Biogeochemical factors influencing net mercury methylation in contaminated freshwater sediments from the St. Lawrence River in Cornwall, Ontario, Canada

The activity of various anaerobic microbes, including sulfate reducers (SRB), iron reducers (FeRP) and methanogens (MPA) has been linked to mercury methylation in aquatic systems, although the relative importance of each microbial group in the overall process is poorly understood in natural sediments. The present study focused on the biogeochemical factors (i.e. the relative importance of various groups of anaerobic microbes (FeRP, SRB, and MPA) that affect net monomethylmercury (MMHg) formation in contaminated sediments of the St. Lawrence River (SRL) near Cornwall (Zone 1), Ontario, Canada. Methylation and demethylation potentials were measured separately by using isotope-enriched mercury species (²⁰⁰Hg²⁺ and MM¹⁹⁹Hg⁺) in sediment microcosms treated with specific microbial inhibitors. Sediments were sampled and incubated in the dark at room temperature in an anaerobic chamber for 96 h. The potential methylation rate constants (K_m) and demethylation rates (K_d) were found to differ significantly between microcosms. The MPA-inhibited microcosm had the highest potential methylation rate constant (0.016 d⁻¹), whereas the two SRB-inhibited microcosms had comparable potential methylation rate constants (0.003 d⁻¹ and 0.002 d⁻¹, respectively). The inhibition of methanogens stimulated net methylation by inhibiting demethylationand by stimulating methylation along with SRB activity. The inhibition of both methanogens and SRB was found to enhance the iron reduction rates but did not completely stop MMHg production. The strong positive correlation between K_m and Sulfate Reduction Rates (SRR) and between K_d and Methane Production Rates (MPR) supports the involvement of SRB in Hg methylation and MPA in MMHg demethylation in the sediments. In contrast, the strong negative correlation between K_d and Iron Reduction Rates (FeRR) shows that the increase in FeRR corresponds to a decrease in demethylation, indicating that iron reduction may influence net methylation in the SLR sediments by decreasing demethylation rather than favouring methylation.     

Gill and head kidney antioxidant processes and innate immune system responses of yellow perch (Perca flavescens) exposed to different contaminants in the St. Lawrence River, Canada

Biomarkers of oxidative stress metabolism and the innate immune response were examined in gill and head kidney tissue of wild-caught yellow perch (Perca flavescens) collected from four sites ranging in type and degree of metal pollution in the St. Lawrence River, Quebec, Canada. Sites were ranked as follows: Île Dorval < Îles aux Sables < Îlet Vert < Beauharnois. Biomarker measurements did not correspond completely to the perceived pollution gradient. Total protein content was highest at a site 4 km downstream of municipal effluents (Îlet Vert) exposed to moderate and high levels of heavy metals and faecal coliforms, respectively. Thiol content was highest at the reference site (Île Dorval) with the lowest contaminant levels. Glutathione-S-transferase (GST) activity was highest in fish from the site furthest downstream that was exposed to moderate metal contamination (Îles aux Sables). Glutathione reductase (GRd) activity was high in both gill and head kidney tissue of fish from the reference site (Île Dorval) and highest in the kidney of fish from the most contaminated site (Beauharnois). Catalase activity was highest in head kidney tissue in fish from this latter site. Ceruloplasmin activity was lowest in head kidney from fish collected at the reference site and highest at Beauharnois. Lysozyme activity was lowest in head kidney tissue from fish at the reference site and highest in tissue from fish at Îlet Vert, downstream of municipal effluents. These results suggest that the direction and magnitude of oxidative stress biomarker response and innate immune function biomarker response vary between tissues and among complex mixtures of contaminants, complicating interpretation of results. Results further suggest that bacterial loading, as measured by faecal coliforms, affects the oxidative stress metabolism and the innate immune response.     

