Tyler Armitage

Kyle Baker

Emily Kampman

Kayley Johnson

Averil Parent

Something’s Fishy:

An Exploratory Study Examining Heavy Metals in Nose Creek Fish

April 17th 2009

ENSC 502

For: Cathy Ryan

Please cite this report as: ENSC502, 2009. Something’s Fishy: An Exploratory Study Examining Heavy Metals in Nose Creek Fish. (Final report prepared for ENSC502 course by T. Armitage, K. Baker, E. Kampman, K. Johnson, A. Parent). Accessed from http://wcmprod2.ucalgary.ca/ensc/node/68.

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Table of Contents

Abstract...............................................................................................................................2

Introduction........................................................................................................................2

Methods............................................................................................................................11

Site Description.....................................................................................................11

Sample Collection.................................................................................................13

Lab Procedure.......................................................................................................13

Results ..............................................................................................................................15

Discussion.........................................................................................................................18

References........................................................................................................................26

List of Tables

Table 1. Comparison of heavy metal concentrations from three Nose Creek sites with freshwater aquatic guidelines.......................................................................…...............................8

Table 2. Type of fish and number of individuals found at each site.............................................16

Table 3. Comparing heavy metal concentrations in Nose Creek fish with descriptive measurements collected from previous studies...........................................................................20

Table 4. Comparison of heavy metal concentrations from Nose Creek water (2007) with concentrations from Nose Creek fish...........................................................................................21

Table 5. Comparison of other toxic element concentrations from three Nose Creek sites with freshwater aquatic guidelines......................................................................................................24

List of Figures

Figure 1. Map of Nose Creek sampling locations in Calgary, Alberta...........................................12

Figure 2. Mercury, Lead, and Arsenic wet weight concentrations in fish at three different sites along Nose Creek..........................................................................................................................17

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Abstract:

In polluted aquatic ecosystems the transfer of metals through food chains can be high

enough to bring about harmful concentrations in the tissues of fish. This experiment

investigated the concentration of four toxic heavy metals (cadmium, lead, arsenic and mercury)

in fish tissue from Nose Creek fish. Electrofishing was carried out at four sites in order to collect

the fish. The fish were then freeze dried and ground into a homogeneous powder for analysis

by ICP-MS with the exception of mercury which was analyzed via cold vapor analysis. Arsenic,

lead and mercury were detected, whereas cadmium was below detection limits. Arsenic was

found in the highest concentration and was the most variable between sites. Mercury

concentrations were below Health Canada consumption guidelines but above CCME freshwater

predator guidelines. This was a pilot study, and the issue warrants further investigation as there

are no published studies found on metal concentrations in fish in the Calgary area.

Introduction:

The aquatic ecosystem is composed of the biological community (producers, consumers

and decomposers), the physical and chemical (abiotic) components as well as their interactions.

Aquatic ecosystems undergo constant change, however an ecosystem has usually developed

over a long period of time and the organisms have become adapted to their environment

(CCME, 1999). Ecosystems also have the ability to undergo stress and the system becomes

unbalanced by natural factors, which include climatic variations or disease, or by factors due to

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humans (CCME,1999). Any rapid changes can have detrimental effects on the system. Adverse

effects due to human activity, such as the presence of toxic chemicals in industrial effluents,

may affect many components of the aquatic ecosystem. As well, health concerns for humans

arising from chemical pollutants found in the atmosphere and hydrosphere have become of

increased importance. Toxins can be released from the earth where they are stored both

naturally and through anthropogenic processes. We are beginning to realize that the

anthropogenic release of toxins by such processes as mining and the burning of fossil fuels can

affect human health. More specifically, heavy metals such as arsenic, mercury, lead, and

cadmium are some of the most toxic pollutants being released into the atmosphere. In this

study the presence of these heavy metals will be measured in Nose Creek fish located in

Calgary, Alberta, Canada.

Pollutants such as toxic heavy metals are especially dangerous because they cannot be

biodegraded (Vouk and Piver, 1983). This means that the element will stay inside an organism

until it is excreted. The element’s toxicity, however, can change while it is inside an organism

through chemical or biochemical transformations (Vouk and Piver, 1983). Human exposure to

these toxins can be directly from the atmosphere by inhalation and ingestion of airborne

particles; as well, toxins can also be added to water and soil through atmospheric deposition or

through groundwater percolation and thus add to human exposure (Vouk and Piver, 1983).

