toluene and 1,1,2,2-tetrachloroethane. The percent recovery for thefive control compounds must be within a window of 80-115%.

10.4 For each lot of 20 samples analyzed, a duplicate control sample (DCS)muat be analyzed after the LCS. The DCS sample is identical to theLCS in composition and so-arce. The 80-115% recovery criterion mustbe met. In addition, the r€:lative percent difference (RPD) for theLCS and DCS must be < 20%.

10.5 A system blank of HC free air must be analyzed after the LCS or DCS.The blank results must indicate that there are no target compoundspresent above the MDL.

10.6 if any of the above criteria are not met, corrective actions must beimplemented before analyses can proceed.

11. Calculations

11.1 The HP data system automatically quantitates the sample results basedon a 500 mL sample size. The results are in ppbv. If the canisterwas pressurized before analysis, the results must be multiplied bythe dilution factor DF (see Section 8.1.2).

11.2 If a sample aize other than 500 mL was used, the result must beadjusted as shown below:

reeult ppbv x flamPle volume i

500 mL


Page 18 of _22Tha Determination of Volatile Organics (VOCB) ~

in Ambient Air >/ GC/M3 - Scan Mode


12. Reporting

12.1 Reporting units are ppbv. If results are to be reported in ng/Luae the following equation:

result ppbv x »°lecular weight of compound _ ng/L

21.5

Note: 24.5 is the standard volume of ideal gas at 25 degreesCentigrade and 1 atm.

12.2 Reporting limitsSee Table 12

12.3 Significant figures12.3.1 All results should be reported to two significant figures.12.3.2 Only report results below detection limit as ND(DL).

12.4 No conversion of the analytical results to the standardconditions is made.

13. References

13.1 Method Source

"EPA Compendium Method TO-14. The Determination of Volatile OrganicCompounds (VOCa) in Ambient Air using SUMMA Paaaivated CanisterSampling and Gaa Chromatographic Analysis."

13.2 Deviations from Method

13.2.1 Dry HC free air is used for the daily blank and fordilution purposes.

13.2.2 TO-14 recommends the uae of a .32 mm column coupled directlyto the MSD. with the HP system, the MSD can only handle flowof 1 mL/min or lees. The .32 mm column provides ~ 3 mL/min.Enseco uaes a .53 mm column through a jet separator.

13.2.3 TO-14 describes an inlet system that uaes a vacuum to pull aslip stream sample through the trap. Enseco uses the pressureof the sample canister to drive the sample through the trap.

SOP

The Determination of Volatilein Ambient Air by GC/H3

STANDAJIDOPERATINGPROCEDURE

Page 19 of _ 22_OrganicB (VOCa)

- Scan Mode

NO: Revision No.: 2.0 Effective Date:CRL-LM-7001

2)3)4)

5)6)7)8)9)

10)11)

12)14)15)16)17)18)19)20)21)22)23)24)25)26)27)28)29)30)31)32)33)34)35)36)37)38)39)40)41)

TABLE 11. Concentration of Daily

Compound

Dichlorodif luoromethane (Freon 12)chlorome thanel,2-Dichloro-l,l,2,2-

tetrafluoroethane (Freon 114)Vinyl chlorideBromoethaneChloroethaneTrichlorof luoromethane (11)cis-1, 2-DichloroetheneCarbon dleulflde1,1,2-Trichloro- 1,2,2-

trif luoroethane (Freon 113)AcetoneMethylene chloridetrana-1, 2-DichloroetheneHexane1 , 1-DichloroethaneVinyl Acetate1, 1-Dichloroethene2-ButanoneChloroform1, 1, 1-TrichloroethaneCarbon tetrachlorideBenzene1 , 2-DichloroethaneTrichloroethene1,2-Dichloropropane1,4-DioxaneBromodichloromethanecie-1, 3-Dichloropropene4-Methy 1-2 -pent anoneToluenetrans-1, 3-Dichloropropene1,1,2-TrichloroethaneTetrachloroethene2-HexanoneDibromochloromethane1 , 2-DibromoethaneChlorobenzeneEthylbenzene1,4-and l,3-(p,m) Xylene

March 1, 1990

Check Standard

Concentration(ppbv)

45.4243.84

42.5044.7444.7442.9642.0647.88

217.44

44.3044.3048.3248.3245.6447.4237.5048.3245.6447.8244.3045.2047.8249.2236.6848.3240.0448.3246.0848.7648.3253.7053.7051.0052.8050.5644.3048.3253.70