Trophic structure and mercury distribution in a Gulf of St. Lawrence (Canada) food web using stable isotope analysis

Even at low concentrations in the environment, mercury has the potential to biomagnify in food chains and reaches levels of concern in apex predators. The aim of this study was to relate the transfer of total mercury (THg) and methylmercury (MeHg) in a Gulf of St. Lawrence food web to the trophic structure, from primary consumers to seabirds, using stable nitrogen (δ¹⁵N) and carbon (δ¹³C) isotope analysis and physical environmental parameters. The energy reaching upper trophic level species was principally derived from pelagic primary production, with particulate organic matter (POM) at the base of the food chain. We developed a biomagnification factor (BMF) taking into account the various prey items consumed by a given predator using stable isotope mixing models. This BMF provides a more realistic estimation than when using a single prey. Lipid content, body weight, trophic level and benthic connection explained 77.4 and 80.7% of the variation in THg and MeHg concentrations, respectively in this food web. When other values were held constant, relationships with lipid and benthic connection were negative whereas relationships with trophic level and body weight were positive. Total Hg and MeHg biomagnified in this food web with biomagnification power values (slope of the relationship with δ¹⁵N) of 0.170 and 0.235, respectively on wet weight and 0.134 and 0.201, respectively on dry weight. Values of biomagnification power were greater for pelagic and benthopelagic species compared to benthic species whereas the opposite trend was observed for levels at the base of the food chain. This suggests that Hg would be readily bioavailable to organisms at the base of the benthic food chain, but trophic transfer would be more efficient in each trophic level of pelagic and benthopelagic food chains.     

Using visual assessment as a foundation for greenway planning in the St. Lawrence River Valley

The growth of the ‘greenway’ as a fundamental planning concept has provided guidance for many communities locally and around the world. In the St. Lawrence River Valley, the idea is providing a common physical and cultural reference for the management of landscapes in communities along a 100 mile international corridor. Over the past 10 years, the College of Environmental Science and Forestry of the State University of New York has worked with the St. Lawrence-Eastern Ontario Commission to examine the unique visual and scenic resources of the region as the foundation for establishing a greenway tracing the St. Lawrence River. Although the idea of a greenway in the St. Lawrence River Valley is not new or unusual, the inventory and assessment of visual or scenic linear resources as a foundation is a departure from typical practice, and an experiment in defensible and rational planning. As a major summer tourism destination, the region is well aware of the critical value of its scenic resources. In our effort to identify and assess various vital resources for planning, we found an indicator in the visual nature of the landscape—both as a resource in and of itself, and as a reflection of the underlying values held by local communities for natural and cultural resources. This paper describes, as a case study, the process used to identify and assess visual and scenic resources in the region, and the use of the resulting database to initiate delineation of the proposed greenway. A discussion of the rationale and significance of the method is presented, including comments on the direction and progress in the region today.     

Genotoxicity in water and sediment extracts from the St Lawrence river system, using the SOS chromotest

Surface water and sediments from the St Lawrence River system (Québec region) were analysed for genotoxicity using the SOS Chromotest, as well as for their chemical concentrations of polycyclic aromatic hydrocarbons and heavy metals. Additionally, chlorobenzenes, polychlorinated biphenyls, organochlorinated pesticides, ammonia and nitrite concentrations in sediments were determined. Water and sediments sampled from twenty-five sites were initially partitioned into their aqueous and particulate phases by tangential flow filtration and centrifugation, respectively. Organic contaminants were extracted from the fractions with dichloromethane. For surface water, fifteen extracts of filtered water and seven of particulates, and for sediments one extract of pore water and three of particulates proved to be weakly genotoxic. All but one of the genotoxic responses observed in the surface water were obtained from samples taken from the highly industrial portion of the St Lawrence River system, with the strongest responses observed in Lake St Louis. Surface water genotoxicants partitioning favours the particulate fraction. Bottom particulates genotoxicity was 1000-fold weaker than suspended particulates, on a per unit weight basis. Additionally, whole sediments were extracted with a 10% dimethylsulfoxide-saline solution. The observed distributions of genotoxicity values did not correlate with observed concentrations of demonstrated SOS inducers, mutagens and/or carcinogens, nor with the presence of other toxic chemicals.     

