Mercury in zooplankton of Northern Wisconsin Lakes: taxonomic and site-specific trends

Mercury content and speciation were determined in freshwater zooplankton from twelve northern Wisconsin (USA) lakes that spanned gradients of dissolved organic carbon (DOC, 1.6 to 20.9 mg/L) and pH (4.6 to 7.2). MeHg in crustacean taxa ranged from 1 to 479 ng/g dry weight, and from 2 to 45 ng/g in the invertebrate predators. Total Hg in the predators ranged from 20 to 153 ng/g. Although the highest MeHg values were found in the herbivores from high DOC lakes (and the experimentally acidified basin of Little Rock Lake), we observed considerable variation in the relationship between MeHg content of zooplankton and lakewater DOC. Bioconcentration factors (BCF) for both MeHg (3.5 to 7.1 log units) and Hg (3.7 to 5.4 log units) decreased with increasing lake DOC, while pH effects were not as apparent. Bioconcentration of MeHg was higher than Hg indicating that MeHg increases while non-methyl Hg declines in progressively higher trophic levels. Biomagnification factors (BMF) for Hg and MeHg were low relative to BCF. The BMF for crustaceans averaged 0.4 log units for MeHg and ?0.5 log units for Hg, indicating that MeHg increased 2.5-fold from seston to crustacean herbivores, while non-MeHg concentrations declined. Unlike BCF, BMF were not related to DOC or pH. In contrast to studies of vertebrate predators, both BCF and BMF in the invertebrate predatorChaoborus, were lower than those in presumed prey. These observations point toward several complexities in the transport of Hg species in the lower levels of aquatic foodwebs.     

Effects of throughfall and litterfall manipulation on concentrations of methylmercury and mercury in forest‐floor percolates

The forest floor was shown to be an effective sink of atmospherically deposited methylmercury (MeHg) but less for total mercury (Hg_total). We studied factors controlling the difference in dynamics of MeHg and Hg_total in the forest floor by doubling the throughfall input and manipulating aboveground litter inputs (litter removal and doubling litter addition) in the snow‐free period in a Norway spruce forest in NE Bavaria, Germany, for 14 weeks. The MeHg concentrations in the forest‐floor percolates were not affected by any of the manipulation and ranged between 0.03 (Oa horizon) and 0.11 (Oi horizon) ng Hg L^–1. The Hg_total concentrations were largest in the Oa horizon (24 ng Hg L^–1) and increased under double litterfall (statistically significant in the Oi horizon). Similarly, concentrations of dissolved organic C (DOC) increased after doubling of litterfall. The concentrations of Hg_total and DOC correlated significantly in forest‐floor percolates from all plots. However, we did not find any effect of DOC on MeHg concentrations. The difference in the coupling of Hg_total and MeHg to DOC might be one reason for the differences in the mobility of Hg species in forest floors with a lower mobility of MeHg not controlled by DOC.     

The role of dissolved organic carbon in the chemistry and bioavailability of mercury in remote Adirondack lakes

A number of recent studies have documented elevated concentrations of mercury (Hg) in fish caught in remote lakes and a pattern of increased concentrations of Hg in fish tissue with decreasing water column pH. Because of the potential linkage between fish Hg and surface water acidification, factors regulating water column concentrations and bioavailability of Hg were investigated in Adirondack lakes through a field study and application of the Mercury Cycling Model (MCM). Concentrations of total Hg and total MeHg were highly variable, with concentrations of total MeHg about 10% of total Hg in lakes which did not show anoxic conditions. In lakes exhibiting anoxic conditions in the hypolimnion during summer stratification, concentrations of total MeHg were elevated. Concentrations of total Hg and total MeHg increased with decreasing pH in remote Adirondack lakes. However, more importantly, concentrations of total Hg and total MeHg increased with increasing concentrations of dissolved organic carbon (DOC) and percent near-shore wetlands in the drainage basin. Mercury concentrations in muscle tissue of yellow perch from Adirondack lakes were elevated above the U.S. FDA action level (1 μg/g Hg) in 7% of the fish sampled or in one or more individual fish from 9 of the 16 lakes sampled. Fish Hg concentrations generally increased with increasing fish length, weight and age. Patterns of increasing Hg concentration with age likely reflect shifts in prey of yellow perch and the bioconcentration of Hg along the food chain. For age 3 to 5 perch, concentrations of Hg increased with increasing concentrations of DOC and percent near-shore wetlands in the drainage basin. However, for a lake with very high DOC concentrations, fish concentrations of Hg declined. Calculations with the MCM also show that concentrations of Hg species increase with increasing DOC due to complexation reactions. Increases in DOC result in increasing concentrations of Hg in biota but decreases in the bioconcentration factor of Hg in fish tissue. This research suggests that DOC is important in the transport of Hg to lake systems. High concentrations of DOC may complex MeHg, diminishing its bioavailability. At high concentrations of monomeric Al, the complexation of MeHg with DOC apparently decreases, enhancing the bioavailability of MeHg.     

