Modeling Mercury Fluxes and Concentrations in a Georgia Watershed Receiving Atmospheric Deposition Load from Direct and Indirect Sources

Abstract

This paper presents a modeling analysis of airborne mercury (Hg) deposited on the Ochlockonee River watershed located in Georgia. Atmospheric deposition monitoring and source attribution data were used along with simulation models to calculate Hg buildup in the subwatershed soils, its subsequent runoff loading and delivery through the tributaries, and its ultimate fate in the mainstem river. The terrestrial model calculated annual watershed yields for total Hg ranging from 0.7 to 1.1 μg/m². Results suggest that approximately two-thirds of the atmospherically deposited Hg to the watershed is returned to the atmosphere, 10% is delivered to the river, and the rest is retained in the watershed. A check of the aquatic model results against survey data showed a reasonable agreement. Comparing observed and simulated total and methylmercury concentrations gave root mean square error values of 0.26 and 0.10 ng/L, respectively, in the water column, and 5.9 and 1 ng/g, respectively, in the upper sediment layer. Sensitivity analysis results imply that mercury in the Ochlockonee River is dominated by watershed runoff inputs and not by direct atmospheric deposition, and that methylmercury concentrations in the river are determined mainly by net methylation rates in the watershed, presumably in wetted soils and in the wetlands feeding the river.     

Modeling mercury fluxes and concentrations in a Georgia watershed receiving atmospheric deposition load from direct and indirect sources

This paper presents a modeling analysis of airborne mercury (Hg) deposited on the Ochlockonee River watershed located in Georgia. Atmospheric deposition monitoring and source attribution data were used along with simulation models to calculate Hg buildup in the subwatershed soils, its subsequent runoff loading and delivery through the tributaries, and its ultimate fate in the mainstem river. The terrestrial model calculated annual watershed yields for total Hg ranging from 0.7 to 1.1 microg/m2. Results suggest that approximately two-thirds of the atmospherically deposited Hg to the watershed is returned to the atmosphere, 10% is delivered to the river, and the rest is retained in the watershed. A check of the aquatic model results against survey data showed a reasonable agreement. Comparing observed and simulated total and methylmercury concentrations gave root mean square error values of 0.26 and 0.10 ng/L, respectively, in the water column, and 5.9 and 1 ng/g, respectively, in the upper sediment layer. Sensitivity analysis results imply that mercury in the Ochlockonee River is dominated by watershed runoff inputs and not by direct atmospheric deposition, and that methylmercury concentrations in the river are determined mainly by net methylation rates in the watershed, presumably in wetted soils and in the wetlands feeding the river.     

Improved preparation of small biological samples for mercury analysis using cold vapor atomic absorption spectroscopy

Concentrations of mercury in biological samples collected for environmental studies are often less than 0.1 microgram/g. Low mercury concentrations and small organ sizes in many wildlife species (approximately 0.1 g) increase the difficulty of mercury determination at environmentally relevant concentrations. We have developed a digestion technique to extract mercury from small (0.1 g), biological samples at these relevant concentrations. Mean recoveries (+/- standard error) from validation trials of mercury fortified tissue samples using cold vapor atomic absorption spectroscopy for analysis ranged from 102 +/- 4.3% (2.5 micrograms/L, n = 15) to 108 +/- 1.4% (25 micrograms/L, n = 15). Recoveries of inorganic mercury were 99 +/- 5 (n = 19) for quality assurance samples analyzed during environmental evaluations conducted during a 24 month period. This technique can be used to determine total mercury concentrations of 60 ng Hg/g sample. Samples can be analyzed in standard laboratories in a short time, at minimal cost. The technique is versatile and can be used to determine mercury concentrations in several different matrices, limiting the time and expense of method development and validation.     