Relationships among total recoverable and reactive metals and metalloid in St. Lawrence River sediment: bioaccumulation by chironomids and implications for ecological risk assessment

The availability and bioaccumulation of metals and metalloids, and the geochemical interactions among them, are essential to developing an ecological risk assessment (ERA) framework and determining threshold concentrations for these elements. The purpose of this study was to explore the relationships among total recoverable and reactive metals and metalloid in sediment and their bioaccumulation by chironomids. In the fall of 2004 and 2005, 58 stations located in the three fluvial lakes of the St. Lawrence River and its largest harbour area in Montreal, Canada, were sampled. Nine total recoverable and reactive metals (Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) and one metalloid (As) were measured in whole sediment using two extraction methods: HCl/HNO(3) and HCl 1N, respectively. The bioaccumulation of six metals (Cd, Cr, Cu, Ni, Pb and Zn) and As by chironomids was evaluated in a subset of 22 stations. Strong collinearities were observed between some total recoverable or reactive metal concentrations in sediment; two principal clusters, including collinear metals, were obtained. The first one included metals of mainly geological origin (Al, Cr, Fe, Mn, Ni), while the second one included As, Cd, Cu, Pb and Zn, which likely derive mainly from point sources of anthropogenic contamination. Each element also showed strong collinearity between their total recoverable and reactive forms (0.65< or =r < or =0.97). We can conclude that both chemical forms are equivalent for use in statistical models needed to explain biological responses and also in screening risk assessment. However, these relationships are not always proportional. Lower availability percentages were observed for Cd, Cu and Zn in the highly mixed-contaminated area of the Montreal Harbour, even though concentrations in sediment were higher. We observed a significant correlation (0.50< or =r < or =0.56) between concentrations in chironomids and concentrations of both total recoverable and reactive Cr and Pb in sediment. Arsenic was an exception, with accumulation by chironomids being highly related to reactive sediment concentrations. Finally, we observed variable influences of explanatory factors (e.g. sediment grain size, Al, Fe, Mn, S, TOC), depending on which metal or metalloid was being predicted in chironomids. In this context, it is difficult to choose a universal predictive method to explain the bioaccumulation of specific metals, and more research is still needed into normalization procedures that consider a combination of explanatory factors.     

Accumulation of mercury and selenium in the brain of river otters (Lontra canadensis) and wild mink (Mustela vison) from Nova Scotia, Canada

Total Hg, methyl-Hg (MeHg) and Se levels were measured in the brain of river otters (Lontra canadensis) and wild mink (Mustela vison) carcasses collected from Nova Scotia, Canada. Total Hg concentrations in the otters' brain were highly variable, ranging from 0.3 to 18.0 μg/g dw and were significantly higher in animals caught from inland areas of the province versus coastal animals. Similarly, inland otters contained significantly more MeHg in the brain than did coastal otters. MeHg was highly correlated with total Hg in both inland and coastal otters and represented on average approximately 82% of the total Hg. Selenium concentrations in the otter brain ranged from 1.0 to 7.8 μg/g dw but unlike Hg, there was no significant difference in Se levels between inland and coastal otters. There was a significant positive relationship between Se and total Hg concentrations in the otters with the molar ratio of Se:Hg approximately 1:1 for animals having an Hg concentration > 18 nmol/g dw.The non-random sampling protocol for the mink precluded extensive statistical analysis of the data. However, unlike otters, virtually all (i.e. 98%) of the total Hg in mink brain was present as MeHg in both inland and coastal mink. Also unlike the otter results, Se concentrations showed no relationship with either total or MeHg in both inland and coastal mink.The data suggest that mink and otters may have different mechanisms for managing high levels of Hg in the brain.     

Calculation of the mercury accumulation in the Idrijca River alluvial plain sediments

From the historic literature on the Idrija mercury mine, it is evident that part of the smelting and mining waste was dumped into the Idrijca River. This waste was transported downstream during floods. The amount of mercury which has accumulated in the alluvial sediments of the Idrijca River until the present was studied. Mapping of Holocene river terraces of the Idrijca River was performed in order to estimate the volume of the alluvial sediment. For the purpose of the assessment of the mercury concentration, we sampled the alluvial sediments on different levels and performed an analysis of variance. The greatest variability is between the floodplain and terraces inside the same alluvial plain. Considering this fact, which determined the methodology employed for calculation, we estimated that about 2029 tons of mercury is stored in the Idrijca River alluvial sediments.     

