Radium-226 in water, sediments, and fish from lakes near the city of Elliot Lake, Ontario, Canada

Ra-226 was measured by alpha-emission spectroscopy in water, sediments, and fish (tissues and gut contents), from five lakes in a watershed containing U mining and milling operations at Elliot Lake, Ontario, and from control lakes in an adjacent non-industrialized watershed. Ra-226 transfer parameters from lake water and sediments to fish tissues, and annual intakes by humans consuming fish, were estimated. Mean dissolved 226Ra levels ranged from approximately 76 mBq litre(-1) in water of the most affected lake, to < 10 mBq litre(-1) in control lakes. Levels in summer were consistently higher than in fall or winter; no consistent variation with depth was noted. Sediment levels ranged from approximately 3000 mBq g(-1) dry wt in one study lake to < 100 mBq g(-1) dry wt of sediment in control lakes. Bone 226Ra concentrations were higher than in muscle. The lake trout (Salvelinus namaycush), a predatory secondary consumer, had bone 226Ra levels (< 20 mBq g(-1) dry wt) that did not show significant site variation. In contrast, bottom feeding whitefish had significantly more 226Ra in bone tissue (to 38 mBq g(-1) dry wt in the lake whitefish, Coregonus clupeaformis, and 76 mBq g(-1) in round whitefish, Prosopium cylindraceum) in study lakes than in controls (< 20 mBq g(-1) dry wt). Ra-226 levels in lake trout muscle were low and showed erratic variation among lakes whereas levels in whitefish muscle did not vary significantly among study and control sites. Lake herring (= cisco, Coregonus artedii), a planktivorous fish taken only from Quirke Lake, had mean 226Ra levels of 18 and 1.4 mBq g(-1) dry wt in bone and muscle, respectively. Gut 226Ra levels, highest in lake trout from McCabe and Quirke Lakes (126 +/- 53, 64 +/- 44 mBq g(-1) dry wt, respectively), and just detectable in McCabe and Elliot Lake whitefish (24 +/- 2, 36 +/- 14 mBq g(-1) dry wt, respectively), were below detection in lake trout and whitefish from other lakes. Concentration ratios (CRs) of 226Ra from water to muscle ranged from 8 to 14 in lake trout, 7 to 14 in whitefish, and 4 to 6 in lake herring. The water to bone CRs varied from 81 to 142, 314 to 548, and 126 to 272 in the same species. CRs were always < 1 between sediments and fish tissues. Annual intake of 226Ra by human consumers of these fish was estimated to provide an effective dose of 0.003 mSv year(-1). This represents a small fraction of both natural background (> 2 mSv year(-1)) and the public dose limit (5 mSv year(-1)).     

Dissecting the spatial scales of mercury accumulation in Ontario lake sediment

Total mercury concentration was analyzed in 171 lakes from pre-industrial (>30 cm depth; Hg_{pre-industrial}) and present-day sediments (0.5–1 cm; Hg_present-day). Numerous hot or cold spots of sediment mercury enrichment (Hg EF; Hg_{pre-industrial}/Hg_present-day) were evident as determined by local tests of autocorrelation, although in most cases, the maximum correlation among sites was not the nearest neighbor, indicating a strong influence of watershed characteristics. Hg EF was correlated with the area of open water (ha) (r = 0.91, p = 0.035), mine tailings (r = 0.94, p = 0.019), and organic deposits in surficial geology of the watershed (r = −0.91, p = 0.034). Through use of local rather than global regression coefficients, R² increased from 0.20 (p = 0.005) to 0.60 (p = 0.013). A broad spatial pattern (>500 km) observed only in Hg_{pre-industrial} was best explained by mean annual precipitation (shared variance = 3.5%), while finer spatial patterns only observed in Hg_present-day and Hg EF were best explained by pH (average shared variance = 10.8%).     

