Soil method performance asbestos eia annapolis 2011 09 16

Ed Cahill

National Director Asbestos Lab Services

[email protected]

EMSL Analytical, Inc.

200 Route 130 North, Cinnaminson, NJ 08108

856-303-2565 www.emsl.com

Asbestos in Soil

Soil is a Great Hiding Place

1% Unconsolidated Chrysotile

1% Consolidated Chrysotile

3

Copyright 2011 EMSL Analytical, Inc.

Soil is a Great Hiding Place for Asbestos

1% asbestos

4


Asbestos

Contamination

Sources of Asbestos in Soil

Natural Occurrences

of Asbestos (NOA) Copyright 2011 EMSL Analytical, Inc.

5

Asbestos Contamination


6

7


8


9


Natural Occurrences of Asbestos (NOA)


10

Staten Island Serpentinite


I 278 road cut. Up to 50% Chrysotile

Picture and info: Brooklyn CUNY.edu

Why is Soil so Hard to Analyze?


12

Why is Soil so Hard to Analyze?

Non-Homogeneity

Grain size


13

Scales of Non-Homogeneity

The Big Picture

Obtaining representative samples in the field can be difficult.

Samples tend to be very non-homogeneous especially over the large areas that are typical on outdoor sites.

How many samples for a baseball field or 100 miles of road or rail bed?


14

Scales on Non-Homogeneity

The Medium

Picture

How deep to go?

What layers to

include?


15


The Fine Picture

Obtaining a

representative sub-

sample in the lab is

important.


16


The presence of even sand sized quartz crystals are a problem.

The Very Fine Picture

stereoscopic view of play sand


17

In Summary

Soil is a problem matrix for field and lab personnel alike.

Careful sampling plans are needed to reduce inconsistencies, and help to carefully define …… “What is the sample?”

The Analytical method used needs to address potential non homogeneity and grain size


18

Analytical Choices What Method to Choose?


19

Limitations of “Standard” PLM

EPA PLM Method (EPA/600/R-93/116) Method for the Determination of Asbestos in Bulk Building Materials

• As the title suggests and the method explains, this is a method for relatively homogenous bulk building materials, not soil.

• The final version of this method is quite flexible though and matrix modification prior to analysis is described


20

Sieving Milling


Two Approaches to Soil

Scenario 1 - Contamination of Soil with ACM

The Main Sieve Methods Available


Some of the sieving Methods available

• EPA Region 1 Screening Protocol

“Protocol for Screening Soil and Sediment Samples for Asbestos Content” used by the EPA Region 1 Lab

- low tech screening method, semi-quantitative at best.

- been around since 1994, revised ’97 and ’99

- stereoscopic (20X mag) estimate of % Asbestos

• ASTM Sieve Method for Soil

Best option yet for sieving protocol for soil, yet to be published


The soil is sub-sampled (only particles < 16mm) Wet sieved through a 60 mesh (250 micron) sieve Only the >250 micron fraction is analyzed Stereoscope (20-40X) used to quantify, and PLM

used to identify Note: This is a screening method. Qualitative or Semi-Quantitative at best

EPA Region 1 Screening Protocol

Scenario 1 - Contamination of Soil with ACM

EPA Region 1 Protocol

Sample Size 250 cc or less

Sieve Stack

• 19 mm (3/4”)

• 2 mm

• 106 micron

DRAFT ASTM Sieve Method


24

Anything larger than 19 mm is not considered part of the sample

1) Sample is dried

2) Weighed

3) Dry Sieved (wet sieving is optional) on sieve shaker for 5 minutes

ASTM Sieve Method


25

ASTM Sieve Method

Coarse and Medium Fractions still too large for straight PLM

4) Weigh each fraction 5) Analyze each fraction


26

This is a common type of sample (mini clods))