The Effect of Fire on Mercury Cycling in the Soils of Forested Watersheds: Acadia National Park,Maine, U.S.A.

This study compares mercury (Hg) and methylmercury (MeHg) distribution in the soils of two forested stream watersheds at Acadia National Park, Maine, U.S.A. Cadillac Brook watershed, which burned in 1947, has thin soils and predominantly deciduous vegetation. It was compared to the unburned Hadlock Brook watershed, with thicker soil and predominantly coniferous vegetation. Soils in both watersheds were primarily well drained. The fire had a significant impact on the Cadillac watershed, by raising the soil pH, altering the vegetation, and reducing carbon and Hg pools. Total Hg content was significantly higher (P > 0.05) in Hadlock soils (0.18 kg Hg ha^-1) compared to Cadillac soils (0.13 kg Hg ha^-1). Hadlock O horizon had an average Hg concentration of 134±48 ng Hg g^-1 dry weight, compared to 103±23 ng Hg g^-1 dry weight in Cadillac O horizon. Soil pH was significantly higher in all soil horizons at Cadillac compared to Hadlock soils. This difference was especially significant in the O horizon, where Cadillac soils had an average pH of 3.41±0.22 compared to Hadlock soils with an average pH of 2.99±0.13.To study the mobilization potential of Hg in the O horizons of the two watersheds, batch adsorption experiments were conducted, and the results were modeled using surface complexation modeling. The results of Hg adsorption experiments indicated that the dissolved Hg concentration was controlled by the dissolved organic carbon (DOC) concentration. The adsorption isotherms suggest that Hg is more mobile in the O horizon of the unburned Hadlock watershed because of higher solubility of organic carbon resulting in higher DOC concentrations in that watershed.Methylmercury concentrations, however, were consistently higher in the burned Cadillac O horizon (0.20±0.13 ng Hg g^-1 dry weight) than in the unburned Hadlock O horizon (0.07±0.07 ng Hg g^-1 dry weight). Similarly, Cadillac soils possessed a higher MeHg content (0.30 g MeHg ha^-1) than Hadlock soils (0.16 g MeHg ha^-1). The higher MeHg concentrations in Cadillac soils may reflect generally faster rates of microbial metabolism due to more rapid nutrient cycling and higher soil pH in the deciduous forest. In this research, we have shown that the amount of MeHg is not a function of the total pool of Hg in the watershed. Indeed, MeHg was inversely proportional to total Hg, suggesting that landscape factors such as soil pH, vegetation type, or land use history (e.g., fire) may be the determining factors for susceptibility to high Hg in biota.     

Mercury Speciation in the Water of Minamata Bay, Japan

The speciation of mercury (Hg) in Minamata Bay (Japan) was studied over a 2-year period (2006?C2008). Concentrations of dissolved total Hg, dissolved methylmercury (MeHg), particulate total Hg, and suspended solids were 0.43?±?0.14 ng/l (mean?±?standard deviation), 0.10?±?0.06 ng/l, 3.04?±?2.96 ng/l, and 5.94?±?2.10 mg/l, respectively. Correlations between concentrations of particulate total Hg and suspended solids at four depths (surface: 0 m; mid-depth: ?6 m, ?10 m; and bottom +1 m layer) were only significant in the bottom +1 m layer. The mean dissolved MeHg concentration and the ratio of dissolved MeHg to dissolved total Hg were considerably higher in summer compared to other seasons. The data suggest that bottom sediment was not the sole source of MeHg, and that MeHg may be produced in the water column by the conversion of divalent Hg eluted from resuspended bottom sediment. The correlation between seawater characteristics such as salinity, temperature, dissolved oxygen (DO), and dissolved MeHg concentration indicates that Hg methylation could be influenced by the heterotrophic activity of microorganisms in the seawater. In particular, inverse correlations were observed between DO, salinity, and MeHg concentration. However, dissolved MeHg concentrations did not correlate with seawater characteristics such as pH or chlorophyll-a.     