Blood mercury levels among fish consumers residing in areas with high environmental burden

Mercury is a ubiquitous, persistent toxicant found in the environment. In water, mercury bioaccumulates up the food chain and leads to high concentrations in fish. Consumption of contaminated fish is the major source of exposure to mercury in the US. The objective of this study was to enroll persons living in areas selected by the Environmental Protection Agency (EPA) to have high mercury concentrations and who consume at least 6 oz of locally caught fish per week to determine the feasibility of monitoring future trends among a population identified as highly exposed. Blood samples were collected at time of interview and analyzed for mercury. Participants (n = 287) were enrolled from North Carolina, Maryland, and South Dakota. Participants reported eating an average of five servings of fish per week. The overall geometric mean for total mercury was 0.75 μg L⁻¹, with North Carolina having the highest mean level (2.02 μg L⁻¹). Overall, 42% of the study population had levels greater than the US geometric mean 0.83 μg L⁻¹. The number of servings of fish consumed was not found to be associated with blood mercury levels. We were able to identify some persons with elevated mercury concentrations living in areas identified by EPA; however, identifying and monitoring a highly exposed population over time would be challenging.     

Determinants of exposure to mercury in hair from inhabitants of the largest mercury mine in the world

Mercury exposure of the local population was assessed in two areas of the Almadén mercury mining district, Spain, which has been the world’s largest producer of this element. Two groups, who are exposed to different sources of mercury, from a point source in Almadén and a diffuse source hundreds of kilometres away in the same region, were studied. Total mercury (THg) in human hair ranged from 0.20 to 9.35 mg kg⁻¹ and the mean value was 2.64 mg kg⁻¹. About 87% of subjects had THg levels in excess of the EPA reference dose (RfD = 1.0 mg kg⁻¹), while a high percentage (68%) of them live in Almadén. There was a clear increase in hair Hg with reported fish consumption and the highest mean hair mercury level was 4 times the RfD in a group who had reported the highest consumption of fish. For the whole group, there was a significant effect of age, gender and fish consumption in relation to Hg concentration in the hair. Nevertheless, when both groups were tested separately by means of a multivariate regression model, there was significant exposure in those living near the mine area. Several factors such as age, gender and fish consumption remained statistically significant and were associated with THg. The main conclusion is that people living close to the hot spot are more impacted by mercury than people living further away. The intake of Hg through consumption of fish is an important parameter for Hg exposure; however, in the case of people living close to the hot spot, their levels are related to the highly Hg-impacted living environment.     

Sediment processes and mercury transport in a frozen freshwater fluvial lake (Lake St. Louis, QC, Canada)

An open-bottom and a closed-bottom mesocosm were developed to investigate the release of mercury from sediments to the water column in a frozen freshwater lake. The mesoscosms were deployed in a hole in the ice and particulate mercury (Hg_P) and total dissolved mercury (TDHg) were measured in sediments and in water column vertical profiles. In addition, dissolved gaseous mercury (DGM) in water and mercury water/airflux were quantified. Concentrations of TDHg, DGM, and mercury flux were all higher in the open-bottom mesocosm than in the closed-bottom mesocosm. In this paper we focus on the molecular diffusion of mercury from the sediment in comparison with the TDHg accumulation in the water column. We conclude that the molecular diffusion and sediment resuspension play a minor role in mercury release from sediments suggesting that solute release during ebullition is an important transport process for mercury in the lake.     

Bioaccumulation of decamethylcyclopentasiloxane in perch in Swedish lakes

Decamethylcyclopentasiloxane (D5), a high production volume chemical used in personal care products, enters the environment both via air and sewage treatment plant (STP) recipients. It has been found in fish, and there is concern that it may be a bioaccumulative substance. In this work D5 was analyzed in perch from six Swedish lakes that did not receive STP effluent, and in perch and sediment from six lakes that received STP effluent. In the lakes receiving the STP effluent, the D5 concentrations in sediment varied over three orders of magnitude and were correlated with the number of persons connected to the STP normalized to the surface area of the receiving body. In the lakes not receiving effluent, the D5 levels in perch were all below the LOQ, while D5 was above the LOQ in almost all perch from lakes that received effluent. The D5 concentrations in perch and sediment from the lakes receiving STP effluent were correlated. This shows that STP effluent is a much more important source of D5 to aquatic ecosystems than atmospheric deposition, and that the risk of adverse effects of D5 on aquatic life will be greatest in small recipients receiving large amounts of STP effluent. The bioaccumulation of D5 was compared to that of PCB 180 on the basis of multimedia bioaccumulation factors (mmBAFs), which describe the fraction of the contaminant present in the whole aquatic environment (i.e. water and surface sediment) that is transferred to the fish. In four of the six lakes the mmBAF of D5 was >0.3 of the mmBAF of PCB 180. Given that PCB 180 is a known highly bioaccumulative chemical, this indicates that the bioaccumulation of D5 in perch is considerable.     