ASTM Sieve Method

The fine fraction is

fine enough and

homogenous enough

for a PLM slide prep

and analysis


27

Wet or Dry? 28


Pros • Washes the suspect

ACM making for easier detection

• Breaks down matrix to its smallest components

Wet Sieving Can Be Better for Some Soils

29


Cons • More labor intensive • More time (drying) • Even more time and possible

fiber loss as fine fraction needs to be sedimented

• Water disposal an issue

“Typical” soil sample

on sieve stack

DRY Sieving on an Automatic sieve shaker

30


Comparison of Dry vs. Wet Sieving

Coarse, Medium and Fine Fractions 31


soil clods fail to make it through the 2mm sieve

Sieve Stack Coarse, Medium

32


Wet Sieving of Same Sample

The Same Sample ! 33


Coarse 86%

Medium 12%

Fine 1%

Dry Sieving

Coarse 34%

Medium 26%

Fine 40%

Wet Sieving

Dry vs. Wet Sieving 34


0.00

10.00

20.00

30.00

40.00

50.00

60.00

70.00

80.00

90.00

100.00

>2mm >106µm <106µm

DRY WET

HAND PICKING SUSPECT ACM

OUT OF COARSE AND MEDIUM FRACTIONS.

35


Visual and Stereomicroscopic Analysis

ASTM Analysis 36


THE ASBESTOS % FOR EACH TYPE OF ACM IS DETERMINED. THE PERCENT ASBESTOS IS EXTRAPOLATED TO THAT FRACTION, AND THEN TO THE ENTIRE SAMPLE.

37


If all three fractions are non detect by PLM then a

TEM analysis is performed.

Optional drop mount Qualitative only (detect/non

detect). This enable us to find asbestos that is not

visible by light microscopy

If drop mount is positive then

grav reduction followed by

Quantitative TEM analysis

Structures/µg

ASTM Sieve Method


38

TEM Quantitative Analysis

100 to 250 mg of the material from the fine fraction is gravimetrically reduced via muffle furnace and acid treatment.

Filtered onto a 0.2µm PC or 0.22µm MCE filter

TEM examination using a direct method consistent with Test Method D6281.

Results reported in Structures per microgram

Is that a useful number?

39


Sieving Milling


Two Approaches to Soil


The MILLING Approach

Disk pulverizer/plate grinder Cross Beater Mill Freezer mill Ball mill, etc.…….

Determination of Asbestos Content of Serpentine Aggregate

This is the current de facto standard for milling methods.

1. One pint (473cc) sample

2. milled to 200 mesh (74 microns)

3. PLM

CA Air Resources Board (CARB) Method 435


42

Milled to reduce the nominal particle size to 75 microns

The sample is dried in a drying oven and material >3/8” is removed by sieving

CARB 435 Method


43

CARB 435 After milling, the sample is analyzed by a PLM 400 or 1000 point count (0.25% or 0.1%)



Analyzed by TEM at 20,000X

TEM CARB Method

How Do They Compare?


46

Study Design

Test the performance of three common

methods for asbestos analysis of soil.

• Soil spiked at 0.1% and 1% by weight • Analysis by

1. “standard” EPA 600 R-93/116 2. ASTM Sieve Method 3. CARB Method 435


47

Phase I

Spiking with Unconsolidated Asbestos

Two chrysotile sources were used

1. The majority was chrysotile asbestos (Plastibest-20) from the Jeffrey mine in Canada. It was left over from an old ingestion study performed by NIEHS. Thanks Jim Millette!

2. Chrysotile from Salt River Canyon in Arizona (just south of Chrysotile, Arizona).


48

Phase 1

Unconsolidated Asbestos

Phase 2

Consolidated (ACM) Asbestos

49


The Big Plan

Asbestos Characterization


50



51

Fiber Size Data for Data Plastibest-20 – 100 fibers by TEM at 20K Mag

Fiber Length (microns)

0

2

4

6

8

10

12

14

16

18

Approx. 20% of fibers are optically visible (> 0.2 microns in width)



52

0

5

10

15

20

25

30

Fiber Size Data for Arizona Chrysotile – 100 fibers by TEM at 20K Mag

Fiber Length (microns)

Approx. 13% of fibers are optically visible (> 0.2 microns in width)

Spiking


53

• Seven Blanks

• Seven samples at 0.1%

• Seven samples at 1%

ASTM Sieve Method EPA 600 CARB Method 435

To eliminate the variability of possible non-homogeneity, no

sub-sampling was performed. 63 individual samples were

prepared.