Mercury species accumulation and trophic transfer in biological systems using the Almadén mining district (Ciudad Real,Spain) as a case of study

The impact of mercury (Hg) pollution in the terrestrial environments and the terrestrial food chains including the impact on human food consumption is still greatly under-investigated. In particular, studies including Hg speciation and detoxification strategies in terrestrial animals are almost non-existing, but these are key information with important implications for human beings. Therefore, in this work, we report on Hg species (inorganic mercury, iHg, and monomethylmercury, MeHg) distribution among terrestrial animal tissues obtained from a real-world Hg exposure scenario (Almadén mining district, Spain). Thus, we studied Hg species (iHg and MeHg) and total selenium (Se) content in liver and kidney of red deer (Cervus elaphus; n?=?41) and wild boar (Sus scrofa; n?=?16). Similar mercury species distribution was found for both red deer and wild boar. Major differences were found between tissues; thus, in kidney, iHg was clearly the predominant species (more than 81 %), while in liver, the species distribution was less homogeneous with a percentage of MeHg up to 46 % in some cases. Therefore, Hg accumulation and MeHg transfer were evident in terrestrial ecosystems. The interaction between total Se and Hg species has been evaluated by tissue and by animal species. Similar relationships were found in kidney for both Hg species in red deer and wild boar. However, in liver, there were differences between animals. The possible underlying mechanisms are discussed.     

Trace elements in canvasbacks (Aythya valisineria) wintering in Louisiana, USA, 1987-1988

We determined trace element concentrations in livers of canvasbacks (Aythya valisineria) collected at Catahoula Lake and the Mississippi River Delta, Louisiana during, the winter of 1987-1988. Forty percent of canvasbacks wintering at Lake Catahoula had elevated concentrations of lead (>6.7 microg g(-1) dry weight) in the liver; 33% had concentrations consistent with lead intoxication (>26.7 microg g(-1)). Based on the number of canvasbacks that winter at Lake Catahoula and the frequency of lead exposure there, more than 5% of the continental population of canvasbacks may be exposed to lead at Lake Catahoula alone. Lead concentrations in livers differed among months and were higher in males than females, but were not different in adults and immatures. Concentrations of selenium and mercury in livers of females differed among months but not by age or location. Cadmium concentrations in livers differed by age, location and month of collection, but not by sex. Frequencies and concentrations of trace elements not commonly associated with adverse effects on avian species (aluminum, arsenic, copper, iron, magnesium, manganese, nickel, silver, vanadium and zinc) are presented. Except for the elevated concentrations of lead at Catahoula Lake, all trace elements were at background concentrations.     

Distribution of mercury in the organs and tissues of five toothed-whale species of the Mediterranean

Mercury levels were determined in the tissues and organs (lung, liver, kidney, skin, muscle, bone) of five toothed-whales stranded along the Corsican coast between November 1993 and February 1996. The species taken into consideration were the bottlenose dolphin Tursiops truncatus, the common dolphin Delphinus delphis, the striped dolphin Stenella coeruleoalba, the pilot whale Globicephala melas and the Risso's dolphin Grampus griseus. The variation in mercury levels between the different tissues and organs (lung, liver, kidney, skin, muscle, bone) of the cetacean species are discussed as regards storage, biotransformation and elimination. In all cases, the liver appears to be the preferential organ for mercury accumulation (with concentrations as high as 4250 microg Hg/g dw and 3298 microg Hg/g in the livers of Tursiops truncatus and Grampus griseus, respectively). The kidney and lung are the next organs in terms of mercury uptake followed by the muscle, bone and skin. The stomach contents of Grampus griseus and D. delphis were determined and consisted of cephalopods for Grampus griseus, and of sardines Sardina pilchardus and mackerels Trachurus sp. for D. delphis. Cephalopods had higher mercury concentrations (25.4 microg Hg/g dw) than fish (ca 1 microg Hg/g). These contents represent only one meal and mercury levels found in livers may integrate mercury uptake having occurred during the whole life span of animals.     

