CHM1410 Metal Report

8/10/2019 CHM1410 Metal Report

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IntroductionBackground/Hypothesis

The Humber River is located in Southern Ontario and it flows through the Greater Toronto Area

(GTA), heavily urbanized part of Canada. The river receives organic and inorganic contaminantsform the urban watershed. This study aims at determining the water quality of the Humber River by analyzing metals and polycyclic aromatic hydrocarbons (PAHs) in surface water, sedimentand plant samples.

PAHs are organic compounds containing multiple aromatic rings and they are present in naturalaquatic system as a result of combustion by-product from anthropogenic sources. PAHs areknown to have environmental and human health impact. EPA listed 16 PAHs as priority

pollutants and 7 of them exhibit carcinogenic effects. PAHs were extracted using solid phaseextraction (SPE) disks and analyzed using GC-MS.

The heavy metals presence in the water can have adverse impact on aquatic species and overall

water quality. The metals accumulate in water as a result of natural process such as disintegrationof soils, and rocks and man-made sources in form of waste from metal processing, chemical andother industries (Warnick et. al). A wide suite of heavy metals were analyzed for this studyincluding but not limited to Na, K, Ca, Mg, Cu, Al, Pb, Zn using an inductively coupled plasmawith atomic emission spectrometer (ICP-AES).

Heavy metals can affect human health through consumption of bio-accumulated fishes, directexposure during recreational activity and accidental ingestion of untreated water. Differentaquatic species and plants can uptake heavy metals and reflect the overall quality of the riverwater. Thus, bioaccumulation pattern in different plants can serve as a promising monitoring

parameter for water quality control.

The objective of this study were as follows:1. To determine the concentration gradient for metals, and PAHs in the Humber River surface

water and sediment samples with possible identification of their sources.2. To understand bioaccumulation pattern in different plants species along the Humber River.3. To assess overall water quality of the Humber River for recreational purpose.

It was hypothesized that the concentration of metals and PAHs would be higher near point 7 and8 which receives water from storm drains near Gardiner Expressway as compared to upstream ofthe river.

Results & Discussion

Surface water, sediment and plant samples along with appropriate QA/QC samples werecollected from 8 different locations along the stretch between the Old Mill Station and theGardiner Expressway. 5 Sample locations (1, 2, 4, 7, and 8) were the stream conditions and thegradient analysis for done these location to obtain a better picture while sample locations 3, 5,and 6 were marshy conditions, which are used for comparative studies.


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Metal Surface Water

22 metals were analyzed in water samples and 9 metals showed significant concentration in thewater. Location 7 had the maximum concentration of all the metals due to presence of stormdrains and this validated our hypothesis. The concentration of location 7 was used forcomparative analysis as it is very unlikely that the concentration in river will exceed this value.Ca (175 mg/L), Mg (30.5 mg/L), showed high concentration and impart hardness to the water. K(40.9 mg/L) and Na were also present in high quantity but Na cannot be quantified due tosaturation of the GC column. Table in appendix presents the concentration of different tracemetals present in the water along with the Canadian guidelines. The concentration of Se (50

ppb), and Ba (1 30 ppb), common elements in the earths crust, exceeded the guideline Lead (Pb)was not detected in the sample which is due to elimination of lead as anti-knock agent ingasoline over last two decades. The concentration of cadmium (8.54 ppb) also exceeded itsguideline of 0.5 ppb. The possible sources for Cd can be due to corrosion of galvanized pipes,waste from metal refineries, battery waste, paints and natural weathering of rocks, sediments. Al(237.65 ppb) was relatively high and can be possibly due to use of alum as coagulant in WWTPswhich is eventually drained out to the river.

The gradient was plotted for metals concentration in water as a function of distance from the OldMill station and the Gardiner expressway. The distance between sampling locations werecomparable and assumed to be same for purpose of this study. The hypothesis of a gradient wasconfirmed with maximum value at location 7 (storm drains) and decreasing on either side of thestorm drains. The gradients are plotted and shown in Figures

Water spikes samples were collected at location 4, 5, and 6 and recovery % was calculated and isshown in Table . . Ca, Mg, Na showed abnormal recovery value as spiking concentrationwas less than the sample concentration. The concentration of the spiking solution is usually 50-100 times higher than the concentration in the samples to facilitate the post-spiking concentrationwithout getting disturbed by the variation in different samples K showed good recovery as weused high spike concentration (100 ppm) as compared to its concentration (5.17 ppm). All otherrecovery value were observed to be between 80-130%. The high recovery value can be due toerrors in preparing of spiked concentration from stock solution. The extraction blank values werededucted from the observed concentration to account for contamination.


