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.     

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.     

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.     

Comparison of total mercury and methylmercury cycling at five sites using the small watershed approach

The small watershed approach is well-suited but underutilized in mercury research. We applied the small watershed approach to investigate total mercury (THg) and methylmercury (MeHg) dynamics in streamwater at the five diverse forested headwater catchments of the US Geological Survey Water, Energy, and Biogeochemical Budgets (WEBB) program. At all sites, baseflow THg was generally less than 1ng L(-1) and MeHg was less than 0.2ng L(-1). THg and MeHg concentrations increased with streamflow, so export was primarily episodic. At three sites, THg and MeHg concentration and export were dominated by the particulate fraction in association with POC at high flows, with maximum THg (MeHg) concentrations of 94 (2.56)ng L(-1) at Sleepers River, Vermont; 112 (0.75)ng L(-1) at Rio Icacos, Puerto Rico; and 55 (0.80)ng L(-1) at Panola Mt., Georgia. Filtered (<0.7microm) THg increased more modestly with flow in association with the hydrophobic acid fraction (HPOA) of DOC, with maximum filtered THg concentrations near 5ng L(-1) at both Sleepers and Icacos. At Andrews Creek, Colorado, THg export was also episodic but was dominated by filtered THg, as POC concentrations were low. MeHg typically tracked THg so that each site had a fairly constant MeHg/THg ratio, which ranged from near zero at Andrews to 15% at the low-relief, groundwater-dominated Allequash Creek, Wisconsin. Allequash was the only site with filtered MeHg consistently above detection, and the filtered fraction dominated both THg and MeHg. Relative to inputs in wet deposition, watershed retention of THg (minus any subsequent volatilization) was 96.6% at Allequash, 60% at Sleepers, and 83% at Andrews. Icacos had a net export of THg, possibly due to historic gold mining or frequent disturbance from landslides. Quantification and interpretation of Hg dynamics was facilitated by the small watershed approach with emphasis on event sampling.     

Manipulation of snow in small headwater catchments at Storgama, Norway: effects on leaching of inorganic nitrogen

We have manipulated the winter-time soil temperature regime of small headwater catchments in a montane heathland area of southern Norway to study the possible effects on concentrations and fluxes of inorganic nitrogen in runoff. The experiments included extra insulation of soils in two catchments to prevent subzero temperatures during winter, and removal of snow in two other catchments to promote soil frost. Increased soil temperatures during winter increased the springtime concentrations and fluxes of ammonium (NH4) and nitrate (NO3) in runoff. By contrast, snow removal with development of significant soil frost showed no systematic effects on mean concentrations or fluxes of inorganic N. The results from our experiments suggest that warmer soils during winter caused by exceptionally mild winters, or alternatively a heavy snowpack, imply a greater risk for inorganic N leaching in this region than a possible increase of soil frost events because of reduced snow cover.     

Effects of environmental and maternally derived methylmercury on the embryonic and larval stages of walleye (Stizostedion vitreum)

The effects of environmental and maternally derived methylmercury (MeHg) on the embryonic and larval stages of walleye (Stizostedion vitreum) were investigated using eggs collected during two successive spawning seasons. Eggs were collected from fish in a mercury (Hg)-polluted environment (Clay Lake, Ontario, Canada), and from fish in two relatively pristine lakes (Lakes Manitoba and Winnipeg, in the province of Manitoba). Both bioaccumulation of Hg into muscle and its mobilization into eggs was significantly higher in Clay Lake females. Maternal muscle MeHg concentration was positively correlated with female length and egg MeHg was positively correlated with muscle MeHg concentration in all three populations. Hatching success of eggs from all three stocks declined significantly with increasing waterborne MeHg (0.1-7.8 ng l-1). Hatching success was not significantly affected by egg MeHg concentration. Embryonic heart rate declined with increasing waterborne MeHg concentration, but larval growth was not affected. Occurrence of larval deformities was negatively correlated with size of female, but was not significantly correlated with MeHg in either eggs or water. Larval MeHg was positively correlated with the concentrations of MeHg in eggs demonstrating transmission of MeHg from females. Uptake of ambient MeHg was higher in larvae exposed to higher waterborne MeHg concentrations.     

A screening model-based study of transport fluxes and fate of airborne mercury deposited onto catchment areas.

Dynamics of airborne mercury deposited onto catchment areas is investigated within the framework of a simulation model. Model results show that, for a particular atmospheric deposition rate, significant interannual variability in mercury transport flux in catchments is caused by climatology and corresponding differences in catchment soil loss rates; in comparison to the normal year, runoff flux increased by a factor of 2-3 for the wet year (rainfall 35% above normal) while for the dry year (rainfall 18% below normal) runoff flux decreased by factors of 5-7. The interaction of parameters describing soil type, topography and vegetation cover causes variability in both transport and emission fluxes among catchments; as soil loss rate increases by a factor of 5 due to variations in these parameters among the examined catchments, annual average transport flux increases by a factor of 3; and annual average emission flux of mercury (as Hg0) from soil to the atmosphere decreases by a factor of 2 due to the decreased levels of soil mercury associated with catchment soil loss increases. Seasonal variability of transport flux is associated with seasonal changes in precipitation and soil loss rates while seasonal changes of emission flux are primarily due to changes in soil moisture regime and temperature. Although modeled results are consistent with observational data from previous studies, they must be interpreted in a relative sense due to the screening-level character of this study.     