Specific accumulation of mercury and selenium in seabirds

Total mercury (T-Hg), methyl mercury (MeHg) and selenium (Se) concentrations were determined to elucidate the relationship between Hg and Se levels in the liver of 10 seabird species. Highest concentrations of T-Hg (mean 267 microg/g dry wt), MeHg (mean 25.5 microg/g dry wt) and Se (mean 113 microg/g dry wt) were in the liver of black-footed albatross (Diomedea nigripes). An equivalent molar ratio of 1:1 between T-Hg and Se was found in the liver of individuals which contain over 100 microg Hg/g. However, such a relationship was unclear in other individuals which had relatively low Hg levels. This suggests that Se plays a role in Hg detoxification for those individuals with high Hg. In seabird tissues, Hg and Se levels should be a most important factor determining the relationship between Hg and Se, and fluctuation of Hg burden through molting and the species-specific demethylation capacity would also influence their relationships.     

Mercury in two fish species from the Paraná river floodplain, Paraná, Brazil

Total mercury concentrations were measured in dorsal muscle tissue of two edible fish species, Prochilodus scrofa 'curimba' and Pseudoplatystoma corruscans 'pintado', respectively detritivorous and carnivorous. Fish species were sampled monthly between February 1993 and January 1994 and bimonthly between April 1994 and February 1995 in three subsystems of Paraná river' system (Ivinhema River/Lake Patos; Baía River/Lake Guaraná and Paraná River/Cortado Channel), between Paraná and Mato Grosso do Sul. Total mercury was determined by HNO3/H2SO4/V2O5 digestion, SnCl2 reduction, and vapour generation method analysis (CGCH 900), adapted to Atomic Absorption Spectrometer (CGAA 7000 ABC). The mean mercury concentrations varied from 82.0 to 310.5 ng g(-1) and from 68 to 294.4 ng g(-1) in 'curimbas' and 'pintados', respectively. Mercury level increases in sexually mature 'curimbas'. Mercury values detected do not exceed the prevailing criteria for issuance of fish consumption advisories (< 500 ng g(-1)).     

Wetland influence on mercury fate and transport in a temperate forested watershed

The transport and fate of mercury (Hg) was studied in two forest wetlands; a riparian peatland and an abandoned beaver meadow. The proportion of total mercury (THg) that was methyl mercury (% MeHg) increased from 2% to 6% from the upland inlets to the outlet of the wetlands. During the growing season, MeHg concentrations were approximately three times higher (0.27ng/L) than values during the non-growing season (0.10ng/L). Transport of Hg species was facilitated by DOC production as indicated by significant positive relations with THg and MeHg. Elevated concentrations of MeHg and % MeHg (as high as 70%) were found in pore waters of the riparian and beaver meadow wetlands. Groundwater interaction with the stream was limited at the riparian peatland due to the low hydraulic conductivity of the peat. The annual fluxes of THg and MeHg at the outlet of the watershed were 2.3 and 0.092microg/m2-year respectively.     

Reproductive success of barn swallows nesting near a selenium-contaminated lake in east Texas, USA

Reproductive success and contaminant levels in 1986 and 1987 were compared between Barn Swallows nesting at selenium-contaminated Martin Lake, Texas, USA, and swallows nesting at a reference site. Nests were initiated about the same time or earlier at Martin Lake than at the reference site and clutch size was similar between the two locations. Nest success was significantly higher at Martin Lake than at the reference site and no embryo or chick deformities were documented. Selenium concentrations in 14 of 20 eggs from Martin Lake were above background (> 3 ppm, dry weight); two of 20 eggs contained > 5 ppm, a concentration associated with a 20% embryo mortality/deformity rate in some bird species. Selenium concentrations in the kidneys of adult swallows were higher at Martin Lake (mean = 14 ppm dry weight) than at the reference site (5.8 ppm). DDE, the only detected organochlorine compound, was in two of 10 eggs from Martin Lake; these concentrations were below those associated with chronic poisoning and reproductive problems. The maximum mercury concentration in livers of adult Barn Swallows (0.83 ppm, dry weight) was within the range for background levels (< 5 ppm).     