Finally, toxic heavy metals can be consumed when humans eat animals such as fish that

bioaccumulate the pollutants from the water they swim in.

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Not only are heavy metals detrimental to ecosystems, but total suspended solids is

another indicator for poor water quality due to its harmful effects on aquatic life. Suspended

matter consists of silt, clay, fine particles, or organic and inorganic matter, soluble organic

compounds, plankton and other microscopic organisms. The TSS in Nose Creek is likely

sediment that is eroded from stream or river banks or is scoured off the bottom. Anthropogenic

activities such as road building and construction near the banks of Nose Creek, as well as

stormwater and natural bank erosion, are a probable cause of the TSS levels in the creek. These

effects on the environment can decrease egg-to-fry survival rates in fish and can affect stream

and benthic macroinvertebrate production (CCME, 2007). Effects on trophic interactions at the

primary and secondary level of productivity will indirectly affect fish community structure.

Direct effects include clogging and abrasion of gills, behavioural effects (movement and

migration), blanketing of spawning gravels, and other habitat changes (CCME, 2007).

Many human health problems can occur when exposed to these heavy metals at either

a high concentration or for prolonged periods of time. For example, arsenism is typically due to

exposure to arsenic through drinking water and can cause bladder, lung, and skin cancers

(Zhang and Smith, 2007). Cadmium poisoning can occur when exposed to low doses of

cadmium for long periods of time. Symptoms of cadmium poisoning include chronic bronchitis,

emphysema, and kidney problems (Bhattacharyya and Bartlett, 1980).

The largest source of lead exposure to humans is from lead-based paint dust found in

older homes, as well as from leaded gasoline still being used in the developing world. There are

many health issues related to lead exposure including learning disabilities, kidney damage,

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anaemia, hearing loss, osteoporosis, and behavioural disorders (Heavey, 2008). Mercury is

probably the most infamous metal due to its many studies on fish consumption and its related

effects. Previous mercury poisonings in the 1950s and 1960s in Japan and Iraq occurred when

people consumed fish containing elevated mercury concentrations (Rasmussen et al. 2005).

These epidemics showed that organic mercury is a potent neurotoxin that is harmful to the

nervous system (Rasmussen et al. 2005). These examples of health risks caused by arsenic,

cadmium, lead, and mercury are the reason why we focussed on assessing these heavy metal

concentrations in Nose Creek fish.

Toxicity in fish is a combination of events involving physical, chemical and biological

processes. Chemicals are released into the environment through a number of sources. They can

enter the aquatic systems through effluents, atmospheric deposition, runoff and groundwater

and become distributed throughout the water and the sediments (Di Guilio & Hinton, 2008).

Mercury is of particular concern in aquatic environments and fish because mercury can be

microbially transformed into methylmercury. Methylmercury can magnify 106 fold through the

food web resulting in high total mercury in fish relative to water (Campbell et al, 2003).

Fish accumulate chemicals both by ingestion of contaminated food as well as through

their skin and gills from contaminated water (Di Guilio & Hinton, 2008). Possible food sources

may include algae, invertebrates, and other small fish. The accumulation of many trace

elements increases with the age of the organism. As well, the concentration increases with

trophic level and magnifies according to how far the contaminated food source travels up the

food chain (Junesa & Blanusa, 2003). Because fish are a low trophic level species they are prey

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for many wildlife predators, including humans, who may get the highest doses of these toxic

substances.

Wildlife in aquatic ecosystems is dependent on aquatic biota such as fish, invertebrates,

and plants as a primary source of food (CCME, 1998). These aquatic sources provide the easiest

route of exposure to toxic and persistent substances that accumulate in food webs. A number

of wildlife species such as bald eagles, osprey, many colonial nesting birds, and aquatic

mammals are dependent on aquatic species such as fish as a primary source of food (CCME,

1998). Fish can accumulate certain metals, organometals and other organic substances from

the water, suspended solids, sediment, and the food they consume (Di Giulio & Hinton, 2008).