Ultra trace level mercury in the Everglades ecosystem,a multi-media canal pilot study

The Florida Everglades ecosystem is composed of the largest deposit (9600 km²) of near neutral peat in the world extending south of Lake Okeechobee to Florida Bay. The federal Central and South Florida Flood Control Project (C&SF) has sectioned the historic Everglades with a system of canals and levees to control water for urban and agricultural development, resulting in pronounced hydrologic modifications to the natural system. As a part of a comprehensive ecological risk assessment of mercury (Hg) contamination in the Everglades ecosystem, a pilot study of canals was initiated in September 1993 to determine the extent and magnitude of total (HgT) and methylmercury (MeHg) in water, sediment and fish. A probability-based random sampling grid was used to obtain consistent estimates of Hg contamination over this large geographic area. Two hundred canal sampling locations were selected as probability samples by associating grid points on the sampling frame with specific canal sections for independent sampling cycles. Of this number 50 locations were randomly selected for sampling in this pilot study. The selected canal points were sampled from north to south during a six day period. Cumulative distributions with 95% confidence intervals were calculated and used to determine a canal system median concentration for selected water, sediment and fish constituents. The percent exceedance of each median, by hydrologic subarea, was determined to demonstrate the existence and direction of spatial gradients in the system. North to south (high to low) gradients were apparent for total phosphorus (TP), sulfate (SO₄), dissolved organic carbon (DOC), conductance, HgT and MeHg in water. However, the gradients were reversed from south to north for HgT in sediments and fish (Gambusia sp). The greatest Hg concentrations inGambusia sp. occurred in the same canals where largemouth bass had previously been found to be most contaminated.     

Mercury and Organic Carbon Dynamics During Runoff Episodes from a Northeastern USA Watershed

Mercury and organic carbon concentrations vary dynamically in streamwater at the Sleepers River Research Watershed in Vermont, USA. Total mercury (THg) concentrations ranged from 0.53 to 93.8 ng/L during a 3-year period of study. The highest mercury (Hg) concentrations occurred slightly before peak flows and were associated with the highest organic carbon (OC) concentrations. Dissolved Hg (DHg) was the dominant form in the upland catchments; particulate Hg (PHg) dominated in the lowland catchments. The concentration of hydrophobic acid (HPOA), the major component of dissolved organic carbon (DOC), explained 41–98% of the variability of DHg concentration while DOC flux explained 68–85% of the variability in DHg flux, indicating both quality and quantity of the DOC substantially influenced the transport and fate of DHg. Particulate organic carbon (POC) concentrations explained 50% of the PHg variability, indicating that POC is an important transport mechanism for PHg. Despite available sources of DHg and wetlands in the upland catchments, dissolved methylmercury (DmeHg) concentrations in streamwaters were below detection limit (0.04 ng/L). PHg and particulate methylmercury (PmeHg) had a strong positive correlation (r ²?=?0.84, p?<?0.0001), suggesting a common source; likely in-stream or near-stream POC eroded or re-suspended during spring snowmelt and summer storms. Ratios of PmeHg to THg were low and fairly constant despite an apparent higher methylmercury (meHg) production potential in the summer. Methylmercury production in soils and stream sediments was below detection during snowmelt in April and highest in stream sediments (compared to forest and wetland soils) sampled in July. Using the watershed approach, the correlation of the percent of wetland cover to TmeHg concentrations in streamwater indicates that poorly drained wetland soils are a source of meHg and the relatively high concentrations found in stream surface sediments in July indicate these zones are a meHg sink.     

