Survey and Origins of Metals in the Humber River

The pollution of river systems by heavy metals has attracted a lot of attention because
unlike organic pollutants, natural processes of decomposition do not remove heavy
metals and are a serious ecological problem1,2,4. They are persistent in the environment
for prolonged periods4. Metals are introduced into the aquatic system as a result of
weathering of soil/rocks and from a variety of human activities involving mining, use of
metals directly and use substances containing metal contaminants such as cement1. Trace
metals entering natural water become part of the water sediment system and their
distribution processes are controlled by a dynamic set of physicalchemical interactions
and equilibria1. Many metals such as Fe, Pb and Cd were found to have anthropogenic
origin such as from industrial activities, municipal sewage, domestic wastes, traffic
sources and atmospheric depositions also contributed to them2. Water samples were taken
from the Humber River in Toronto to determine the origin the metals in the water as
being either anthropogenic or natural.
The Humber River is in the Great Lakes-St Lawrence Lowlands physiographic region of
Canada and empties in Lake Ontario. This landscape is flat to rolling and limestone
(calcium carbonate) sedimentary rocks are found just below the surface3. This fact
accounts for the large concentration of Ca found in the Humber River (107 ug/mL).
Although calcium carbonate is insoluble, a small amount of if dissolves when water
passes over it and the average calcium ion concentration in North America is
approximately 5.3 10 4 M 9, but the Humber River shows a concentration which is
2.7 10 3 M -- almost five times more than a pristine river. The main reason for this
elevated calcium ion concentration is anthropogenic de-icing of roads during winter using
calcium chloride salt. As the river is near downtown Toronto where there is a large
amount of construction, the calcium concentrations could also come from the
cement/concrete being used as well.
The sodium ion concentration for the Humber River (73.21 ug/mL) is almost as large as
the calcium ion concentration. This high sodium level in a sweet-water river is an
anomaly. Once again the major source is this is the de-icing salt sodium chloride. In the
metropolitan area of Toronto alone, an annual average of 100,000 tonnes of de-icing salts
are used to maintain bare pavement conditions during winter months11. The majority of
de-icing salts are transported by highway runoff into roadside soils and adjacent streams.
This results in elevated concentrations of sodium and chloride in the Humber and Don
Rivers especially throughout the spring runoff season and summer months11. Many major
roads run along the sampled sites of the Humber River and it is expected this measured
value will be elevated from the current 73.21 ug/mL if measured during April instead of
October when these measurements were done. Studies have revealed that approximately
55% of de-icing salts applied to roadways is retained within drainage basins11.
Furthermore the clay-rich soils underlying the wetlands inhibit the flushing of the system
resulting in the prolonged retention of sodium ions11. When sediment samples of the
Humber River were taken, it was shown that very little sodium exists in it; (the sediment
samples that were taken were approximately 0.1 g, the then digested to a volume of 30
mL) the upsteam (site 2) showed sodium concentration of 0.43 ug/mL and the sediment

sample in from the storm strain was 3.51 ug/mL. This proves that Na and Ca samples are
not from the surrounding soils, but are anthropogenic. Even through metals such as, Na,
K and Ca do not possess any danger to the environment even at high
concentrations -- K in the presence of phosphorus and nitrogen may enhance
eutrophication of water bodies8 such as Lake Ontario.
The average measured concentration of aluminium ion in the Humber River was 0.17
ug/mL. Since the concentration of aluminium in water is greatly dependant on the pH of
the river7, in an industrial region of North America where the waters of Ontario have
being acidified from acid rain. This has mobilized aluminium from the soil to the aquatic
environment12. In an urban area where water is tapped to households and businesses the
water purification process also contributes to the high aluminium concentration in urban
areas. The use of alum coagulants for water purification causes aluminium concentration
to be higher in finished waters (a lot ends up in city streams) than in raw pristine waters12.
Metals are used for domestic and industrial purposes and thus dispersed in to biosphere4.
There can be significant temporal and spatial variability in water concentrations of heavy
metal contaminants which sometimes leads to problems in obtaining representative
samples5. For example during summer where temperatures are higher, high water
evaporation leads to elevated concentration in water6. Sediments, on the other hand,
integrate contaminants over time and are the ultimate sink of contaminants in the aquatic
system8.
Sediment is the loose sand, clay, silt and other soil particles that is deposited at the
bottom of body of water or accumulated at other depositional sites. Sediments can
emanate from the erosion of bedrocks and soil or from the decomposition of plants and
animals8. Toronto being in a cold environment with ample green vegetation means that
plant matter is not decomposed as rapidly and a lot of it ends up in the rivers such as the
Humber. The water samples were taken during the Fall when trees shed their leaves thus
the river had new clean sedimentation which could possibly underestimate heavy metal
concentrations. Furthermore this problem can be further amplified because these floating
particulates (leaves) adsorb heavy metals on their surface. This heavy metal does not get
measured either in the water or sediment samples. If the sediment analysis were taken
during the winter it is expected that the sediments will show a larger concentration of
heavy metals. When the suspended material settles out during the winter, the toxic
material forms a sink or reservoir9.
Chromium (0.05 ug/mL) was detected in the sediment which is most likely from
Torontos historical fur/leather processing5. In the upsteam sample (site 2) iron
concentrations were 42.58 ug/mL and 193.05 ug/mL in the storm drain sediment. The
high concentrations of Fe found in the sediments may be mainly result from the
anthropological deposits from the construction industry, where Fe is one of the chemicals
used for drilling operations for building tall buildings (piling)10. Pb (0.06 (site 2), 0.19
(storm drain)) values in the sediments consistently higher than Cd (0.01, 0.01) may be
explained by the fact that Cd in sediment is associated with the carbonate fraction and Cd
will be mobilized from sediment to water8. Pb on the other hand showed in the sediment,