These substances persist in aquatic biota because of the slow rates at which they are

metabolized and excreted (CCME, 1998). As a consequence, eating the contaminated fish

provides the main route of exposure to persistent toxic substances that bioaccumulate in

aquatic based wildlife species.

Methyl-mercury (MeHg) is also of special concern not only because of its toxicity, but

because of its tendency to biomagnify in upper trophic levels of aquatic food webs (CCME,

2003). Methyl-mercury passes easily through the digestive wall and bioconcentrates in tissues,

whereas inorganic mercury is more likely to be excreted (CCME, 2003). Organisms at lower

trophic levels usually contain the lowest proportion of total mercury as MeHg and uptake is

primarily a passive process occurring by adsorption. Diet is the most important route of uptake

of MeHg for organisms higher in the food chain, like piscivorous fish (e.g. walleye, lake trout),

aquatic birds (loons and herons), piscivorous mammals (mink and otters) and marine mammals.

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These animals contain a very high proportion of total mercury as MeHg in muscle tissue (90-

100%) (CCME, 2003).

Agriculture, forestry, resource extraction, recreation and residential areas have

impacted the river valleys and riparian areas along Nose Creek (BRBC, 2005). These activities

have caused nutrients, bacteria, total dissolved solids, metals and pesticides present in the

creek to exceed water quality guidelines. Data collected between 1991 and 2001 for Nose Creek

rated the water quality to be poor (BRBC, 2005). For water quality values obtained in 2007,

mercury and cadmium exceed water quality guidelines and lead is close to the guideline for

freshwater species, which indicates this water may be toxic to aquatic life. Bacterial

concentrations also exceeded recreational guidelines indicating that swimmers could face risks

for skin, eye, or ear irritations if in direct contact with Nose Creek waters (BRBC, 2005).

Table 1 contains 2007 heavy metal water quality data for three sites along Nose Creek.

These sites are close to the sites we used for our own sampling and therefore are fairly accurate

representations of the water quality in our sampling areas. All of the values in this table are for

samples collected by Alberta Environment. The values were in micrograms per liter, or parts per

billion (ppb) for better comparison. Arsenic and lead did not exceed the CCME guidelines. One

hundred percent of the cadmium samples taken exceeded the CCME guideline at all three sites.

The water was found to contain less than 0.05 ppb of mercury at all three sites however all of

the samples taken exceed the CCME guideline. Since the water quality indicates a presence of

heavy metals, two of which (cadmium and mercury) exceed guidelines affecting ecosystems, we

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believe that fish will also contain these metals and may possibly contain even higher

concentrations due to the bioaccumulation process.

Table 1. Comparison of heavy metal concentrations from three Nose Creek sites (2007) with freshwater aquatic guidelines. All values are in parts per billion.

Site Metal1

Number of

Samples Mean Median Standard Deviation Minimum Maximum

CCME Guidelines2

Percent of Samples

Exceeding (%) Nose Creek E. Branch

Arsenic 7 2.7 2.7 1.1 1.3 4 5 none Cadmium 7 0.6 0.5 2.6 0.5 0.9 0.017 100 Lead 7 1.2 1.3 4.7 0.7 0.9 7 none Mercury <0.05 0.05 0 0.05 0.05 0.026 100

Nose Creek Mouth Arsenic 9 1.6 1 1.1 0.5 3.4 5 none Cadmium 9 0.7 0.5 3.8 0.5 1.7 0.017 100 Lead 9 2.3 2 8.2 0.5 3.8 7 none Mercury <0.05 0.05 0 0.05 0.05 0.026 100

Nose Creek West Arsenic 7 1.4 1.5 4.6 0.5 1.6 5 none Cadmium 7 0.006 0.5 1.3 0.5 0.8 0.017 100 Lead 7 0.08 0.6 4.6 0.5 1.6 7 none Mercury <0.05 0.05 0 0.05 0.05 0.026 100

1Metal Concentrations in Nose Creek Water were taken from City of Calgary Water Quality Data (2007) 2Freshwater Aquatic Guidelines were taken from CCME

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The poor water quality of Nose Creek may negatively impact fish. This is important

because fish can accumulate toxicity from the water through bioaccumulation and pass these

toxic elements to higher trophic level species including birds, wildlife and even humans. Fish are

a better indicator for the presence of heavy metals compared to water because substances are

more likely to be detected in the tissues of aquatic organisms or sediments rather than the

water (CCME, 1998). Metal concentrations in the creek can also be temporally variable, which

can make it difficult to assess the overall state of the creek over longer time periods. However,

fish integrate the metal over time, allowing for a less variable measurement of concentrations

in the ecosystem.