Solid-Solution Metal Partitioning for the Upper Mero River Basin (NW Spain)

This study determines the seasonal variability of metal partition coefficients [aluminium (Al), iron (Fe), manganese (Mn), copper (Cu), and zinc (Zn)] and analyses the importance of suspended sediments (SS), dissolved organic carbon (DOC) concentrations, pH, and discharge (Q) on the seasonal variability of metal partition coefficients (K_Ds) in the headwaters of the Mero River catchment, which drains an agroforestry area in northwestern Spain. Metal partition coefficients were used as an approach to relate dissolved and particulate fractions. Water samples were collected over 3 years (2005–2008) at the catchment outlet. The mean metal dissolved concentrations were: Fe (43.5 μg L^?1) > Al (23.3 μg L^?1) > Zn (1.8 μg L^?1) > Mn (1.2 μg L^?1) > Cu (0.3 μg L^?1). Partition coefficients followed the order Mn > Al > Fe > Zn > Cu, and their values exhibited low variability. Al, Cu, and Zn partition coefficients presented the greatest values in summer, except during 2007–2008, when the greatest K_Ds value was observed in autumn, whereas the K_Ds of Fe showed the greatest values in winter. The K_D of Mn has no seasonality. For Al, Cu, and Zn, the seasonal SS concentrations were closely related to Kd. For Fe, Kd was more closely related to DOC concentration than to SS concentration.     

Mercury Cycling in Lake Gordon and Lake Pedder,Tasmania (Australia). I: In-lake Processes

The processes affecting the concentrations of total mercury (total Hg) and methylmercury (MeHg) in a freshwater system comprising two connected reservoirs in southwest Tasmania were investigated. Surface concentrations of total mercury (total Hg)were temporally and spatially uniform in both Lake Gordon (2.3±0.4 ng L^-1, n = 27) and Lake Pedder (2.3±0.3 ng L^-1, n = 11). The surface concentrations of MeHg in Lake Gordon (0.35±0.39 ng L^-1, n = 25) were more variable than total Hg and MeHg typically comprised 10–20% of total Hg. The relatively high amount of total mercury present as MeHg in Lake Gordon was attributed to the high proportion of wetlandsin the upper catchment (50% of total area) and in-lake contributions (ca. 40% of total MeHg). Despite the close proximity of the two lakes, MeHg concentrations in Lake Pedder were consistently lower than in Lake Gordon. This phenomenon canbe explained in part by the greater contribution of direct rainfall to Lake Pedder leading to the dilution of MeHg. Water column MeHg concentrations were higher in warmer months in bothlakes, reflecting increased net methylation of inorganic mercury.Unlike previous studies of seasonally anoxic lakes, depth profiles of total mercury and MeHg in Lake Gordon were uniform and were not affected by water column stratification occurringin the summer months, and oxygen depletion with depth. This suggests that redox cycling and accumulation of MeHg in the hypolimnion following seasonally-induced anoxia is not a significant part of the mercury cycle in Lake Gordon. The primary location of MeHg production within the lake's water column is not conspicuous. Mercury speciation measurements made above and below the lake system over a period of 19 months indicates that after 20 yr of impoundment, the reservoirs are not significantly affecting MeHg concentrations in the downstreamriverine environment.     

Partitioning of Hg Between Solid and Dissolved Organic Matter in the Humus Layer of Boreal Forests

The mobility of mercury (Hg) deposited on soils controls the concentration and toxicity of Hg within soils and in nearby streams and lakes, but has rarely been quantified under field conditions. We studied the in situ partitioning of Hg in the organic top layer (mor) of podsols at two boreal forest sites differing in Hg deposition and climatic regime (S. and N. Sweden, with pollution declining to the north). Soil solution leaching from the mor layer was repeatedly sampled using zero-tension lysimeters over 2 years, partly in parallel with tension lysimeters. Concentrations of Hg and dissolved organic carbon (DOC) were higher while pH was lower at the southern site (means ± SD: Hg?=?44?±?15 ng L^?1, DOC?=?63.0?±?31.3 mg L^?1, pH?=?4.05?±?0.53) than at the northern site (Hg?=?22?±?6 ng L^?1, DOC?=?41.8?±?12.1 mg L^?1, pH?=?4.28?±?0.43). There was a positive correlation over time between dissolved Hg and DOC at both sites, even though the DOC concentration peaked during autumn at both sites, while the Hg concentration remained more constant. This correlation is consistent with the expected strong association of Hg with organic matter and supports the use of Hg/C ratios in assessments of Hg mobility. In the solid phase of the overlying O_f layer, both Hg concentrations and Hg/C ratios were higher at the southern site (means ± SD: 0.34?±?0.06 μg g^?1 dw and 0.76?±?0.14 μg g^?1 C, respectively) than at the northern site (0.31?±?0.05 μg g^?1 dw and 0.70?±?0.12 μg g^?1 C, respectively). However, concentrations in the solid phase differed less than might be expected from the difference in current atmospheric input, suggesting that the fraction of natural Hg is still substantial. At both sites, Hg/C ratios in the upper half of the mor layer were only about two thirds of those in the lower half, suggesting that the recent decrease in anthropogenic Hg deposition onto the soil is offset by a natural downward enrichment of Hg due to soil decomposition or other processes. Most interestingly, comparison with soil leachate showed that the average Hg/C ratios in the dissolved phase of the mor layers at both sites did not differ from the average Hg/C ratios in the overlying solid organic matter. These results indicate a simple mobilisation with negligible fractionation, despite differences in Hg deposition patterns, soil chemistry and climatic regimes. Such a straight-forward linkage between Hg and organic matter greatly facilitates the parameterisation of watershed models for assessing the biogeochemical fate, toxic effect and critical level of atmospheric Hg input to forest soils.     