Mercury in the environment and riverside population in the Madeira River Basin, Amazon, Brazil

This work presents quality control results on the mercury concentrations in different environmental (river sediments, forest soils, river suspended matter and fish) and human samples from the lower Madeira River, Amazon sampled between 2001 and 2003, about 15-20 years after the nearly cessation of gold mining activities in the region, which reached its peak in the late 1980s. The study aimed to compare mercury concentrations in these environmental samples with those reported by other authors during the gold rush of the Madeira River Basin. Today, in the Madeira River the releases of mercury register a sudden reduction due the gold price fall in the international trade. However, about 100 t of Hg were released to the atmosphere and to aquatic systems in the region during the gold rush. The present survey shows that notwithstanding the reduction of Hg emissions to the Madeira River Basin from gold mining proper, concentrations in fish and humans are similar to those measured during the gold rush. Reduction in Hg concentrations is restricted to areas close to old point sources and only for abiotic compartments (air and sediments). Remobilization of Hg from bottom sediments plus re-emission from soils due to land use changes are probably responsible for keeping high Hg concentrations in biological samples.     

Temporal and spatial trends of mercury in fish collected in the English-Wabigoon river system in Ontario, Canada

The First Nations communities of Grassy Narrows and Wabaseemong (Ontario, Canada) have been impacted by mercury pollution since the 1960s. This study was implemented with the objective of providing these communities with information on current mercury concentrations in their catch, in order to make appropriate fish consumption choices. A total of 851 fish samples, including Walleye, Northern Pike, Large-mouth Bass, and Whitefish, were collected from thirteen lakes and rivers. Total mercury was measured and the relationship between fish length, mercury concentration, and lake of origin were assessed. It was found that fish from most of the lakes exhibit a positive relationship between length and mercury accumulation. Mercury concentrations in fish collected from Clay Lake, closest to the original source of contamination, are higher than those from other lakes. Mercury concentrations have declined over the last 25 years but the gradient of contamination was still observed. Results were communicated to the communities for public health purposes.     

Historic brownfields and industrial activity in Kingston, Ontario: Assessing potential contributions to mercury contamination in sediment of the Cataraqui River

The waterfront of historic Kingston, Ontario (pop: 113,000) has been used for industrial activities for over a century. More than 40 industries have existed within the inner harbour, and while many of these industries are no longer present, the properties that they operated on remain as potential sources of persistent contamination to the present day, including mercury. To assess the extent and distribution of total mercury (THg) contamination, 21 sediment cores as well as pore water samples were collected within the inner harbour of Kingston. The spatial distribution of THg in the surface sediment is not homogenous; with concentrations in the surface sediment along the southwestern shoreline, adjacent to the former industrial properties, are significantly greater (p < 0.01) than the rest of the inner harbour, and were above the Federal severe effect limit (> 2000 ug/kg;) guideline for sediment. MeHg was detected in some sediment cores, and was found to have a significant, positive correlation with [THg] in the surface sediment (0-5 cm). THg was not found in storm sewer discharges, but was detected in terrestrial soil near the Kingston Rowing Club at a concentration of more than 4000 ug/kg. Significant [THg] was detected in runoff draining from contaminated shoreline soils, indicating that erosion from terrestrial sources may be an ongoing source of Hg to the sediment. It can be concluded that there is an increased risk over time to surrounding ecosystems where properties with historical contamination are not remediated until they are developed.     

Comparison of mercury and zinc profiles in peat and lake sediment archives with historical changes in emissions from the Flin Flon metal smelter, Manitoba, Canada

The copper-zinc smelter at Flin Flon, Manitoba, was historically the largest single Hg point-source in Canada, as well as a major source of Zn. Although emissions were reported by industry to have declined significantly since the late 1980s, these reductions have never been independently verified. Here, the histories of Hg and Zn deposition over the past century or more were determined at five lake sediment and three peat study sites in the surrounding region. At sites spanning the range from heavy to minor pollution, lake sediment Hg and Zn concentration and flux profiles increased significantly in the early 1930s after the smelter opened. Two of the three peat archives were wholly or partially compromised by either physical disturbances or biogeochemical transitions which reduced their effectiveness as atmospheric metal deposition recorders. But the remaining peat records, including a detailed recent 20 yr record at a moderately polluted site, appeared to show that substantive reductions in metal levels had occurred after the late 1980s, coincident with the reported emission reductions. However, the lake sediment results, taken at face value, contradicted the peat results in that no major declines in metal concentrations or fluxes occurred over recent decades. Mercury and Zn fluxes have in fact increased substantially since 1988 in most lakes. We suggest that this discrepancy may be explained by catchment soil saturation by historically deposited metals which are now mobilizing and leaching into lakes, as has been reported from other smelter polluted systems in Canada, whereas the upper sections of the peat cores reflected recent declines in atmospheric deposition. However, further research including instrumented wet and dry deposition measurements and catchment/lake mass balance studies is recommended to test this hypothesis, and to provide definitive data on current atmospheric metal deposition rates in the area.     