Nose Creek is classified as a Class D creek. Class D is described by Alberta Environment

(2001) as having low sensitivity which means there is no timing restriction on activities that may

disrupt the bed or banks of the creek. Fish species are not present in Class D water bodies as

defined under the Code of Practice for Pipelines and Telecommunication Lines Crossing a Water

Body. However, the Fisheries Management Information System (FMIS) database shows

evidence of several species of fish that were studied in Nose Creek (Alberta Sustainable

Resource Development, 2009). Not only were there several species of cyprinidae but also

several sport fish. Sport fish are a higher trophic level of fish, such as brown trout, rainbow

trout and mountain whitefish. It is for this reason the Nose Creek Watershed Water

Management Plan (Nose Creek Watershed Partnership (NCWP), 2007) addresses their concern

that Nose Creek should be classified as Class C instead of Class D. Class C is described as having

moderately sensitive habitat areas that are sensitive enough to be potentially damaged by

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unconfined or unrestricted activities within a water body. Class C is further described as having

broadly distributed habitats that support local fish species populations (Alberta Environment,

2001). The NCWP (2007) states that by changing the Class of Nose and West Nose Creek from

Class D to Class C, timing restrictions and stricter conditions would be placed on an activity

scheduled for the Creek increasing the protection of aquatic health in the watershed.

The fish used in this study were longnose dace and lake chub. These fish species are

both considered to be mid trophic level minnows in the aquatic food chain. Longnose dace and

lake chub are both widespread in Alberta and occur in lakes, rivers, and small creeks. Longnose

dace feed primarily on aquatic insect larvae while lake chub will feed on crustaceans, aquatic

insects, as well as algae (Nelson and Paetz, 1992). Individuals from both species can live up to

five years and have a mobility range of between 0.5 and 1.0 kilometers (Nelson and Paetz,

1992).

Due to the presence of heavy metals in Nose Creek water, it is hypothesized that fish

species in Nose Creek will contain heavy metals. Since fish are at a higher trophic level than

other organisms in the system (such as invertebrates), the metals from the water and

sediments are expected to be passed up to these fish by absorption and prey consumption.

Therefore, this study will use fish as a proxy to indicate water quality. The main objective of this

study is to determine the concentration of arsenic, cadmium, mercury, and lead in Nose Creek

fish. Once known, these values will be compared to heavy metal concentrations found in similar

studies and to values from various guidelines. This will determine whether the fish in Nose

Creek are affected and potentially harmful to humans or wildlife. An inventory of all fish found

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at each of the study sites will also be collected. Lastly, this study will act as a pilot study to

determine whether future projects are necessary to assess and compare heavy metal

concentrations in Nose Creek fish as well as the surrounding area. Our goal is to make people

aware of toxic heavy metals in fish and how fish can pass these persistent chemicals on to

wildlife and even humans.

Methods:

Site Description:

Nose Creek originates near the northern boundary of the municipal district of Rockyview

and the Town of Crossfield, and flows south through the City of Airdrie, joining the Bow River in

the City of Calgary near the Calgary Zoo. The West Nose Creek joins Nose Creek near Deerfoot

Trail (Queen Elizabeth II Highway), directly west of the Calgary International Airport (Nose

Creek Watershed Partnership, 2009). Fish were collected from four sites along Nose Creek

(Figure 1) on November 4th, 2008. The first site visited (N5) was Nose Creek at the mouth

(708887.2 N, 5657355 E), the second site (N4) was at McKnight Blvd off Edmonton Trail

(706377.5 N, 5664796.4 E), the third site (WN2) was West Nose Creek at Beddington Trail

(704906.6 N, 566899.6 E), and the fourth and final site (N3) was at Country Hills Blvd in Harvest

Hills (707436.9 N, 5671174.5 E).

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Figure 1. Map of Nose Creek sampling locations in Calgary, Alberta (modified from Cross, 2001). Sampling occurred at the sites marked with red dots (N5, N4, N3, and WN2). The City of Calgary collected water samples of Nose Creek in 2007 at N5, N3, and WN1.