Application of the Regional Mercury Cycling Model (RMCM) to Predict the Fate and Remediation of Mercury in Onondaga Lake,New York

Onondaga Lake exhibits elevated concentrations of total mercury (HgT) and methyl-mercury (MeHg) in the water column, sediments and fish tissue due to industrial inputs, wastewater discharge and urban runoff. The steady-state Regional Mercury Cycling Model (RMCM) was calibrated to Onondaga Lake and applied to evaluate various remediation scenarios. Because of detailed data available for Onondaga Lake, the RMCM was effectively calibrated. Model predictions of water column and fish concentrations of Hg generally agreed with measured values. The model underestimated concentrations of Hg in sediments. Mass balance calculations show that inputs of HgT largely originate from tributary and wastewater inflows to the lake. In contrast, MeHg is largely derived from internal production. Model calculations suggest that elimination of Hg inputs from wastewater effluent and of drainage from a former chlor-alkali facility could greatly decrease Hg concentrations in fish tissue.     

Mercury speciation in Lake Baikal

Research on mercury (Hg) distribution and speciation was carried out in Lake Baikal, a large, strong-oligotrophic freshwater reservoir in Siberia, Russia, during June 1992 and march 1993. In summer, total Hg in the water column ranged from 0.14 to 0.77 ng Hg/L, with the highest concentrations observed in the central basin of the lake in surface water samples. Labile inorganic Hg was found to be 7 to 20 % of the total Hg content. Highest total Hg concentrations were found in river waters: up to 2 ng Hg/L. Labile methylmercury (MeHg) concentrations ranged from 2 to 38 pg Hg/L in the water column, with the higher concentrations in the central part of the lake, and showing a slight increase in near bottom waters. Labile MeHg makes up 1 to 15 % of the total Hg content in the water column, with larger fractions in deep waters. The slight increase of the MeHg gradient with depth corresponds with the O₂ minimum region. Highest MeHg concentrations were observed in river waters (up to 145 pg Hg/L) and in some bays of the lake (up to 160 pg Hg/L). In these high temperature- and phytoplankton-rich water masses, the MeHg-fraction increased up to 35 % of total Hg. Labile MeHg concentrations in water samples taken in winter in the southern basin (under the ice cover), showed slightly higher concentrations than in summer, possibly due to an early spring bloom. In rainwater, total Hg ranged from 3 to 20 ng Hg/L and MeHg from 0.1 to 0.25 ng Hg/L. In snow, a large fraction of total Hg is bound to particulate matter; concentrations of total Hg ranged from 8 to 60 ng Hg/L and labile MeHg from 0.1 to 0.25 ng Hg/L. Atmospheric Hg was found to be 0.73 to 2.31 ng/m³ as gaseous Hg and 0.005 to 0.02 ng/m³ in its particulate form. Spatial distribution patterns of atmospheric Hg show slightly higher concentrations over the central part of the lake and the Selenga river delta. In winter, atmospheric Hg values (measured in the southern region), ranged from 1.2 to 6.1 ng/m³ as total gaseous Hg and 0.02 to 0.09 ng/m³ as total particulate Hg, and are higher than in summer, probably influenced by coal burning and traffic by the local population. MeHg contents in fish ranged from 20 ng Hg/g dry weight in small Cottocomephorus to 300 ng Hg/g dry weight in pike and trout species, which were caught in organic-rich waters.     