Leeches as indicators of dietary mercury exposure in non-piscivorous waterfowl in central Ontario, Canada

We collected and analysed 113 leeches (Hirudinea) from 17 small lakes in the acid-stressed Muskoka region of central Ontario, Canada to examine the relationship between lake chemistry and mercury (Hg) concentrations in leeches, and thus determine whether leeches and other benthic invertebrates posed a dietary risk of Hg exposure for non-piscivorous waterfowl. Hg concentrations in leeches were generally low and only a few-fold above the detection limit (0.78 ng g(-1) wet weight (ww)). Mean Hg concentration in the bloodsucker Macrobdella decora was 6.94 +/- 0.78 SE ng g(-1) ww (n=49) and was 5.98 +/- 0.46 ng g(-1) ww (n=64) in the scavenger Percymoorensis marmoratis. Leech Hg concentrations were correlated with calcium and dissolved organic carbon concentrations in the water, respectively. These data suggest that leeches are not suitable monitors of Hg (usually as methylmercury) biomagnification in central Ontario lakes, and do not pose a dietary risk to non-piscivorous waterfowl.     

Mercury in sediment and fish from North Mississippi Lakes

Sediments and/or fish were collected from Sardis, Enid and Grenada Lakes, which are located in three different watersheds in North Mississippi, in order to assess mercury contamination. The mean total mercury concentration in sediments from Enid Lake in 1997 was 0.154 mg Hg/kg, while 1998 sediment concentrations in Sardis, Enid and Grenada Lakes were 0.112, 0.088 and 0.133 mg Hg/kg, respectively. Sediment mercury concentrations in 1999 were similar in all three lakes but, generally lower than 1998. Mean total mercury concentrations in edible fillets of fish collected from Enid Lake in 1998 were above the human health FDA action level (>1.0 mg Hg/kg) for bass (1.40), crappie (1.69) and gar (1.89); however, tissue concentrations were less than 1.0 mg Hg/kg in carp (0.63) and catfish (0.82). Human hazard indexes for each species was 1 for both adults and children, indicating that there is a potential for toxic effects to occur. In addition, calculated consumption limits indicate that adults may consume 4–12 oz. of fish per month, depending on the species consumed. For children, 2 oz. per month may be consumed. Further studies are needed to determine the exact environmental consequences and human health impacts associated with mercury contamination in North Mississippi and the Southeastern United States.     

Mercury levels in dental surgeries and dental personnel in Slovenia

The level of mercury exposure in Slovenian dental practice was studied by measurement of air mercury levels in 63 surgeries and by analysis of the mercury content in blood and urine samples of professionally exposed and control groups (total of 77 participants).

The mean ambiental mercury concentration for all investigated surgeries was 2.8 ug Hg/m³ (range: 0.4–8.2), which is considerably below the health-based occupational exposure limit of 25 ug/m³. No significant relationships between age or type of surgeries, or the time during the working day and the air mercury levels were found.

The mean value for mercury in blood was 3.0 ng Hg/g (range: 0.9–7.7), which can be considered as the normal range for the general population. The occupational profile of the workers, years in the profession, as well as sex, showed a nonsignificant effect on blood mercury.

Urinary mercury levels were also low. Only 3 of 44 values exceeded 15 ng Hg/g. No influence of sex or occupational profile was found; however, a significant negative linear relationship (r=−0.473; P=0.0012) was observed between the concentration of mercury in urine and years in the profession.

The data indicate good mercury hygiene in Slovenian dentistry.     

Mercury and cadmium in common cormorants (Phalacrocorax carbo)

Mercury (Hg) and cadmium (Cd) in common cormorants (Phalacrocorax carbo) collected in Lake Biwa, Japan and Tokyo, Japan, were investigated to elucidate the biological behaviors of these elements, and to assess exposure to these pollutants of wild, fish-eating birds. Hg and Cd concentrations were highest in the liver and kidneys, respectively. The lowest levels of both elements were observed in chicks. Hg concentrations in all tissues except brain increased significantly with growth from chicks to juveniles (p<0.05, U-test). Cd concentrations in the kidneys and liver also increased significantly during growth from juvenile to adult (p<0.005, U-test). When comparing hepatic Hg and Cd in adult birds between 10 samples from Lake Biwa and nine samples from Tokyo, the Cd concentrations in the Lake Biwa samples (1.4+/-0.37 microg/g dry wt) (mean+/-SD) were significantly higher than those from Tokyo (0.32+/-0.16 microg/g dry wt) (p<0.005, U-test), while no statistically significant difference was found in the Hg concentrations. Possible causes of these differences were discussed in relation to their prey.     