N5

N4

N3

N2

N1

WN1

WN2

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Sample Collection:

A Fish Research License (FRL) was obtained from the Fish and Wildlife Division of Alberta

Sustainable Resource Development (SRD). All field work was done with the assistance of Brian

Meagher, the Provincial Biologist with Trout Unlimited Canada. All fish collected were

identified, weighed and enumerated. A total of 22 composite fish samples representing 2

species were collected by electrofishing. The electrofishing unit used was a Smith-Root 12-B

with an anode ring, the current type was pulsed direct current, and was set at an amperage of

0.20A. The output voltage was 300V, with a pulse rate of 30.0Hz and pulse duration of 4.0ms.

Species targeted for collection and analysis were longnose dace (Rhinichthys cataractae) and

lake chub (Couesius plumbeus). The 22 fish collected consisted of seventeen longnose dace and

5 lake chub (Table 2). After all of the fish were identified, weighed and measured, those not

being used for the study were released back into the creek. Those being used for the study

were placed in a bottle of 10% formalin to be euthanized. They were then placed into Ziploc

bags and labelled with the date and the sample site location. Upon completion all data

collected under the authority of the FRL were submitted into the Alberta provincial Fisheries

Management Information System (FMIS) database.

Lab Procedure:

The fish were taken out of the labelled Ziploc plastic bags and weighed with an

analytical balance and the wet weights were recorded. Fish from site N5 and site N4 were

combined into a single location as the sample size at site N5 was too small to represent its own

sample. The fish were then placed into one of three bags, making up three samples (site N5/N4,

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site WN2 and site N3). Site N5/N4 and site WN2 were composed of longnose dace, whereas site

N3 was composed of lake chub. Once placed into their respective bags, the bags were labelled

with the site in which they were captured and they were then placed in the freezer.

After being frozen, the individual longnose dace samples and the lake chub sample were

placed inside a large container was filled with dry ice (CO2(S)) prior to being dipped into liquid

nitrogen using stainless steel utensils. They were then placed back in their bags and placed into

the container of dry ice to keep frozen during their transfer to the freeze drier. The samples

were freeze dried for a period of 96 hours to ensure they were thoroughly dried.

Once back in the lab, a mortar and pestle were thoroughly sanitized with nitric acid and

rinsed with distilled water. Stainless steel utensils were also washed and rinsed with distilled

water to prevent cross contamination. All utensils and equipment were thoroughly cleaned

between the preparations of each sample. The dried fish were homogenized with a mortar and

pestle and reduced to a powder. Pieces of skin that could not be ground up were removed. The

powder samples from each of the three sites were placed into three sample vials. The three

samples (site N5/N4, site WN2 and site N3) were sent to Midwest Labs Canada Ltd. to be

analyzed using an ICP-MS for lead, cadmium and arsenic. Cold vapor was used to detect

mercury. Sampling methods were similar to those described by Nash and McSheehy (2005).

In this experiment whole, uneviscerated fish were used as this was much more practical

with the small sizes of the fish. Although, other studies, such as those conducted by Has-Schön

et al (2007) and Roméo et al (1999), found that metals were found in higher concentration in

the organs of the fish. Therefore, it can be inferred that the concentrations obtained will be

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lower than if just the organs had been analyzed. Another reason we used whole fish as opposed

to organs was that the consumption guidelines give values for whole uneviscerated fish in wet

weight.

The dry weight metal concentrations received from the analytical lab were converted

into wet weight. Contaminant concentrations calculated on the basis of dry weight are

approximately 3.6 times higher than those calculated on the basis of wet weight (Braunbeck et

al. 1998). The results of our study were converted from dry weight to wet weight by dividing

the dry weight by a factor of 3.6. This standard is used because the percent weight of water in

fish is 72% (Braunbeck et al. 1998).

Results:

The type of fish species and the number of individuals found at each site was recorded

(Table 2). Sites N5 and N3 were the most diverse as they each had six fish species present. Site

N4 had the lowest amount of species diversity as it was home to longnose dace exclusively. By

far the greatest number of individuals was found at site N3.