Measurement of methylmercury and mercury in run-off,lake and rain waters

During one year, samples from eight drainage lakes, seven run-off stations and three deposition sites from various geographical areas in Sweden were collected and analyzed for methyl Hg (MeHg) and total Hg (Hg-tot). The MeHg concentrations ranged from 0.04 to 0.64 ng L^?1, 0.04 to 0.8 ng L^?1, and <0.05 to 0.6 ng L^?1 in run-off, lake water and rain water, respectively. The corresponding Hg-tot concentrations were found in the range 2 to 12 ng L^?1, 1.35 to 15 ng L^?1, and 7 to 90 ng L^?1, respectively. A Hg-tot level of about 60 ng Hg L^?1 was found in throughfall water. The MeHg and Hg-tot concentrations are positively correlated in both run-off and lake water, but not in rain and throughfall water. A strong positive correlation between the MeHg, as well as the Hg-tot concentration, and the water color is observed in both run-off and lake waters, which suggests that the transport of MeHg and other Hg fractions from soil via run-off water to the lake is closely related to the transport of organic substances; and is a consequence of the biogeochemical processes and the water flow pathway. The ratio between the mean values of MeHg and Hg-tot seems to be an important parameter, with an indicated negative coupling to the mean value of pH for run-off water, but a strong positive correlation to Hg-content in fish, the ratio between the area of the catchment and the lake, as well as to the retention time of lake.     

Mercury cycling in the Allequash Creek watershed,northern Wisconsin

Although there have been recent significant gains in our understanding of mercury (Hg) cycling in aquatic environments, few studies have addressed Hg cycling on a watershed scale. In particular, attention to Hg species transfer between watershed components (upland soils, groundwater, wetlands, streams, and lakes) has been lacking. This study describes spatial and temporal distributions of total Hg and MeHg among watershed components of the Allequash Creek watershed (northern Wisconsin, USA). Substantial increases in total Hg and MeHg were observed as groundwater discharged through peat to form springs that flow into the stream, or rivulets that drain across the surface of the wetland. This increase was concomitant with increases in DOC. During fall, when the Allequash Creek wetland released a substantial amount of DOC to the stream, a 2–3 fold increase in total Hg concentrations was observed along the entire length of the stream. Methylmercury, however, did not show a similar response. Substantial variability was observed in total Hg (0.9 to 6.3) and MeHg (<0.02 to 0.33) concentrations during synoptic surveys of the entire creek. For the Allequash Creek watershed, the contributing groundwater basin is about 50% larger than the topographic drainage basin. Total Hg concentrations in groundwater, the area of the groundwater basin, and annual stream flow data give a watershed-yield rate of 1.2 mg/km²/d, which equates to a retention rate of 96%. The calculated MeHg yield rate for the wetland area is 0.6 to 1.5 mg/km²/d, a value that is 3–6 fold greater than the atmospheric deposition rate.     

Mercury Partitioning in Surface Sediments of the Upper St. Lawrence River (Canada): Evidence of the Importance of the Sulphur Chemistry

An intensive survey of mercury speciation was performed at a site on the Upper St. Lawrence River near Cornwall, Ontario, Canada with a history mercury contamination in sediments. Surface sediments were collected every 1.50 h. Total mercury (Hg_total), methylmercury (MeHg), organic carbon, inorganic and organic sulphur were determined in the solid fraction. Dissolved Hg_total, MeHg and dissolved organic carbon (DOC) were measured in pore waters. Concentrations of Hg_total in the upper layers (first 5 cm) were high, ranging from 1.42 to 25.8 nmol g^?1 in solids and from 125 to 449 pM in pore waters. MeHg levels were also high, ranging from 4.34 to 34.1 pmol g^?1 in solids and from 40 to 96 pM in pore waters. This amounts to up to 1.4% of Hg_total present as MeHg in solids and 64% in pore waters. A daily pattern for Hg_total was observed in the solid fraction. The MeHg distribution in solids and pore waters was not correlated with Hg_total or DOC_, suggesting that the concentrations of MeHg are probably more influenced by the relative rates of methylation/demethylation reactions in the sediment–water interface. Acid volatile sulphide levels and DOC were inversely correlated with organic sulphur (S_org) levels suggesting that both parameters are involved in the rapid production of S_org. A positive correlation was also observed between Hg_total and S_org in solids (R?=?0.87, p?<?0.01) illustrating the importance of organic sulphur in the retention and distribution of Hg in the solid fraction of the sediments. The results suggest that variations of Hg_total concentrations in Upper St. Lawrence River surface sediments were strongly influenced by the formation/deposition/retention of organic sulphur compounds in the sediment–water interface.     