Mercury in the River Nura and its floodplain, Central Kazakhstan: I. River sediments and water

The River Nura in Central Kazakhstan has been heavily polluted by mercury originating from an acetaldehyde plant. Mercury in the riverbed is mainly associated with power station fly ash, forming a new type of technogenic deposit. A systematic survey of the bed was carried out to establish the location, extent and nature of the contaminated sediments, and to evaluate the potential for sediment transport. The bed sediments were found to contain very high concentrations of mercury, particularly in the first 15 km downstream of the source of the pollution. Average total mercury concentrations in this section of the river are typically between 150 and 240 mg/kg, falling rapidly with increasing distance downstream. The estimated total volume of silts in the riverbed between Temirtau, the origin of the pollution, and Intumak Reservoir, located 75 km downstream, has been calculated as 463500 m3, containing an estimated 9.4 tonnes mercury. Forty-six percent of the total volume of contaminated silts containing almost 95% of the mercury are located in the upper 25 km of the river, however. The data clearly support the hypothesis that large quantities of polluted sediment are not transported long distances downstream but are removed from the aquatic environment in times of flood and deposited on the low-lying lands adjacent to the river. This process, however, does not stop mercury moving further downstream in the water column.     

The recent deposition of persistent organic pollutants and mercury to the Dasuopu glacier, Mt. Xixiabangma, central Himalayas

High mountains may serve as condensers for persistent organic pollutants (POPs) and the ice/snow core can provide long-term records of atmospheric deposition of pollutants. In this study, organochlorine pesticides (OCPs) and polycyclic aromatic hydrocarbons (PAHs) in firn core from Dasuopu Glacier were analyzed and the seasonal variation and deposition flux of these pollutants were investigated. PCB 28 was always detected in samples from different firn core layers and concentrations of PCB 28 were in the range of 0.09-0.3 ng/l. Hexachlorobenzene (HCB) and total DDTs (p-p'-DDD and p-p'-DDT) were not always detected and were only present in some samples. No p-p'-DDE and hexachlorocyclohexane (HCH) were detected above the level of determination limits. Concentrations of HCB ranged from 0.04 to 0.07 ng/l, and total DDTs were in the range of 0.15-0.3 ng/l. Total glacier PAHs was below 26 ng/l. The levels of OCPs and PAHs in Dasuopu glacier were roughly similar to values from the European mountain areas but lower than those from Lys glacier (Italy) and glacier from Rocky Mountain. Hg concentration (2-35 ng/l) in firn core samples was higher than that of remote region of Arctic. PCB 28 didn't show obvious variation in different seasons, however for major PAH compounds higher values were observed in summer than in winter. With regard to Hg, it displayed winter maximum. Deposition flux of OCPs, PAHs and mercury showed similar results with maximum flux occurring in the 2000s. After 2000/2001, deposition flux decreased and reflected the possible decrease of emissions of these atmospheric pollutants in the adjacent region.     

Changes in mercury and cadmium concentrations and the feeding behaviour of beluga (Delphinapterus leucas) near Somerset Island, Canada, during the 20th century

Beluga (Delphinapterus leucas) continues to be an important food species for Arctic communities, despite concerns about its high mercury (Hg) content. We investigated whether Hg and cadmium (Cd) concentrations had changed during the 20th century in beluga near Somerset Island in the central Canadian Arctic, using well-preserved teeth collected from historical sites (dating to the late 19th century and 1926-1947) and during subsistence hunts in the late 1990s. Mercury concentrations in both historical and modern teeth were correlated with animal age, but 1990s beluga exhibited a significantly more rapid accumulation with age than late 19th century animals, indicating that Hg concentrations or bioavailability in their food chain had increased during the last century. The geometric mean tooth Hg concentration in modern 30 year old animals was 7.7 times higher than in the late 19th century, which corresponds to threefold higher concentrations in muktuk and muscle. Teeth from 1926 to 1947 were similar in Hg content to the late 19th century, suggesting that the increase had occurred sometime after the 1940s. In contrast, tooth Cd was not correlated with animal age and decreased during the last 100 years, indicating that anthropogenic Cd was negligible in this population. Late 19th century beluga displayed a greater range of prey selection (tooth delta15N values: 15.6-20.5 per thousand) than modern animals (delta15N: 17.2-21.1 per thousand). To prevent this difference from confounding the temporal Hg comparison, the Hg-age relationships discussed above were based on historical animals, which overlapped isotopically with the modern group. Tooth delta13C also changed to isotopically more depleted values in modern animals, with the most likely explanation being a significant shift to more pelagic-based feeding. Industrial Hg pollution is a plausible explanation for the recent Hg increase. However, without further investigation of the relationship between the range exploitation of modern beluga and their possible exposure to regional marine food chains with (naturally) higher Hg contents than their historical counterparts, we cannot unequivocally conclude that the increase was anthropogenically driven.     