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Table

Metal Average Spikeconcentration (g/mL)

Average Concentration(4, 5 and 6) (g/mL)

%Recovery

Al 10.04 0.16 110.64As 10.03 ND 124.83Ba 10 0.09 134.86Be 10.03 0.01 101.38Ca 10 96.77 -842.32Cd 10.11 0.00 152.77Co 9.98 0.00 129.12Cr 10.12 0.00 127.58Cu 10.1 0.00 120.28Fe 10.06 0.11 125.20

K 100.5 5.17 116.12Mg 10.09 21.36 -87.46Mn 10.05 0.00 144.09 Na 10.08 72.50 -613.61 Ni 10.03 0.00 130.85Pb 10.07 ND 128.64Sb 10.02 0.00 128.31Se 10.03 0.04 136.99Si 5.01 4.02 50.70Ti 9.93 0.00 135.97

V 9.99 ND 126.63Zn 10.06 0.00 129.53


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Table

Metal Concentration (Location 7) CWQG/PWQG GuidelinesAl 237.65 5-100

Cd 8.542203 0.5Co 8.996397 5Cu 2.836167 2-4Fe 17.8645 300Pb 0 1-7 Ni 2.786925 20-150Zn 3.810087 20-30Se 50 10Ba 130 11Be 7.724275 NA

Cr 1.598045 8.9Mn 19.15729 NATi 5.214938 NA

Appendix


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Fig 1:

Fig 2

0.00

0.05

0.10

0.15

0.20

0.25

0.30

1 2 3 4 5 6 7 8

Al

BaFe

Se

-5.00

15.00

35.00

55.00

75.00

95.00

115.00

135.00155.00

175.00

1 2 3 4 5 6 7 8

Ca

K

Mg

Si

0

5

10

15

20

25

C o n c

( p p

b )

Trace Metals-Location 7


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Metal Sediments

0.00

20.00

40.00

60.00

80.00

100.00

120.00

140.00

160.00

180.00

200.00

Ca 317.933 K 766.490 Mg 285.213 Si 251.611

c o n c

( p p m

)

Other Metals-Location 7

0.00

50.00

100.00

150.00

200.00

250.00

Al 396.153 Ba 233.527 Se 196.026

C o n c .

( p p

b )

Metals Location 7


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Table :

Metals Site 1(g/g)

Site 2(g/g)

Site 3(g/g)

Site 4(g/g)

Site 5(g/g)

Site 6(g/g)

Site 7(g/g)

Site 8(g/g)

Al 10.12 117.81 80.50 176.92 196.53 162.87 442.69 343.79

Ba 0.15 2.04 1.08 2.29 2.39 2.09 4.46 3.48

Ca 78.16 2157.36 929.70 2160.89 2016.75 2293.50 3724.80 3690.20

Co 0.02 0.19 0.10 0.21 0.22 0.21 0.52 0.35

Cr 0.07 0.45 0.24 0.48 1.08 0.68 0.98 0.90

Cu 0.06 0.77 0.43 1.04 1.11 1.10 2.19 2.34

Fe 56.96 417.01 169.72 392.66 412.62 482.91 1072.52 727.59

K 2.32 28.40 14.31 31.27 26.65 33.55 71.82 51.21

Mg 79.68 281.18 127.92 317.31 296.63 309.62 558.95 575.30

Mn 4.59 16.57 9.28 17.61 20.13 17.25 33.46 29.10

Na 1.18 4.18 2.97 23.62 8.03 7.20 19.51 11.73

Ni 0.05 0.38 0.16 0.38 0.37 0.41 1.03 0.68

Pb 0.25 0.60 0.23 0.58 0.59 1.11 1.07 1.15

Si 4.24 29.81 15.32 24.29 30.67 13.08 56.35 14.54

Ti 0.47 3.44 1.84 4.05 3.35 3.50 7.59 5.31

Zn 0.43 3.06 1.36 3.11 3.35 2.95 5.87 5.88


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0

500

1000

1500

2000

2500

3000

3500

4000

1 2 4 7 8

M e t a l C o n c e n t a r t i o n

( u g / g )

Distance from Old Mill Station

Al 396.153

Ca 317.933

Fe 238.204

Mg 285.213

0

1

2

3

4

5

6

7

8

1 2 3 4 5 6 7 8

M e t a l C o n c e n t r a t i o n

( u g / g )


Ba 233.527

Co 228.616

Cr 267.716

Cu 327.393

Ni 231.604

Pb 220.353

Ti 334.940

Zn 206.200

-5

5

15

25

35

45

55

65

75

1 2 3 4 5 6 7 8

M e t a l C o n c e n t r a t i o n

( u g / g )


K 766.490

Mn 257.610

Si 251.611

Na 589.592

CHM1410 Metal Report

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