The influence of mariculture on mercury distribution in sediments and fish around Hong Kong and adjacent mainland China waters

To study the influence of mariculture on mercury (Hg) speciation and distribution in sediments and cultured fish around Hong Kong and adjacent mainland China waters, sediment samples were collected from six mariculture sites and the corresponding reference sites, 200-300 m away from the mariculture sites. Mariculture activities increased total mercury, organic matter, carbon, nitrogen and sulfur concentrations in the surface sediments underneath mariculture sites, possibly due to the accumulation of unconsumed fish feed and fish excretion. However, methylmercury (MeHg) concentrations and the ratio of MeHg to THg (% MeHg) in sediments underneath mariculture sites were lower than the corresponding reference sites. The % MeHg in sediments was negatively correlated (r = −0.579, p < 0.05) with organic matter (OM) content among all sites, indicating that OM may have inhibited Hg methylation in surface sediments. Three mariculture fish species were collected from each mariculture site, including red snapper (Lutjanus campechanus), orange-spotted grouper (Epinephelus coioides) and snubnose pompano (Trachinotus blochii). The average MeHg concentration in fish muscle was 75 μg kg⁻¹ (wet weight), and the dietary intake of MeHg through fish consumption for Hong Kong residents was 0.37 μg kg⁻¹ week⁻¹, which was lower than the corresponding WHO limits (500 μg kg⁻¹ and 1.6 μg kg⁻¹ week⁻¹).     

Dynamic modelling of recovery from acidification of lakes in Killarney Park,Ontario, Canada

During much of the 1900s, the lakes in Killarney Provincial Park have been exposed to high levels of acid deposition due to sulfur emissions from the nearby metal smelters in Sudbury. The sulfur emissions from this large point source have decreased to about 10% of what they were in the 1960s. Lake water quality in Killarney Park has greatly changed in response to reduced emissions, with noticeable declines in sulfate, aluminum and calcium concentrations. Here we apply the dynamic acidification model MAGIC to 3 lakes in Killarney Park. The lakes, which have different buffering capacities and response times, were selected to represent fast, intermediate and slow recovery from acidification. The model was calibrated to match observed data for the lakes and 4 different forecast scenarios for future sulfur deposition reductions were applied. The results indicate that there is still a large potential for improvement in the water quality in Killarney. The recovery time for the different lakes varies greatly. For the lake having the slowest response time several decades are needed for the chemistry to stabilize after implementation of deposition reductions.     

Geochemical processes of mercury in Wujiangdu and Dongfeng reservoirs, Guizhou, China

The geochemical processes of mercury in Dongfeng (DF) and Wujiangdu (WJD) reservoirs, which were constructed in 1992 and 1979, respectively in Wujiang River, which is the upper branch of Yangtze River were investigated. One sampling site was chosen upriver of 1 km from the dam for each reservoir. Three sampling campaigns were conducted at these sampling sites in December 2003, April 2004 and July 2004, respectively. The distributions of different mercury species in the water column, sediment, and sediment pore water were studied. We found that the sediment is the net source of both inorganic and MeHg to the water column for both reservoirs. The MeHg diffusion fluxes in WJD reservoir at all sampling campaigns were significantly higher than those in DF reservoir. Our study demonstrated that the high primary productivity in the reservoir produced elevated organic matter content that would favor the methylmercury production in sediment.     