103.36


Page 20 of _22_The Determination of Volatile Organica (VOCe)

in Ambient Air by OC/MS - Scan Mode-

SOP NO: Revision No.: 2.0 Effective DatetCRL-LH-7001 March 1, 1990

TABLE 11. Concentration of Daily Check Standard

ConcentrationCompound (ppbv)

42) l,2-(ortho) Xylene 50.1243) Styrene 55.9244) Bromoform 37.5845) 1,1,2,2-Tetrachloroethane 55.4846) Benzyl chloride 32.9847) 4-Ethyltoluene 39.8248) 1,3,5-Trimethylbenzena 42.5049) 1,2,4-Trimethylbenzene 41.1650) 1,3-Dichlorobenzene 34.3651) 1,4-Dichlorobenzene 46.5452) 1,2-Dichlorobenzene 55.9253) 1,2,4-Trichlorobenzene 40.1854) Hexachlorobutadiene 35.98

The Determinat J.on ofin Ambient Air

SOP NO:CRL-LM-7001

Table 12

Compound

2) Dlchlororiif luoromethane (Freon 13) chloromethane1) 1,2-Dicliloro-l, 1,2,2-

tetraf luoroethiino {Freon 11*1)5) Vinyl chloride6) Bromoethane7) Chloroethane0) Trlchlorot'luoromethane (H)9} cia-1 , 2-Dichloroechene

10) Carbon diaulfide11) 1,1,2-Trichloro- 1,2,2-

trif luoroethano (Freon 113)12) Acetone11) Hethylene chloride15) trana-1 , 2-Dichloroethene16) Hexane17) 1, 1-Dichloroethane10) Vinyl Acetate19) 1, 1-Dichloroethene20) 2— Dutanone21) Chloroform22) 1,1,1-Trlchloroethane23) Carbon tetrachloride21) Benzene25) 1, 2-Dichloroethane26) Trichloroethene27) 1, 2-Dichloropropane20) 1,4-Dloxane29) Bromodichloromethane30) cia-1, 3-Dichloropropene31) 1-Hethyl-2-pentanone32) Toluene33) trana-1, 3-Dichloropropene34) 1,1,2-Trichloroethane35) Tetrachloroethene36) 2-llexanone37) Dibromochloromethane38) 1,2-Dibromoethane39) Chlorobenzena40) Ethylbenzena41) 1,4-and l,3-(p,m) Xyleno


Paga 21 of 22Volatile Organica (VOCa) . ~

by OC/H3 - floan Moda

Reviaion No.: 2.0 Effective Date:March 1, 1990

. VOC Reporting Limits

Reporting Limita(ppbv)

2) 2.02.5

2.02.53.05.01.02.0

10

2.0104.04.00.02.52.52.03.O2.O2.02.03.02.02.SU.O7.02.03.03. .63.03.03.03.05.03.02.02.52.55.0


PageThe Determination of Volatile Organica (VOCa)

in Ambient Air by QC/H3 - Scan Mode


Table 12. VOC Reporting Llmita

Reporting LimitsCompound (Ppbv)

42) l,2-(ortho) Xylane 2.043) Styrene 7.044) Dromoform 2.045) 1,1,2,2-TetrachloroetIiano 4.046) Benzyl chloride 2.047) 4-Etliyltoluene 4.048) 1,3, 5-Trimethylbenzene 2.549) 1,2,4-Trimathylbenzene 3.050) 1,3-Dichlorobenzeno 3.051) 1,4-Dlchlorobenzena 4.052) 1,2-Dichlorobenzene 5.053) 1,2,4-Trlchlorobenzena 7.054) llexachlorobutadlene 5.0

• ^ Enseco —i

Enseco - Air Toxics Laboratory9537 Telslar Avenue, Suite 118 • El Monte, CA 91731

(818) 442-8400 • FAX: (818) 442-3758

Preventive Maintenance on Hewlett Packard 5890Gas Chromatograph with HP 5970B mass selectivedetector and Nutech 8533 cryogenic trap concentrator.

This system is used in Enseco SOP No. CRL-LM-7001for the analysis of VOC's in air (EPA Method TO-14).

Preventive Maintenance Schedule

Inspect/change injector septa every weekCheck column head pressure at 30°c every weekClean source on MSD every 3 months

HP preventive maintenance - HP service every 6 monthstechnician changes oil in rough pumpsand checks turbo pump. Runs checkson MSD (eg. autotune)

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