Of these fish, only longnose dace and lake chub were collected and tested for heavy

metals. Longnose dace was found at sites N5/N4, and WN2. Lake chub were found at site N3.

The average dry weight metal concentrations determined were converted into wet weight

metal concentrations.

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Arsenic, lead, and mercury concentrations were detected in fish tissue (Figure 2). The

concentration of cadmium was below detection limits in all three samples of fish. The metal

found in the highest concentration was arsenic. This metal also had the most variable

concentration among the three sites. Mercury concentrations in the fish were similar at all

three sites. Lead was detected at sites N5/N4 and N3, but below detection limits at site WN2.

Table 2. Type of fish and number of individuals found at each site

Fish Type Site

N5 N4 WN2 N3 Sportfish

Brown Trout 1 0 0 0 Rainbow Trout 4 0 0 0

Mountain Whitefish 2 0 0 2 Non-Sportfish

Lake Chub 0 0 2 76 Fathead Minnow 0 0 0 6 Longnose Dace 4 9 6 0

Brook Stickleback 0 0 1 2 Longnose Sucker 2 0 1 3

White Sucker 2 0 0 10 Total number of

Species 6 1 10 6

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Figure 2. Mercury, Lead, and Arsenic wet weight concentrations in fish at three different sites along Nose Creek. All concentrations are measured in parts per million. Cadmium was below detection limits at all three sites. The Health Canada fish consumption guideline (0.5ppm) for mercury as well as the CCME methylmercury guideline for the protection of freshwater predators (0.033ppm) are shown. Sites N5/N4 as well as site WN2 contain longnose dace. Site N3 contains lake chub.

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Discussion:

In general, the results from this study support the hypothesis. This study shows that

Nose Creek fish accumulate toxic heavy metals from the water. The results of this study can be

compared to the results of studies done in other parts of North America (Table 3). Overall, Nose

Creek fish have lower lead concentrations than those found in previous studies (Schmitt and

Brumbaugh, 1989, and Kidwell et al. 1994). Mercury concentrations in Nose Creek fish are also

found to be lower than those previously recorded (Schmitt and Brumbaugh, 1989, Kidwell et al.

1994, Cai et al. 2007, and Swanson et al. 2003). Nose Creek fish have and a higher arsenic

concentration than those detected in previous studies (Schmitt and Brumbaugh, 1989, Kidwell

et al. 1994, and Williams et al. 2006).

Rainbow trout consumption by humans was tested by Health Canada. The rainbow trout

tested were found to have a mean mercury level of 0.04 ppm and a maximum level of 0.10 ppm

(Health Canada, 2008). Health Canada’s human safety guideline for fish consumption

concerning mercury level is 0.5 ppm (Health Canada, 2007). The level of mercury found in Nose

Creek fish does not exceed this guideline.

From the US Environmental Protection Agency’s (EPA) risk-based consumption limits,

the average mercury concentration in Nose Creek fish falls into the range of 0.078 ppm to 0.12

ppm. Within this range, the EPA suggests that a person should not consume more than eight

0.23 kg meals of fish per month. For arsenic, the average concentration in Nose Creek fish falls

into the range of 0.35 ppm to 0.7 ppm. For this range, a person should not consume more than

four 0.23 kg meals of fish per month. The EPA also suggests restricting meals based on

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cadmium intake if concentrations are above 0.088 ppm (United States EPA, 2009). Since

cadmium was not detected, the fish in Nose Creek fall below that guideline. Nose Creek fish are

not used for human consumption.

The bioaccumulation process is important to understand the connection between a

small trophic level species like the long nose dace and a rainbow trout, a sportfish that could be

consumed by humans or wildlife. In our field work, rainbow trout were found at the mouth

where Nose Creek empties into the Bow River. Rainbow trout consume basically every species

of fish including long nose dace (Braunbeck et al. 1998). Not only are the rainbow trout exposed

to the heavy metals in the water and sediments, but due to bioaccumulation, rainbow trout

receive even higher doses of mercury and the other heavy metals because of their consumption

of long nose dace or other low trophic level species. Since the rainbow trout are free to enter

into the Bow River, they pose a threat to anglers who may consume these contaminated fish.