The effects of tertiary treated municipal wastewater on fish communities of a small river tributary in Southern Ontario, Canada

Fish community changes associated with a tertiary treated municipal wastewater effluent outfall in the Speed River, Ontario, Canada, were evaluated at nine sites over two seasons (2008) using standardized electrofishing. Habitat evaluations were conducted to ensure that the riffle sites selected were physically similar. The fish community was dominated by several species of darters that differed in their response to the effluent outfall. There was a significant decrease in Greenside Darter (Etheostoma blennioides) but an increase in Rainbow Darter (E. caeruleum) abundance directly downstream of the outfall. Stable isotope signatures (δ¹³C and δ¹⁵N), which indicate shifts in energy utilization and flow, increased in Rainbow Darter downstream, but showed no change in Greenside Darter. Rainbow Darter may be exploiting a food source that is not as available at upstream sites giving them a competitive advantage over the Greenside Darter immediately downstream of the outfall.     

Lake variability: key factors controlling mercury concentrations in New York State fish

A 4year study surveyed 131 lakes across New York State beginning in 2003 to improve our understanding of mercury and gather information from previously untested waters. Our study focused on largemouth and smallmouth bass, walleye and yellow perch, common piscivorous fish shown to accumulate high mercury concentrations and species important to local fisheries. Fish from Adirondack and Catskill Forest Preserve lakes generally had higher mercury concentrations than those from lakes in other areas of the state. Variability between nearby individual lakes was observed, and could be due to differences in water chemistry, lake productivity or the abundance of wetlands in the watershed. We found the following factors impact mercury bioaccumulation: fish length, lake pH, specific conductivity, chlorophyll a, mercury concentration in the water, presence of an outlet dam and amount of contiguous wetlands.     

Effects of sediment composition on inorganic mercury partitioning, speciation and bioavailability in oxic surficial sediments

Artificially prepared sediments were used to assess the effects of sediment composition on inorganic Hg partitioning, speciation and bioavailability. Organic coating in sediment greatly increased the Hg partitioning and the amount of bioavailable Hg bound with the clay and the Fe and Mn oxides, but had little effect on that bound with the quartz and calcium carbonate as a result of weaker binding of humic acids and fulvic acids. The clay content increased the concentration of Hg in the sediments but inhibited the gut juice extraction due to the strong binding of Hg-organic matter (OM) complexes. Most Hg in the sediments was complexed by OM (mainly distributed in the organo-complexed phase and the strongly complexed phase), and the Hg-OM complexes (especially Hg in the strongly complexed phase) in sediments contributed much to gut juice extraction. Redistribution of Hg-OM complexes between sediments and gut juices may occur during gut juice extraction and modify Hg bioavailability and speciation in sediments.     

Patterns of mercury and methylmercury bioaccumulation in fish species downstream of a long-term mercury-contaminated site in the lower Ebro River (NE Spain)

Since the 19th century, large amounts of industrial waste were dumped in a reservoir adjacent to a chlor-alkali plant in the lower Ebro River (NE Spain). Previous toxicological analysis of carp populations inhabiting the surveyed area have shown that the highest biological impact attributable to mercury pollution occurred downstream of the discharge site. However, mercury speciation in fish from this polluted area has not been addressed yet. Thus, in the present study, piscivorous European catfish (Silurus glanis) and non-piscivorous common carp (Cyprinus carpio) were selected, to investigate the bioavailability and bioaccumulation capacities of both total mercury (THg) and methylmercury (MeHg) at the discharge site and downstream points. Multiple Correspondence Analysis (MCA) was applied to reduce the dimensionality of the data set, and Multiple Linear Regression (MLR) models were fitted in order to assess the relationship between both Hg species in fish and different variables of interest. Mercury levels in fish inhabiting the dam at the discharge site were found to be approximately 2-fold higher than those from an upstream site; while mercury pollution progressively increased downstream of the hot spot. In fact, both THg and MeHg levels at the farthest downstream point were 3 times greater than those close to the waste dump. This result clearly indicates downstream transport and increased mercury bioavailability as a function of distance downstream from the contamination source. A number of factors may affect both the downstream transport and increased Hg bioavailability associated with suspended particulate matter (SPM) and dissolved organic carbon (DOC).     