Biodegradation of Synthetic Dyes—A Review

The upper Great Egg Harbor River watershed in New Jersey’s Coastal Plain is urbanized but extensive freshwater wetlands are present downstream. In 2006–2007, studies to assess levels of total mercury (THg) found concentrations in unfiltered streamwater to range as high as 187 ng/L in urbanized areas. THg concentrations were <20 ng/L in streamwater in forested/wetlands areas where both THg and dissolved organic carbon concentrations tended to increase while pH and concentrations of dissolved oxygen and nitrate decreased with flushing of soils after rain. Most of the river’s flow comes from groundwater seepage; unfiltered groundwater samples contained up to 177 ng/L of THg in urban areas where there is a history of well water with THg that exceeds the drinking water standard (2,000 ng/L). THg concentrations were lower (<25 ng/L) in unfiltered groundwater from downstream wetland areas. In addition to higher THg concentrations (mostly particulate), concentrations of chloride were higher in streamwater and groundwater from urban areas than in those from downstream wetland areas. Methylmercury (MeHg) concentrations in unfiltered streamwater ranged from 0.17 ng/L at a forest/wetlands site to 2.94 ng/L at an urban site. The percentage of THg present as MeHg increased as the percentage of forest + wetlands increased, but also was high in some urban areas. MeHg was detected only in groundwater <1 m below the water/sediment interface. Atmospheric deposition is presumed to be the main source of Hg to the wetlands and also may be a source to groundwater, where wastewater inputs in urban areas are hypothesized to mobilize Hg deposited to soils.     

Transformation of beech forest litter as a factor that triggers arsenic solubility in soils developed on historical mine dumps

Purpose

Soils that develop on the dumps in historical arsenic mining sites contain high concentrations of As thus constituting a serious environmental risk. This study was aimed to examine the changes in arsenic solubility in mine soils as induced by organic matter introduced with forest litter.

Materials and methods

Four large samples of initially developed soils were collected from the dumps remaining in former mining sites and were incubated for 90 days at various moistures: 80% of maximum water holding capacity and 100% (flooded conditions), with and without addition of beech forest litter (BL), 50 g/kg. Soils contained up to 5.0% As. Soil pore water was collected periodically with MacroRhizon suction samplers and examined on As, Mn, and Fe concentrations, pH, Eh, and dissolved organic carbon (DOC). The properties of dissolved organic matter were characterized by UV-VIS spectroscopic parameters A4/A6 and SUVA₂₅₄.

Results and discussion

Application of BL resulted in an intensive release of As from soils, particularly at 100% moisture. As concentrations in soil pore water increased strongly during the first 2 or 4 weeks of incubation and then started to decrease in all cases, except for one flooded soil. As was released particularly intensively from carbonate-containing soils. The mechanisms of As mobilization, including reductive dissolution of Mn and Fe oxides and the competition with DOC for sorption sites on the oxides, were discussed as related to soil properties. Pore water concentrations of DOC were increasing at the beginning of incubation and started to decrease after two or four weeks. Spectroscopic parameters of dissolved organic matter in ZS soils indicated increasing aromaticity and progress of humification.

Conclusions

Forest litter introduced to mine dump soils causes a mobilization of As into soil pore water. This effect, particularly strong in carbonate-rich soils, is apparently related to high concentrations of DOC and usually declines with time, which may be explained by the progress in humification. The relationships between DOC properties and As speciation in soil pore water should be dissected for better interpretation of experimental results.

     