Modelling sediment-microbial dynamics in the South Nation River, Ontario, Canada: Towards the prediction of aquatic and human health risk

Runoff from agricultural watersheds can carry a number of agricultural pollutants and pathogens; often associated with the sediment fraction. Deposition of this sediment can impact water quality and the ecology of the river, and the re-suspension of such sediment can become sources of contamination for reaches downstream. In this paper a modelling framework to predict sediment and associated microbial erosion, transport and deposition is proposed for the South Nation River, Ontario, Canada. The modelling framework is based on empirical relationships (deposition and re-suspension fluxes), derived from laboratory experiments in a rotating circular flume using sediment collected from the river bed. The bed shear stress governing the deposition and re-suspension processes in the stream was predicted using a one dimensional mobile boundary flow model called MOBED. Counts of live bacteria associated with the suspended and bed sediments were used in conjunction with measured suspended sediment concentration at an upstream section to allow for the estimation of sediment associated microbial erosion, transport and deposition within the modelled river reach. Results suggest that the South Nation River is dominated by deposition periods with erosion only occurring at flows above approximately 250 m³ s⁻¹ (above this threshold, all sediment (suspended and eroded) with associated bacteria are transported through the modelled reach). As microbes are often associated with sediments, and can survive for extended periods of time, the river bed is shown to be a possible source of pathogenic organisms for erosion and transport downstream during large storm events. It is clear that, shear levels, bacteria concentrations and suspended sediment are interrelated requiring that these parameters be studied together in order to understand aquatic microbial dynamics. It is important that any management strategies and operational assessments for the protection of human and aquatic health incorporate the sediment compartments (suspended and bed sediment) and the energy dynamics within the system in order to better predict the concentration of indicator organism.     

Ozone treatment and the depletion of detectable pharmaceuticals and atrazine herbicide in drinking water sourced from the upper Detroit River, Ontario, Canada

The depletion and degradation of pharmacologically active compounds (PhACs) and pesticides as a function of ozonation in drinking water treatment processes is not well studied. The A.H. Weeks drinking water treatment plant (DWTP) serves the City of Windsor, Ontario Canada, and incorporates ozone treatment into the production of drinking water. This DWTP also operates a real-time, scaled down pilot plant, which has two parallel streams, conventional and ozone plus conventional treatments. In this study water samples were collected from key points in the two streams of the pilot plant system to determine the depletion and influence of seasonal changes in water processing parameters on eighteen major PhACs (and metabolites) and seven s-triazines herbicides. However, only carbamazepine (antiepileptic), caffeine (stimulant), cotinine (metabolite of nicotine) and atrazine were consistently detectable in the raw water intake (low to sub-ng/L level). Regardless of the seasonality, the flocculation-coagulation and dual media filtration steps without ozone treatment resulted in no decrease in analyte concentrations, while decreases of 66-100% (undetectable, method detection limits 0.05-1 ng/L) of the analyte concentrations were observed when ozone treatment was part of the water processing. These findings demonstrate that ozone treatment is highly effective in depleting carbamazepine, caffeine, cotinine, and atrazine, and thus is highly influential in the fate of these compounds in drinking water treatment regardless of the seasonal time frame. Currently very few Canadian DWTPs incorporate ozonation into conventional treatment, which suggests that human exposure to these compounds via drinking water consumption may be an issue in affected communities.     