Phase 1 Samples


54

Analyst Credentials 55


Samples submitted blindly to 6 separate

analysts at separate locations including

external labs.

• minimum 10 years experience PLM

• 2 have over 30 years exp.

• 2 attended McCrone PLM course

• 2 have BS Geology

• 1 MS Analytical mineralogy

56


Phase 1 EPA 600 Method Results

EPA 600 Results for Blanks Phase I


57

Analyst 1 Analyst 2 Analyst 3 Analyst 4 Analyst 5 Analyst 6

Sample Number

Asbestos % Actual Result

% Recovery Result

% Recovery Result

% Recovery Result

% Recovery Result

% Recovery Result

% Recovery

EPA 600 2 0.00 0 NA 0 NA 0 NA 0 NA 0 NA 0 NA

EPA 600 3 0.00 0 NA 0 NA 0 NA 0 NA trace NA 0 NA



EPA 600 16 0.00 0 NA 0 NA 0 NA 0 NA trace NA 0 NA

EPA 600 17 0.00 trace NA 0 NA 0 NA 0 NA 0 NA 0 NA


0

1

2

3

4

5

6

7

8

1 2 3 4 5 6 7Sample

Perc

ent

Asb

est

os


58

Each color represents an analyst

Overall Percent Recovery: 2063 % Overall (pooled) RSD: 0.51

EPA 600 Results at 0.1% Phase I

Sample

Perc

ent

Asb

est

os


59

0

5

10

15

20

25

30

1 2 3 4 5 6 7

Overall Percent Recovery: 835 % Overall (Pooled) RSD: 0.56

EPA 600 Results at 1% Phase I

EPA 600 Summary Phase I

60


Overall (Pooled) Percent Recovery : 1574 %

Overall (Pooled) RSD : 0.54

ASTM Sieve Method Results


61

ASTM Results for Blanks Phase I


62

Analyst 1 Analyst 2 Analyst3 Analyst 4 Analyst 5 Analyst 6

Sample Number


% Recovery Result

% Recovery Result

% Recovery Result

% Recovery Result

% Recovery Result

% Recovery

ASTM 02 0.00 0.0 NA 0.0 NA 0.0 NA 0.0 NA 0.0 NA 0.0 NA







63


TEM Drop

Mount

Analyst 1

PLM Results TEM Results

Label # Analyst 1 True % Drop Mount Detect/Non

Detect

ASTM 02 0.00 0.0 ND

ASTM 05 0.50 0.0 ND

ASTM 09 0.00 0.0 ND

ASTM 14 0.00 0.0 ND

ASTM 15 0.00 0.0 ND

ASTM 16 0.00 0.0 ND

ASTM 18 0.00 0.0 ND

ASTM 01 2.46 0.1 Detect














Sample

Perc

ent

Asb

est

os


64

0.00

0.50

1.00

1.50

2.00

2.50

3.00

3.50

4.00

4.50

1 2 3 4 5 6 7

Overall Percent Recovery : 1432 % Overall (Pooled) RSD : 0.39

ASTM Results at 0.1% Phase I

Sample

Perc

ent

Asb

est

os


65

0.0

2.0

4.0

6.0

8.0

10.0

12.0

14.0

16.0

1 2 3 4 5 6 7

Overall Percent Recovery : 569 % Overall (Pooled) RSD : 0.23