Mercury and Methylmercury Dynamics in the Hyporheic Zone of an Oregon Stream

The role of the hyporheic zone in mercury (Hg) cycling has received limited attention despite the biogeochemically active nature of this zone and, thus, its potential to influence Hg behavior in streams. An assessment of Hg geochemistry in the hyporheic zone of a coarse-grained island in the Coast Fork Willamette River in Oregon, USA, illustrates the spatially dynamic nature of this region of the stream channel for Hg mobilization and attenuation. Hyporheic flow through the island was evident from the water-table geometry and supported by hyporheic-zone chemistry distinct from that of the bounding groundwater system. Redox-indicator species changed abruptly along a transect through the hyporheic zone, indicating a biogeochemically reactive stream/hyporheic-zone continuum. Dissolved organic carbon (DOC), total Hg, and methylmercury (MeHg) concentrations increased in the upgradient portion of the hyporheic zone and decreased in the downgradient region. Total Hg (collected in 2002 and 2003) and MeHg (collected in 2003) were correlated with DOC in hyporheic-zone samples: r ²?=?0.63 (total Hg-DOC, 2002), 0.73 (total Hg-DOC, 2003), and 0.94 (MeHg-DOC, 2003). Weaker Hg/DOC association in late summer 2002 than in early summer 2003 may reflect seasonal differences in DOC reactivity. Observed correlations between DOC and both total Hg and MeHg reflect the importance of DOC for Hg mobilization, transport, and fate in this hyporheic zone. Correlations with DOC provide a framework for conceptualizing and quantifying Hg and MeHg dynamics in this region of the stream channel, and provide a refined conceptual model of the role hyporheic zones may play in aquatic ecosystems.     

Benthic fluxes of mercury during redox changes in pristine coastal marine sediments from the Gulf of Trieste (northern Adriatic Sea)

Purpose

The Gulf of Trieste (northern Adriatic Sea) is an example of a coastal environment contaminated with mercury (Hg). Contamination is a consequence of nearly 500?years of activity at the Idrija Mine (western Slovenia), which is the second largest Hg mine in the world. Oxygen depletion can be common in the Gulf of Trieste due to late summer stratification of the water column and accumulation of labile organic matter. Since changing redox conditions can have an impact on Hg transformations, we studied the effect of oxygen depletion, in parallel with sulphide, iron (Fe), manganese (Mn), fluorescent dissolved organic matter (FDOM) and nitrogen (N) and phosphorus (P) availability, on total Hg and methylmercury (MeHg) fluxes from sediments.

Materials and methods

Pore water concentrations and benthic fluxes of total dissolved Hg and MeHg were studied in situ and in microcosm laboratory experiments using flux chambers encompassing three different stages: oxic, anoxic and reoxidation.

Results and discussion

Our experiments showed that in the oxic stage there were small effluxes of MeHg to the water column, which increased in the anoxic stage and dropped rapidly in a subsequent reoxic stage, showing influx. Our results support the hypothesis that MeHg desorption from reduced metal hydroxides under anoxic conditions, and co-precipitation with Fe-oxides and MeHg demethylation in the reoxidation stage, may play a major role in determining MeHg benthic fluxes. For Hg and MeHg, it appears that there is little relationship between their pore water distribution and flux and that of FDOM, i.e. humics.

Conclusions

The results indicate that there was no significant difference in Hg and MeHg pore water levels and their benthic fluxes between the contaminated northern and central parts of the Gulf of Trieste and the pristine southern part. This suggests that shallow and stratified coastal marine environments, in general, represent areas with a risk of high benthic release of toxic MeHg.     

Mercury Transport in a High-Elevation Watershed in Rocky Mountain National Park, Colorado

Mercury (Hg) was measured in stream water and precipitation in the Loch Vale watershed in Rocky Mountain National Park, Colorado, during 2001–2002 to investigate processes controlling Hg transport in high-elevation ecosystems. Total Hg concentrations in precipitation ranged from 2.6 to 36.2 ng/L and showed a strong seasonal pattern with concentrations that were 3 to 4 times higher during summer months. Annual bulk deposition of Hg was 8.3 to 12.4 μ g/m² and was similar to deposition rates in the Midwestern and Northeastern U.S. Total Hg concentrations in streams ranged from 0.8 to 13.5 ng/L and were highest in mid-May on the rising limb of the snowmelt hydrograph. Stream-water Hg was positively correlated with dissolved organic carbon suggesting organically complexed Hg was flushed into streams from near-surface soil horizons during the early stages of snowmelt. Methylmercury (MeHg) in stream water peaked at 0.048 ng/L just prior to peak snowmelt but was at or below detection (< 0.040 ng/L) for the remainder of the snowmelt season. Annual export of total Hg in Loch Vale streams ranged from 1.2 to 2.3 μ g/m², which was less than 20% of wet deposition, indicating the terrestrial environment is a net sink of atmospheric Hg. Concentrations of MeHg in stream water and corresponding watershed fluxes were low, indicating low methylation rates or high demethylation rates or both.