Mercury in fish from three rift valley lakes (Turkana,Naivasha and Baringo), Kenya,East Africa

Total mercury (THg) concentrations were measured for various fish species from Lakes Turkana, Naivasha and Baringo in the rift valley of Kenya. The highest THg concentration (636 ng g(-1) wet weight) was measured for a piscivorous tigerfish Hydrocynus forskahlii from Lake Turkana. THg concentrations for the Perciformes species, the Nile perch Lates niloticus from Lake Turkana and the largemouth bass Micropterus salmoides from Lake Naivasha ranged between 4 and 95 ng g(-1). The tilapiine species in all lakes, including the Nile tilapia Oreochromis niloticus, had consistently low THg concentrations ranging between 2 and 25 ng g(-1). In Lake Naivasha, the crayfish species, Procambrus clarkii, had THg concentrations similar to those for the tilapiine species from the same lake, which is consistent with their shared detritivore diet. THg concentrations in all fish species were usually consistent with their known trophic position, with highest concentrations in piscivores and declining in omnivores, insectivores and detritivores. One exception is the detritivore Labeo cylindricus from Lake Baringo, which had surprisingly elevated THg concentrations (mean=75 ng g(-1)), which was similar to those for the top trophic species (Clarias and Protopterus) in the same lake. Except for two Hydrocynus forskahlii individuals from Lake Turkana, which had THg concentrations near or above the international marketing limit of 500 ng g(-1), THg concentrations in the fish were generally below those of World Health Organization's recommended limit of 200 ng g(-1) for at-risk groups.     

Studies of mercury pollution in a lake due to a thermometer factory situated in a tourist resort: Kodaikkanal, India

Kodaikkanal, India, suffered mercury contamination due to emissions and waste from a thermometer factory. Kodai Lake is situated to the north of the factory. The present study determined mercury in waters, sediment and fish samples and compared the values with those from two other lakes, Berijam and Kukkal. Total mercury (Hg(T)) of 356-465 ng l(-1), and 50 ng l(-1) of mercury in methyl mercury form were seen in Kodai waters while Berijam and Kukkal waters showed significantly lower values. Kodai sediment showed 276-350 mg/kg Hg(T) with about 6% methyl mercury. Berijam and Kukkal sediments showed Hg(T) of 189-226 mg/kg and 85-91 mg/kg and lower methylation at 3-4% and 2%, respectively. Hg(T) in fish from Kodai lake ranged from 120 to 290 mg/kg. The results show that pollution of the lake has taken place due to mercury emissions by the factory.     

Total mercury, methyl mercury, and carbon in fresh and burned plants and soil in Northwestern Ontario

Terrestrial plants and soil contain substantial amounts of organic carbon (C) and mercury. Flooding terrestrial areas stimulates microbial methyl mercury (MeHg) production and fish obtain elevated MeHg concentrations. Our purpose was to determine the loss of C, total mercury (THg), and MeHg from boreal plants and soil after burning to assess the potential of burning before flooding to lower MeHg. Fresh plants contained 4 to 52 ng g(-1) dry weight (dw) of THg and 0.1 to 1.3 ng g(-1) dw of MeHg. Upland soils contained 162+/-132 ng g(-1) dw of THg and 0.6+/-0.6 ng g(-1) dw of MeHg. Complete burning caused plants to lose 96, 98, 97, and 94% of the mass, C, THg, and MeHg, respectively. Upland soil lost 27, 95, 79, and 82% of the mass, C, THg, and MeHg, respectively. Our results demonstrated that a substantial loss of C, THg, and MeHg was caused by burning.     