Evidence of biological recovery in acid-stressed lakes near Sudbury, Canada

Reductions in the emissions of SO2 and trace metals from the Sudbury smelters have resulted in substantial improvements in water quality in many surrounding lakes. Significant biological changes have accompanied the chemical improvements. Evidence of relatively rapid recovery was found for benthic filamentous algae, phytoplankton, zooplankton, mobile species of benthic invertebrates, and some fish populations. Organisms with low dispersal ability (e.g. Hyalella azteca) have not yet recolonized these lakes. The partial recovery observed to date shows movement toward re-establishment of biological communities typical of natural Precambrian Shield lakes in this area. These findings offer strong support for further efforts to reduce industrial emissions of pollutants to the atmosphere.     

Persistent organic pollutant in a fish community of a sub-alpine lake

This study investigated the presence of organochlorine pollutants in abiotic and biotic samples from Lake Como (Italy). DDTs and PCBs were found to be the major contaminants, ranging from 0.04 to 4.25 and from 0.25 to 40.8 μg/g lipid respectively. Evidence of biomagnification according to the trophic role of the investigated organisms was highlighted by means of Stable Isotope Analysis. A Trophic Magnification Factor (TMF) was calculated for the chemicals of interest and the applicability of the method for global use was confirmed. Statistically significant correlation has been found between the calculated trophic level and the concentrations of more lipophilic compounds, while for the less lipophilic (e.g., HCH, 3CBs) the relationship is no statistically significant and the TMF is close to 1.The role of the foraging area in affecting PCB and DDT concentrations within aquatic ecosystems has been highlighted by a Principal Component Analysis (PCA).     

Temporal changes in the distribution, methylation, and bioaccumulation of newly deposited mercury in an aquatic ecosystem

Our objective was to examine how the behavior of atmospheric mercury (Hg) deposited to boreal lake mesocosms changed over time. We added inorganic Hg enriched in a different stable isotope in each of two years, which allowed us to differentiate between Hg added in the first and second year. Although inorganic Hg and methylmercury (MeHg) continued to accumulate in sediments throughout the experiment, the availability of MeHg to the food web declined within one year. This decrease was detected in periphyton, zooplankton, and water mites, but not in gomphid larvae, amphipods, or fish. We suggest that reductions in atmospheric Hg deposition should lead to decreases in MeHg concentrations in biota, but that changes will be more easily detected in short-lived pelagic species than long-lived species associated with benthic food webs.     

Spatial trends and impairment assessment of mercury in sport fish in the Sacramento–San Joaquin Delta watershed

A three-year study was conducted to examine mercury in sport fish from the Sacramento–San Joaquin Delta. More than 4000 fish from 31 species were collected and analyzed for total mercury in individual muscle filets. Largemouth bass and striped bass were the most contaminated, averaging 0.40 μg/g, while redear sunfish, bluegill and rainbow trout exhibited the lowest (<0.15 μg/g) concentrations. Spatial variation in mercury was evaluated with an analysis of covariance model, which accounted for variability due to fish size and regional hydrology. Significant regional differences in mercury were apparent in size-standardized largemouth bass, with concentrations on the Cosumnes and Mokelumne rivers significantly higher than the central and western Delta. Significant prey–predator mercury correlations were also apparent, which may explain a significant proportion of the spatial variation in the watershed.     

Radionuclides (lead-210, polonium-210, thorium-230, and -232) and thorium and uranium in water, sediments, and fish from lakes near the city of Elliot Lake, Ontario, Canada