Temporal trends (1987-2002) of persistent, bioaccumulative and toxic (PBT) chemicals in beluga whales (Delphinapterus leucas) from the St. Lawrence Estuary, Canada

Temporal trends of persistent, bioaccumulative and toxic (PBT) chemicals were examined in beluga whales (Delphinapterus leucas) from the St. Lawrence Estuary (SLE), Canada. Blubber samples of 86 adult belugas were collected from animals stranded on the shore of the SLE between 1987 and 2002 and analyzed for several regulated PBTs, including polychlorinated biphenyls (PCBs), p,p'dichlorodiphenyltrichloroethane (DDT) and its metabolites, chlordane (CHL) and related compounds, hexachlorocyclohexane (HCH) isomers, hexachlorobenzene (HCB) and Mirex. In addition, time trends of tris(4-chlorophenyl)methane (TCPMe) and tris(4-chlorophenyl)methanol (TCPMOH), two compounds that may origin from DDT formulations, were also examined. Concentrations of most of the PBTs examined had exponentially decreased by at least a factor of two (half-life time (t(1/2))<15 years) in beluga between 1987 and 2002 while no increasing trends were observed for any of the PBTs measured. The decreasing trends of PBT concentrations in SLE beluga may be due to a decline in contamination of its diet following North American and international regulations on the use and production of these compounds or by a change in its diet itself or by a combination of both. Some PBTs did not exhibit any significant trends in beluga possibly because the most intense elimination phase subsequent to legislative regulations occurred prior to the 1987-2002 time period. Other chemicals, such gamma-HCH, did not significantly decrease likely because they are still currently used in some restricted applications. Conversely, alpha-HCH showed a significant decreasing trend indicating that SigmaHCHs is not representative of all HCHs. Both TCPMe and TCPMOH exhibited no trends in beluga during the time period examined. The metabolic capacity of SLE beluga has apparently accelerated the depletion of at least one PBT, namely CB-28/31. A significant relationship between the half-life of PBTs in beluga and log Kow was observed for most of the chemicals examined. Several factors are expected to have influenced the temporal changes of PBT concentrations in beluga which limit the usefulness of this species as a bioindicator of changes in PBT contamination in the SLE ecosystem.     

Assessment of mercury and methylmercury pollution with zebra mussel (Dreissena polymorpha) in the Ebro River (NE Spain) impacted by industrial hazardous dumps

Large amounts of industrial waste containing high concentrations of mercury (up to 436 microg/g) are dumped in a reservoir adjacent to a chlor-alkali plant in Flix (Catalonia, Spain), on the lower Ebro River. In order to assess the spatial redistribution of mercury from the point source and its bioavailability to the aquatic food web, zebra mussels (Dreissena polymorpha) were collected at several sites. The highest total Hg (THg) and methylmercury (MeHg) concentrations ever reported for zebra mussels were found (THg: 0.02 to 0.81 microg/g ww; MeHg: 0.22 to 0.60 microg/g ww). At the most polluted site, close to the waste dump, the mean values were 20 times greater than the local background level. Concentrations decreased with increasing mussel size at all sites. The MeHg/THg ratio was ca. 60% (range: 50-80%). A comparison of similar size classes clearly indicated the hot spots of Hg bioavailability to the aquatic food web and downstream transport.     

Relationship of mercury with aluminum, iron and manganese oxy-hydroxides in sediments from the Alto Pantanal, Brazil

Sediments from nine floodplain lakes in Pantanal were analyzed for a large-scale (300 km) survey of mercury (Hg) load in sediments and soils of the Alto Pantanal and to study the relationship between Hg and reactive aluminum, iron, and manganese oxy-hydroxides. The results were compared with the Hg content in river and stream sediments from the Poconé gold mining area, where Hg has been extensively used and still is in use. The results indicate that the Hg concentrations were elevated in river sediment close to the mining area in Bento Gomes river basin (average in the < 74-microm fraction 88.9 ng Hg g(-1) dry wt.; interquartile range 50.3-119.5), but there was no clear indication that the local Hg emissions have contaminated the remote floodplain lakes, where concentrations were surprisingly low (average in the < 74-microm fraction 33.2 ng Hg g(-1) dry wt. sediment; interquartile range 18.4-46.8), in particular when considering geochemical characteristics of the sediment. The sediment from the floodplain lakes contained less Hg-tot and more reactive iron oxy-hydroxides than soils from the Tapajós area in the Amazon basin. This resulted in a mass ratio between Hg and amorphous oxy-hydroxides of only 5 x 10(-6) for Hg-tot/Fe-oxa (interquartile range 3-7 x 10(-6).