Methylmercury production in the water column of an ultraoligotrophic lake of Northern Patagonia, Argentina

Methyl-mercury (CH3Hg+) production was studied in freshwaters from lake Moreno, an ultraoligotrophic system belonging to Northern Patagonia. Hg2+ labelled with high specific activity 197Hg was spiked to water samples in concentrations of 10 ng l(-1), and incubated in laboratory for 3d time trends under different conditions. Experimental water was sampled daily to evaluate CH3(197)Hg+ production. Lake water used in the experiments was sampled just below the upper limit of the metalimnion ( approximately 30 m depth), where maximum values of chlorophyll a have been measured previously. Sampling was performed in late autumn, when the plankton fraction <50 microm exhibited mercury concentrations up to 260 microg g(-1) dry weight. The experiments analysed lake water filtered through 50, 20, and 0.2 microm (filter-sterilized) mesh nets. ASTM grade 1 water was also incubated for control. All the experiments were run in an environmental chamber under controlled temperature and light regime. High Hg2+ conversion to CH3Hg+, up to 50%, was measured in lake water, in a process stimulated by light. CH3Hg+ production was two-fold higher after 3d of incubation with illumination compared to total darkness. Sterile lake water showed conversions up to 30%, while the planktonic components seem to enhance the CH3Hg+ production. Overall, our results provide evidence that lake Moreno waters favour CH3Hg+ production in processes stimulated by light. Although biotic components certainly contribute to enhance mercury methylation, water chemistry plays a key role in this process. We hypothesize that dissolved organic matter, particularly its quality, could be decisive.     

Distribution and speciation of mercury in the peat bog of Xiaoxing'an Mountain,northeastern China

Most reports on mercury (Hg) in boreal ecosystems are from the Nordic countries and North America. Comparatively little information is available on Hg in wetlands in China. We present here a study on Hg in the Tangwang River forested catchment of the Xiaoxing'an Mountain in the northeast of China. The average total Hg (THg) in peat profile ranged from 65.8 to 186.6 ng g(-1) dry wt with the highest at the depth of 5-10 cm. THg in the peat surface was higher than the background in Heilongjiang province, the Florida Everglades, and Birkeness in Sweden. MethylHg (MeHg) concentration ranged from 0.16 to 1.86 ng g(-1) dry wt, with the highest amount at 10-15 cm depth. MeHg content was 0.2-1.2% of THg. THg and MeHg all decreased with the depth. THg in upland layer of soil (0-20 cm) was comparable to the peat surface, but in deeper layers THg concentration in peat was much higher than that in the forested mineral soil. THg in the peat bog increased, but MeHg decreased after it was drained. THg content in plant was different; THg contents in moss (119 ng g(-1) dry wt, n=12) were much higher than in the herbage, the arbor, and the shrubs. The peat bog has mainly been contaminated by Hg deposition from the atmosphere.     

Spatial patterns in wet and dry deposition of atmospheric mercury and trace elements in central Illinois,USA

An intensive 1-month atmospheric sampling campaign was conducted concurrently at eight monitoring sites in central Illinois, USA, from June 9 to July 3, 2011 to assess spatial patterns in wet and dry deposition of mercury and other trace elements. Summed wet deposition of mercury ranged from 3.1 to 5.4 μg/m² across sites for the total study period, while summed dry deposition of reactive mercury (gaseous oxidized mercury plus particulate bound mercury) ranged from 0.7 to 1.6 μg/m², with no statistically significant differences found spatially between northern and southern sites. Ratios of summed wet to summed dry mercury deposition across sites ranged from 2.2 to 4.9 indicating that wet deposition of mercury was dominant during the study period. Volume-weighted mean mercury concentrations in precipitation were found to be significantly higher at northern sites, while precipitation depth was significantly higher at southern sites. These results showed that substantial amounts of mercury deposition, especially wet deposition, occurred during the study period relative to typical annual wet deposition levels. Summed wet deposition of anthropogenic trace elements was much higher, compared to summed dry deposition, for sulfur, selenium, and copper, while at some sites summed dry deposition dominated summed wet deposition for lead and zinc. This study highlights that while wet deposition of Hg was dominant during this spring/summer-season study, Hg dry deposition also contributed an important fraction and should be considered for implementation in future Hg deposition monitoring studies.