Radionuclides (210Pb, 210Po, 230Th, and 232Th) and chemical Th and U were measured in water, sediments, and fish tissues (bone, muscle, and gut contents of laketrout, Salvelinus namaycush, whitefish, Coregonus clupeaformis and Prosopium cylindraceum) from four lakes in a watershed affected by U mining and milling operations at Elliot Lake, Ontario, and from control lakes in an adjacent, non-industrialized, watershed. Radionuclide concentration ratios between tissue levels and sediment and water levels were calculated. Annual radionuclide intakes and resulting doses were estimated for humans consuming fish from the watershed. Bone 210Pb levels were higher (186 mBq g(-1) dry wt in laketrout and 230 mBq g(-1) dry wt in one lake whitefish) than in muscle (< 50 mBq g(-1) dry wt in all cases), and generally higher in fish from study lakes than from controls, but no consistent differences were observed among fish species. Similarly, 210Po levels were higher in bone (208 +/- 33 mBq g(-1), in laketrout) than muscle (maximum 26 +/- 4 mBq g(-1), in laketrout), and in study lake populations compared to controls. Laketrout 210Po bone concentrations were higher than previously reported in Canada. Levels of 230Th, 232Th, and Th were below detection limits (20 mBq g(-1), 0.05 microg g(-1)) in body tissues in all fish species. Bone levels of U (14.6 +/- 3.0 microg g(-1), in lake whitefish) were higher than in muscle (most < 0.05 microg g(-1), except 0.12 +/- 0.04 and 0.08 +/- 0.03 microg g(-1) in lake whitefish) in fish from waters affected by industrial activity. In control lakes, bone and muscle levels were lower and not significantly different from each other. Muscle levels did not vary consistently with location. Concentration of 210Pb and U was seen from water and 'gut' material (taken as a surrogate for diet) to bone in laketrout and whitefish, and of U from water to muscle in whitefish, but in no case from sediments to tissues. Human intakes of 210Pb, 210Po, 230Th, 232Th, and U from consuming one meal of fish (375 g) per week could, in aggregate, represent an annual effective dose < 15% of the public dose limit (5 mSv). Monitoring biota living near the decommissioned Elliot Lake U operations, especially of 210Pb levels in fish muscle, with further assessment of human doses attributable to local fish and other animals in the diet, should continue. Because radionuclide effects on fish health (and on other non-human organisms) are of increasing concern, neoplasms, malformations, and reproductive anomalies in local fish deserve examination.     

Sexual difference in mercury concentrations of lake trout (Salvelinus namaycush) from Lake Ontario

We determined total mercury (Hg) concentrations in 50 female lake trout (Salvelinus namaycush) and 69 male lake trout from Lake Ontario (Ontario, Canada and New York, United States). Results showed that, on average, males were 8% higher in Hg concentration than females in Lake Ontario. We also used bioenergetics modeling to determine whether a sexual difference in gross growth efficiency (GGE) could explain the observed sexual difference in Hg concentrations. According to the bioenergetics modeling results, male GGE was about 3% higher than female GGE, on average. Although the bioenergetics modeling could not explain the higher Hg concentrations exhibited by the males, a sexual difference in GGE remained a plausible explanation for the sexual difference in Hg concentrations of the lake trout. In an earlier study, male lake trout from Lake Ontario were found to be 22% higher in polychlorinated biphenyl (PCB) concentration than females from Lake Ontario. Thus, although males were higher in both Hg and PCB concentrations, the degree of the sexual difference in concentration varied between the two contaminants. Further research on sexual differences in Hg excretion rates and Hg direct uptake rates may be needed to resolve the disparity in results between the two contaminants.     

Ecological effects, transport, and fate of mercury: a general review

Mercury at low concentrations represents a major hazard to microorganisms. Inorganic mercury has been reported to produce harmful effects at 5 μg/l in a culture medium. Organomercury compounds can exert the same effect at concentrations 10 times lower than this. The organic forms of mercury are generally more toxic to aquatic organisms and birds than the inorganic forms. Aquatic plants are affected by mercury in water at concentrations of 1 mg/l for inorganic mercury and at much lower concentrations of organic mercury. Aquatic invertebrates widely vary in their susceptibility to mercury. In general, organisms in the larval stage are most sensitive. Methyl mercury in fish is caused by bacterial methylation of inorganic mercury, either in the environment or in bacteria associated with fish gills or gut. In aquatic matrices, mercury toxicity is affected by temperature, salinity, dissolved oxygen and water hardness. A wide variety of physiological, reproductive and biochemical abnormalities have been reported in fish exposed to sublethal concentrations of mercury. Birds fed inorganic mercury show a reduction in food intake and consequent poor growth. Other (more subtle) effects in avian receptors have been reported (i.e., increased enzyme production, decreased cardiovascular function, blood parameter changes, immune response, kidney function and structure, and behavioral changes). The form of retained mercury in birds is more variable and depends on species, target organ and geographical site. With few exceptions, terrestrial plants (woody plants in particular) are generally insensitive to the harmful effects of mercury compounds.