The Canadian Council of Ministers of the Environment (CCME) has established Canadian

Environmental Quality Guidelines for methylmercury as it is a highly bioaccumulative heavy

metal which produces significant negative health effects in most organisms (CCME, 2000). A

value of 0.033 ppm wet weight for methylmercury was set by the CCME as the guideline for the

protection of freshwater predators. The average total mercury concentration determined in

Nose Creek fish was 0.075 ppm wet weight, and since more than 90% of total mercury in most

fish tissue is methylmercury, our value likely exceeds the guideline (Hall et al. 1997).

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Table 3. Comparing heavy metal concentrations in Nose Creek fish with descriptive measurements collected from previous studies. All average concentrations are in wet weight parts per million.

Sample Type Geographic Location

Trophic Status Parts of Fish Analysed

Mercury Lead Arsenic Author

Bottom feeders and predatory fish

United States Low to medium

Whole fish 0.1 0.11 0.14 Scmittt and Brumbaugh (1989)

Bottom feeders United States and

Great Lakes Low Whole fish 0.08 0.18 0.16 Kidwell et al.

(1994) Various fish United States Medium to

high Whole fish <0.20 Williams et al.

(2006) Pelagic fish Northern Gulf of

Mexico Medium to high

Dorsal muscle tissue

<0.3 Cai et al. (2007)

Various species NW Ontario Lakes Medium to

high Dorsal muscle tissue

0.25-0.75 Swanson et al. (2003)

Longnose dace and lake chub

Nose Creek Calgary

Low Whole fish 0.08 0.05 0.46 Armitage et al. (2009)

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A comparison between Nose Creek heavy metal concentrations in the water and those

found in fish tissue can be seen in Table 4. With the exceptions of cadmium at all sites and lead

at Nose Creek west that had concentrations below detection limits, all of the heavy metal

concentrations found in fish tissue were higher than those found in the water. This conclusion is

in accordance with the bioaccumulation process. Correlations between arsenic, lead, and

mercury in water and fish concentrations are hard to make as no visible patterns are apparent.

It would have been helpful to sample for heavy metal concentrations in the water at the same

time fish sampling took place.

Table 4. Comparison of heavy metal concentrations from Nose Creek water (2007) with concentrations from Nose Creek fish. All values are in parts per million.

Site Metal1 Number of

Samples Mean Standard Deviation

Fish Concentration Mean

Nose Creek E. Branch Arsenic 7 0.0027 0.0011 0.23 Cadmium 7 0.0006 0.0026 0 Lead 7 0.0012 0.0047 0.23 Mercury <0.00005 0 0.1 Nose Creek Mouth Arsenic 9 0.0016 0.0011 0.83 Cadmium 9 0.0007 0.0038 0 Lead 9 0.0023 0.0082 0.09 Mercury <0.00005 0 0.72 Nose Creek West Arsenic 7 0.0014 0.0046 0.31 Cadmium 7 0.000006 0.0013 0 Lead 7 0.00008 0.0046 0 Mercury <0.00005 0 0.05 1Metal Concentrations in Nose Creek Water were taken from City of Calgary Water Quality Data (2007)

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There are many possible sources of heavy metals in the Calgary area. The main natural

sources of arsenic in Canada are weathering and erosion of rocks and soils that contain arsenic.

Nose Creek lies on the Paskapoo Formation which is made of a sandstone-shale complex (Burns

et al. 2005). Sandstones can be cemented together by substances such as hematite which is an

iron-oxide, as well as by other minerals including pyrite, barite, and gypsum, which are all rich

in sulphur compounds (Nelson, 2000). These cements allow for a possible connection as the

source of arsenic in the fish samples as sulphide minerals and iron oxides release arsenic to

groundwater which may then enter surface waters like Nose Creek (Welch et al. 2000).

Anthropogenic sources are also a potential contributor, as fossil fuels such as coal and

petroleum contain significant amounts of arsenic (Korte & Fernando, 1991 and Smedley &

Kinniburgh, 2002).

In conclusion, mercury and lead concentrations in Nose Creek fish are generally lower

than those found in fish across North America. Mercury concentrations are much lower than

most related studies as well as the Health Canada human consumption guidelines. Mercury

values do however exceed the CCME guideline for the protection of wildlife consumers of

aquatic biota. Arsenic concentrations found in Nose Creek fish are high compared to related

studies. EPA guidelines suggest no more than four meals per month for fish with these high

arsenic levels. Cadmium was not detected, and the detection limit for the ICP-MS is lower than

the EPA guidelines. Therefore cadmium does not exceed EPA guidelines for any restricted

consumption.