but not in the water sample is because of the historical usage of the gasoline additive
tetramethyl lead (Pb(CH4)) as an engine anti knocking agent9. The high concentrations
of the studied elements may be attributed to the effect of intrusion of water borne Fe,
Mg, Cu, Zn, Pb and Cd coming from agricultural, domestic and industrial effluents,
and the small grain size of the sediment facilitates the adsorption of these metals to
bottom sediments8.
Works Cited:
[1] Jain C. Metal fractionation study on bed sediments of River Yamuna, India. Water
Research 2004; 38: 569-578.
[2] Manoj K. Study of Heavy Metal Contamination of the River Water through Index
Analysis Approach and Environmetrics. Bulletin of Environment, Pharmacology and Life
Sciences 2012; 1: 7-15.
[3] Bone R. The Regional Geography of Canada. Oxford, 2014.
[4] Ghorade I. ASSESSMENT OF HEAVY METAL CONTENT IN GODAVARI
RIVERWATER. International Journal of Research in Applied, Natural and Social
Sciences 2014; 2: 23-36.
[5] Binning K. Survey of heavy metals in the sediments of the Swartkops River Estuary,
Port Elizabeth South Africa. Water SA 2001; 27: 461-466.
[6] Reza R. Heavy metal contamination and its indexing approach for river water. Int. J.
Environ. Sci. Tech. 2010; 7: 785-792.
[7] Begum A. Analysis of Heavy metals in Water, Sediments and Fish samples of
Madivala Lakes of Bangalore, Karnataka. International Journal of ChemTech Research
2009; 1: 245-249.
[8] Akpan I. Assessment of heavy metal contamination of sediments along the
cross river channel in Cross River state, Nigeria. IOSR Journal of Environmental Science,
Toxicology And Food Technology 2013; 2: 20-28.
[9] Baird C. Environmental Chemistry. W.W. Freeman and Company, 2012.
[10] El Bouraie M. Heavy metal concentrations in surface river water and bed sediments
at Nile Delta in Egypt. Suoseura Finnish Peatland Society 2010; 61: 1-12.
[11] Sadowski E. The impacts of chloride concentrations on wetlands and amphibian
distribution in the Toronto region. Prairie Perspectives 1999; 1: 144-162.
[12] Miller R. The Occurrence of Aluminum in Drinking Water. Journal of American
Water Works Association 1984; 76: 84-91.

Appendix:
Table 1: Average metal concentrations in Humber River water
Metal
Al
Ba
Ca
K
Mg
Se
Si
Fe
Na

Concentration (ug/mL)
0.17
0.10
107.71
9.47
22.18
0.04
4.51
0.08
73.21

Table 2: Metal concentrations in upstream (site 2) and storm drain (site 7) sediment
Average soil sample 0.1 g, digested to approximately 30 mL
Metal
Al
Ba
Ca
Cl
Co
Cr
Cu
Fe
Mg
Mn
Na
Ni
Pb
Si
Ti
V
Zn

Site 2 (ug/mL)
12.03
0.21
220.27
0.01
0.02
0.05
0.08
42.58
28.71
1.69
0.43
0.04
0.06
3.04
0.35
0.02
0.31

Site 2 (ug/mg)
3.61
0.06
66.08
0.002
0.006
0.04
0.02
12.77
8.61
0.51
0.13
0.01
0.02
0.91
0.10
0.01
0.09

Site 7 (ug/mL)
73.68
0.80
670.46
0.01
0.09
0.18
0.39
193.05
100.61
6.02
3.51
0.19
0.19
10.14
1.37
0.11
1.06

Site 7 (ug/mg)
23.90
0.24
201.44
0.002
0.03
0.05
0.12
57.92
30.18
1.80
1.05
0.06
0.06
3.04
0.41
0.03
0.32