ASTM Results at 1% Phase I

Summary of ASTM Results - Phase I

66


Overall (Pooled) Percent Recovery: 1090 %

Overall (Pooled) RSD: 0.32

ASTM Round Robin Results Soil spiked with 0.2% Asbestos

Lab A Lab B Lab C Lab D Mean

% asbestos in

>2mm fraction *

0.5 0.75 0.72 2.0 0.99

% asbestos in 2mm

– 100um fraction *

2.0 2.5 0.87 3.7 2.3

% asbestos in

<100um fraction *

0.5 0.5 0 0.25 0.31

Total percent

asbestos *

1.7 2.15 0.73 3.1 1.9

% asbestos by

point-count

0.5 0.5 0.25 0.25 0.375

Drop mount

estimate

Trace <0.1 1% Trace <1%

Structures per

microgram

5,700 520 15,000 7,700 7,200

950% recovery


67

CARB Method 435 Results


68

CARB 435 Results on Blanks Phase I


69


Sample Number


% Recovery Result

% Recovery Result

% Recovery Result

% Recovery Result

% Recovery Result

% Recovery

CARB 3 0.00 0 NA 0 NA 0 NA 0 NA 0 NA 0 NA








70

Sample 0

0.5

1

1.5

2

2.5

3

3.5

4

1 2 3 4 5 6 7

Overall Percent Recovery: 787 % Excluding False Negatives Overall (Pooled) RSD: 0.73

CARB 435 Results at 0.1% Phase I


71

Per

cen

t A

sbes

tos

Sample

0

2

4

6

8

10

12

14

16

18

1 2 3 4 5 6 7

Overall Percent Recovery: 475 % excluding false negatives Overall (Pooled) RSD: 0.52

CARB 435 Results at 1% Phase I

CARB 435 Performance Phase I

72




0

500

1000

1500

2000

2500

EPA ASTM CARB Target

0.1% Spiked Sample 1% Spiked sample

Excluding false negatives

73


Method Performance Phase I Accuracy

Perc

ent

Reco

very

Perc

ent

Reco

very

0

100

200

300

400

500

600

700

800

900

EPA ASTM CARB Target

0.1% Spiked Sample 1% Spiked sample

Relative Standard Deviation

74


Method Performance Phase I Precision

Relative Standard Deviation

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

EPA ASTM CARB

0

1

2

3

4

5

6

7

EPA ASTM CARB

Score Card Phase I Pooled Data for the Round

EPA600 ASTM Sieve CARB 435 %

Recovery 1540 1090 650

RSD 0.55 0.32 0.64


75

False Negatives for CARB 435 are a concern

Phase II


Everything up to this point has compared how the methods perform at detecting and quantifying unconsolidated milled asbestos in soil Now let’s see what happens when we spike with ACM.

Phase II

Spiking with Consolidated Asbestos (ACM)