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No published studies on metal concentrations on fish in the Calgary area were found.

However, there have been studies done on endocrine disruptors of fish in the Bow River

(Jackson et al, 2008). As this study is one of the first of its kind in this area and because of that

there are a few things that must be improved upon in the future in order to get more

information on this topic. It would be useful to have a significant increase in sample sizes.

Measuring only one sample per site does not allow for the calculation of standard error or the

ability to perform statistics. An increase in sample size will also allow for more accurate results

and lower detection limits from the lab. It would be easy to implement this, as enough samples

to do triplicates could just be collected in the same day.

This study was restricted to having a license to study only two species of fish. This does

not allow for a true representation of the Nose Creek fish community. Increasing the number of

species involved in the study would produce a more accurate snapshot of toxic heavy metal

contamination in the creek. It would also allow for a comparison between different species

within the creek.

Another possible future study would be to sample for other harmful elements that have

been found in high concentrations in Nose Creek water (Table 5). These elements have all

exceeded the CCME guidelines for the protection of aquatic life. Selenium is a mineral that in

certain amounts can actually be beneficial to humans. Part of this future study could look at the

effects of selenium on the heavy metal concentrations found in Nose Creek fish. Selenium

appears to protect us from the toxic effects of heavy metals and other substances and helps

counteract the effect of mercury buildup (Perrault, 2007). Selenium binds both inorganic and

24

methylmercury; and mercury selenide is formed and excreted in fecal matter. Selenium also

prevents further cadmium absorption (Haas and Levin, 2006). Aside from the likely antioxidant

influence, the specific mechanism by which selenium affords this protection is not known,

although the effect is confirmed by some research (Haas and Levin, 2006). Although selenium

exceeds the guidelines, it may have a beneficial impact on mercury and cadmium toxicity in

Nose Creek fish.

Table 5. Comparison of other toxic element concentrations from three Nose Creek sites (2007) with freshwater aquatic guidelines. All values are in parts per billion.

Site Metal1 Number of

Samples Mean Median Standard Deviation Minimum Maximum

CCME Guidelines2

Percent of Samples

Exceeding (%) Nose Creek E. Branch Aluminum 7 434 261 324 199 943 100 100 Copper 7 6.8 6.9 1.2 4.5 8.2 6 100 Iron 7 731 558 368 458 1313 300 100 Selenium 7 2.3 2.0 0.4 2.0 2.8 1 100 Silver 7 0.6 0.5 0.2 0.5 1.0 0.1 100 Nose Creek Mouth Aluminum 9 470 310 321 239 1214 100 100 Copper 9 6.7 6.5 1.2 4.8 8.8 6 100 Iron 9 828 649 369 565 1697 300 100 Selenium 9 7.5 7.0 5.5 2.1 19.0 1 100 Silver 9 0.5 0.5 0.1 0.5 0.7 0.1 100 Nose Creek West Aluminum 7 296 300 228 72 769 100 84 Copper 7 4.6 4.5 1.2 3.0 6.9 6 100 Iron 7 657 629 288 322 1257 300 100 Selenium 7 2.9 2.9 0.8 2.0 4.2 1 100 Silver 7 0.6 0.5 0.3 0.5 1.4 0.1 100

1Metal Concentrations in Nose Creek Water were taken from City of Calgary Water Quality Data (2007) 2Freshwater Aquatic Guidelines were taken from CCME

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While this study was limited to measuring heavy metals, tests of other bioaccumulative

toxins would allow for a deeper assessment of the health of the creek. Chemicals such as

pesticides, endocrine disruptors, and dioxins are also becoming huge health issues. There is also

a lack of data on heavy metals in fish in the local water bodies of the Calgary area. It would be

useful to sample fish from nearby water bodies in order to compare with environments similar

to Nose Creek. Comparing metal concentrations in Nose Creek fish to Bow River fish would also

be very interesting. This would allow for the testing of sport fish which prey on the cyprinids

sampled in this study. This would be more relevant to compare with human consumption of

fish guidelines.

26

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