Introduction

Background/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 contaminants
form 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, sediment
and plant samples.
PAHs are organic compounds containing multiple aromatic rings and they are present in natural
aquatic system as a result of combustion by-product from anthropogenic sources. PAHs are
known 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 phase
extraction (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 disintegration
of soils, and rocks and man-made sources in form of waste from metal processing, chemical and
other industries (Warnick et. al). A wide suite of heavy metals were analyzed for this study
including but not limited to Na, K, Ca, Mg, Cu, Al, Pb, Zn using an inductively coupled plasma
with atomic emission spectrometer (ICP-AES).
Heavy metals can affect human health through consumption of bio-accumulated fishes, direct
exposure during recreational activity and accidental ingestion of untreated water. Different
aquatic species and plants can uptake heavy metals and reflect the overall quality of the river
water. 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 and
8 which receives water from storm drains near Gardiner Expressway as compared to upstream of
the river.
Results & Discussion
Surface water, sediment and plant samples along with appropriate QA/QC samples were
collected from 8 different locations along the stretch between the Old Mill Station and the
Gardiner Expressway. 5 Sample locations (1, 2, 4, 7, and 8) were the stream conditions and the
gradient 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.

Metal Surface Water

22 metals were analyzed in water samples and 9 metals showed significant concentration in the
water. Location 7 had the maximum concentration of all the metals due to presence of storm
drains and this validated our hypothesis. The concentration of location 7 was used for
comparative 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 to
saturation of the GC column. Table in appendix presents the concentration of different trace
metals present in the water along with the Canadian guidelines. The concentration of Se (50
ppb), and Ba (130 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 in
gasoline over last two decades. The concentration of cadmium (8.54 ppb) also exceeded its
guideline 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 WWTPs
which is eventually drained out to the river.
The gradient was plotted for metals concentration in water as a function of distance from the Old
Mill station and the Gardiner expressway. The distance between sampling locations were
comparable and assumed to be same for purpose of this study. The hypothesis of a gradient was
confirmed with maximum value at location 7 (storm drains) and decreasing on either side of the
storm 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 is
shown in Table .. Ca, Mg, Na showed abnormal recovery value as spiking concentration
was less than the sample concentration. The concentration of the spiking solution is usually 50100 times higher than the concentration in the samples to facilitate the post-spiking concentration
without getting disturbed by the variation in different samples K showed good recovery as we
used high spike concentration (100 ppm) as compared to its concentration (5.17 ppm). All other
recovery value were observed to be between 80-130%. The high recovery value can be due to
errors in preparing of spiked concentration from stock solution. The extraction blank values were
deducted from the observed concentration to account for contamination.

Table
Metal

Average Spike
concentration (g/mL)

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

%
Recovery

Al
As
Ba
Be
Ca
Cd
Co
Cr
Cu
Fe
K
Mg
Mn
Na
Ni
Pb
Sb
Se
Si
Ti
V
Zn

10.04
10.03
10
10.03
10
10.11
9.98
10.12
10.1
10.06
100.5
10.09
10.05
10.08
10.03
10.07
10.02
10.03
5.01
9.93
9.99
10.06

0.16
ND
0.09
0.01
96.77
0.00
0.00
0.00
0.00
0.11
5.17
21.36
0.00
72.50
0.00
ND
0.00
0.04
4.02
0.00
ND
0.00

110.64
124.83
134.86
101.38
-842.32
152.77
129.12
127.58
120.28
125.20
116.12
-87.46
144.09
-613.61
130.85
128.64
128.31
136.99
50.70
135.97
126.63
129.53

Table
Metal
Al
Cd
Co
Cu
Fe
Pb
Ni
Zn
Se
Ba
Be
Cr
Mn
Ti

Appendix

Concentration (Location 7)
237.65
8.542203
8.996397
2.836167
17.8645
0
2.786925
3.810087
50
130
7.724275
1.598045
19.15729
5.214938

CWQG/PWQG Guidelines
5-100
0.5
5
2-4
300
1-7
20-150
20-30
10
11
NA
8.9
NA
NA

0.30
0.25
0.20

Al

0.15

Ba
Fe

0.10

Se

0.05
0.00
1

Fig 1:
175.00
155.00
135.00
115.00

Ca

95.00

75.00

Mg

55.00

Si

35.00
15.00
-5.00

Fig 2

Trace Metals-Location 7
Conc (ppb)

25
20
15
10
5
0

conc (ppm)

Other Metals-Location 7
200.00
180.00
160.00
140.00
120.00
100.00
80.00
60.00
40.00
20.00
0.00
Ca 317.933

K 766.490

Mg 285.213

Metals Location 7
250.00

Conc. (ppb)

200.00
150.00
100.00
50.00
0.00
Al 396.153

Metal Sediments

Ba 233.527

Se 196.026

Si 251.611

Table :
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

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

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

Metals

2293.50 3724.80 3690.20

Metal Concentartion (ug/g)

4000
3500
3000
2500

Al 396.153

2000

Ca 317.933

1500

Fe 238.204

1000

Mg 285.213

500
0
1

Distance from Old Mill Station

Metal Concentration (ug/g)

8
7

Ba 233.527

Co 228.616

Cr 267.716

Cu 327.393

Ni 231.604

Pb 220.353

Ti 334.940
Zn 206.200

0
1

Distance from Old Mill Station

75

Metal Concentration (ug/g)

65
55
45

K 766.490
Mn 257.610

35

Si 251.611

25

Na 589.592

15
5
-5 1

Distance from Old Mill Station