- Transite supplied by RTI

- Estimated Chrysotile percentage = 14%


77

78


Phase II EPA 600 Method Results

EPA 600 - Blanks - Phase II


Sample Number


% Recovery Result

% Recovery Result

% Recovery Result

% Recovery Result

% Recovery Result

% Recovery


EPA 600 8 0.00 0 NA 0.5 NA 0 NA 0 NA 0 NA 0 NA

EPA 600 9 0.00 0.5 NA 0 NA 0 NA 0 NA 0 NA 0 NA




EPA 600 21 0.00 0 NA 0 NA 0.5 NA 0 NA 0 NA 0.5 NA

79


EPA 600 - 0.1% - Phase II 80


0

0.5

1

1.5

2

2.5

3

3.5

1 2 3 4 5 6 7

Overall Percent Recovery : 726 % Overall (Pooled) RSD: 0.43

EPA 600 - 1% - Phase II 81


0

2

4

6

8

10

1 2 3 4 5 6 7

Overall Percent Recovery for this Sample: 214 %

Overall (Pooled) RSD for this Sample: 0.32

EPA 600 Summary Phase II

82


Overall (Pooled) Percent Recovery 535 %

Overall (Pooled) RSD : 0.38

Phase II ASTM Sieve Method Results


83

ASTM – Blanks - Phase II 84



Sample Number


% Recovery Result

% Recovery Result

% Recovery Result

% Recovery Result

% Recovery Result

% Recovery








ASTM - 0.1% - Phase II 85


0.00

0.50

1.00

1.50

2.00

2.50

3.00

3.50

4.00

1 2 3 4 5 6 7

Overall Percent Recovery: 519 % Overall (Pooled) RSD for this Sample: 0.6

ASTM - 1% - Phase II 86


0.00

1.00

2.00

3.00

4.00

5.00

6.00

7.00

8.00

9.00

10.00

1 2 3 4 5 6 7

Overall Percent Recovery : 188 %


ASTM Summary Phase II

87



Overall (pooled) RSD: 0.5

Phase II CARB Method 435 Results


88

Phase II - CARB - Blanks 89



Sample Number


% Recovery Result

% Recovery Result

% Recovery Result

% Recovery Result

% Recovery Result

% Recovery




CARB 11 0.00 0 NA 0.125 NA 0 NA 0 NA 0 NA 0 NA




Phase II - CARB - 0.1% 90


0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1 2 3 4 5 6 7

Overall Percent Recovery for this Sample: 218 %

Overall (Pooled) RSD for this Sample: 0.65

Phase II – CARB - 1% 91


0

0.5

1

1.5

2

2.5

3

1 2 3 4 5 6 7

Overall Percent Recovery : 91 % Overall (Pooled) RSD: 0.46

Phase II CARB Summary

92


Overall (Pooled) Percent Recovery : 167 %


Final Score Card 93


EPA600 ASTM Sieve CARB 435

% Recovery 1540 1090 650 RSD 0.55 0.32 0.64

EPA600 ASTM Sieve CARB 435

% Recovery 535 391 167

RSD 0.38 0.5 .57

Phase I

Phase II

Summing Up

• Well known

• fast / cost effective

• pretty good at finding the

asbestos

Straight EPA 600 Pros Cons

94


• Gross over estimation,

esp. at low percentages

• Since method not

designed for this matrix

not legally defensible?

Summing Up

• Once published it will be

defensible (“fit for use”)

• Allows for a forensic analysis as

it does not alter the asbestos or

ACM as it exists in the sample

• TEM follow up on NAD

circumvents to some extent the

0.25 micron width limitation

ASTM Sieve Method Pros Cons

95


• Most time consuming

• potential cross

contamination due to sieves

(difficult to clean)

• cost

•Course and medium fraction

still not amenable to PLM

Summing Up

• Homogenizes the entire sample

prior to analysis.

• Reduces grain size of entire sample

• Less labor intensive than sieving

• Potentially better quantification

• mentioned in the EPA framework

document

• options for better DL 0.25 , 0.1 or even

lower

• Milled sample is also amenable to

TEM

CARB 435 Pros Cons

96


• Potential to create fibers (cleavage

fragments with large aspect ratios)

from non asbestiform minerals.

• Alters fiber sizes dimensions

97


• CARB 435 mentioned

• 1% is not an appropriate action level for asbestos in soil

Thanks!

• Jim Millette of MVA

• Owen Crankshaw and Todd Ennis at RTI

• Alan Segrave and BV

• Howard Varner and EHS

98


Real World Test Drive of the Methods

99


CharlesTown Timeline

Early 1900s:Constructed by gun manufacturer Savage Arms Corporation, which continued to use the site through World Wars I and II.

1950s: Sperry Univac makes the complex the center of its manufacturing operations in the Mohawk Valley. Employment peaks in the thousands, then gradually declines.

1977: Charles A. Gaetano buys the property and announces plans for a factory-outlet complex, which becomes a reality and is successful for several years until it declines in the late 1980s.

1991: The CharlesTown Factory Outlet Center officially becomes the CharlesTown Business Complex, with only three retail stores remaining.

2007: Property is purchased by local developer Michael Cancilla, who plans to work with two Massachusetts developers to obtain grant money and redevelop the site into a mix of residential and retail.

2010: Lack of grant money and environmental problems have stalled the site, and the EPA is preparing to clean up and demolish dilapidated buildings.

100


Savage Arms 101


102


Charlestown Mall

Photo Taken by NY DOL on First Walk Through of Site

103


104


Charlestown Mall

105


Utica NY

Charlestown Mall

106


Charlestown Mall

107


Perimeter Air Samples 108


Controlled Demo 109


School Across the Street 110


111


Non-Scientific Study

4 grab samples collected from various areas

No careful sampling pan :o(

Unlike the formal study these samples need to be riffle split (remember non homogeneity issue) into 3 separate sub-samples for

EPA 600

CARB 435

ASTM Sieve Method

112


Riffle Splitting

One way to

help

homogenize

the samples

either in the

field or after

submittal to

the lab


Charlestown Nuggets 114


Conclusions? 115


0

1

2

3

4

5

6

1CN 1GV 2CN 2GV 3CN 3GV 4CN 4GV

EPA 600

CARB 435

ASTM Sieve

All conclusions need to be taken with a grain (block?) of salt. Remember that each sample was split into 3 sub-samples. Each sample is therefore a unique sample unto itself.

• CARB seemed to miss asbestos at low percentages

• Generally good agreement between EPA 600 and ASTM


Another Approach Fiber Releasability

• Determining the percentage of asbestos in

soil is useful for knowing that there is a

potential for exposure.

• But it does not give us a clue as to what the

risk actually is.

• 1% is not an acceptable action level to use

for asbestos in soil


Fiber Releasability Risk Assessment

• If we can determine the amount of

respirable asbestos fibers that are

released from a soil upon agitation

then we have an insight into risk

• The EPA is all about minimizing risk to

the population.

Risk Assessment Methods

The Elutriator Method


The Elutriator Method Superfund EPA 540-R-97-028 With this method a soil sample is gravimetrically tracked through sieving into course and fine fractions The fine fraction is then tumbled in a closed chamber and any respirable dust generated is collected on air cassettes Analysis is performed by ISO 10312 counting rules This method is peer reviewed and (arguably) acceptable for risk assessment studies


Tumbler

apparatus

filled with

soil




Tumbler inside enclosed humidity chamber




Isokinetic sampling at

top of elutriator stack to

catch only the

respirable fraction of

fibers released from

the soil.

ISO 10312 Analysis

Results in structures/g




Field Alternatives to the Elutriator

The EPA uses other techniques in the field

that also collect and measure releasable

fibers from soil.

• Activity Based air Sampling (ABS)

• Releasable Asbestos Field (RAF) Unit

• Fluidized Bed Asbestos Segregator(FBAS)


Activity Based Air Sampling

Personnel (and sometimes area) monitoring

is performed while samplers mimic likely

activity for that location.

Activity Based Air Sampling

RAF Unit


Fluidized Bed


Air is injected at a precise flow rate to get the soil sample behaving like a fluid.

Then air samples are collected from above.

Fluidized Bed


Summing Up


“I see building material debris in the soil. Does it have asbestos and if so how much? Do I need to dispose of it as hazardous waste?”

ASTM Sieving Method

“I don’t necessarily see suspect asbestos but I think it might be there either from contamination (ex brake shops) or from NOA.”

PLM CARB 435 (down to 0.25% or 0.1%)

TEM CARB 435 (EPA 600 Mass Analysis)

ASTM Sieving Method with TEM

Does the Soil Contain Respirable / Releasable Fibers?

EPA 540-R-97-028 Superfund Method (Elutriator)

Activity based air sampling

RAFS / FBAS

The answer depends on the question…

Soil method performance asbestos eia annapolis 2011 09 16

Documents

Transcript of Soil method performance asbestos eia annapolis 2011 09 16