Mercury fluxes and pools in three subtropical forested catchments, southwest China

Forested catchments are an important part of the mercury (Hg) cycle and a link between the atmospheric and the aquatic environments. In this study, Hg input and output fluxes and its retention were investigated at subtropical forested catchments in southwest China. Significantly enhanced atmospheric Hg inputs were observed, and the contribution of litterfall Hg plays a more important role at these subtropical forested catchments. The ratios of Hg output fluxes from stream water to total input were 2.5% and 1.2% for LGS and TSP, which were markedly lower than those reported from Europe and North America. The current annual input Hg only accounted for 0.8 and 1.8 per mille to the Hg stored in the upper 90 cm of soil in LGS and TSP. These suggest that subtropical forested catchments are important for retention of atmospheric mercury deposition in southwest China.     

Heavy metal budgets for two headwater forested catchments in background areas of Finland.

Mean annual (1994-1996) budgets for Cd, Cu, Ni, Pb and Zn at two background, forested catchments, VK and HJ, in Finland are presented. Budgets for plots (VK3, HJ1 and HJ4) included throughfall (TF), litterfall (LF) and soil leaching fluxes, and for catchments terrestrial retention and leaching and lake sedimentation fluxes. Total deposition (TD) loads were relatively low (Cd < 0.1, Cu < 2, Ni < 1, Pb < 3 and Zn < 5 mg m-2 year-1) and that even in these areas almost half of the TD was in the form of dry deposition. Retention of TD within catchments was > or = 77% for all metals, except for Ni at VK (54%). For Cu and Pb, the retention was 94-97%. Most of the retention (74-97%) took place in the terrestrial part of the catchment, lake sedimentation accounting for the remainder. Plot-scale soil leaching fluxes at 40 cm of Cd, Cu (VK3) and Ni (VK3) were greater (> or = 100%) than TD inputs. Most of the catchment retention must therefore have taken place either deeper in the soil or in the lowland peatland areas. The humus layer was particularly effective in retaining Cu and Cd (65-81% and 51-78% of total inputs to the forest floor (TF + LF)). The retention of Pb by the humus layer was less than expected (26-54% of TF + LF). Litterfall was a particularly important internal flux for Zn.     

Concentrations of methylmercury in invertebrates from wetlands of the Prairie Pothole Region of North America

Prairie wetlands may be important sites of mercury (Hg) methylation resulting in elevated methylmercury (MeHg) concentrations in water, sediments and biota. Invertebrates are an important food resource and may act as an indicator of MeHg exposure to higher organisms. In 2007-2008, invertebrates were collected from wetland ponds in central Saskatchewan, categorized into functional feeding groups (FFGs) and analyzed for total Hg (THg) and MeHg. Methylmercury and THg concentrations in four FFGs ranged from 0.2-393.5 ng · g(-1) and 9.7-507.1 ng · g(-1), respectively. Methylmercury concentrations generally increased from gastropods with significantly lower average MeHg concentrations compared to other invertebrate taxa. Surrounding land use (agricultural, grassland and organic agricultural) may influence MeHg concentrations in invertebrates, with invertebrate MeHg concentrations being higher from organic ponds (457.5 ± 156.7 ng · g(-1)) compared to those from grassland ponds (74.8 ± 14.6 ng · g(-1)) and ponds on agricultural lands (32.8 ± 6.2 ng · g(-1)).     

Manipulation of snow in small headwater catchments at Storgama, Norway: effects on leaching of total organic carbon and total organic nitrogen

Projected increases in winter temperature due to future climate change may cause decreased snow accumulation at lower and intermediate altitudes in northern temperate regions. The resulting changes in soil temperature and water regime may affect the leaching of total organic carbon (TOC) and total organic nitrogen (TON). We manipulated the snow cover of small headwater catchments in a montane heathland area of southern Norway to quantify its effect on concentrations and fluxes of TOC and TON in runoff. Manipulations included snow removal, to promote soil frost, and insulation, to prevent soil frost. Snow removal resulted in increased TOC and TON concentrations, but decreased fluxes. Insulation caused a slight decrease in concentrations and fluxes of TOC. Our experiments show that a change in snow depth, and thus soil temperature, is not likely to have serious effects on TOC and TON leaching in the montane heathland area studied.     

Wet deposition mercury fluxes in the Canadian sub-Arctic and southern Alberta,measured using an automated precipitation collector adapted to cold regions

This paper reports mercury (Hg) concentrations and fluxes in precipitation that was collected from 2006 to 2008 at three sites in Canada: sub-Arctic boreal forest, sub-Arctic coast, and southern Alberta, using cold-adapted precipitation collectors which operated reliably at temperatures below ?30 °C during the study. The southern Alberta site (Crossfield) may be influenced by Calgary urban air, whereas the sub-Arctic coastal (Churchill, Manitoba) and boreal forest (Fort Vermilion, Alberta) sites are in more remote northern areas. Annual mean Hg concentrations in precipitation (5.0–9.2 ng L^?1) at the study sites were in the lower half of the range reported for southern Canada and the USA by the Mercury Deposition Network (MDN). But owing to typically low precipitation rates, gross wet Hg fluxes (0.54–2.0 μg m^?2 yr^?1) were among the lowest reported by MDN, with Crossfield having about twice the flux in 2007 of the other two sites. Flux was significantly correlated with precipitation, and thus was highest in summer (June–August) and lowest during winter, a pattern typical of other temperate continental locations. There was no evidence of higher wet Hg fluxes or concentrations in springtime at Churchill where atmospheric mercury depletion events (AMDEs) occur. Measured gross deposition fluxes at the study locations were ～2–8 times lower than estimated by GEOS-Chem and GRAHM atmospheric models. The largest discrepancy occurred for Churchill, which raises the question of how well Hg deposition from AMDEs is described by current models. Better agreement between measurements and models was obtained from MDN stations in Alberta and Alaska, where wet Hg fluxes were 2–10 times higher than the study sites either because of power plant emissions (Alberta), or because of high precipitation rates (Alaska).     

Characteristics of mercury speciation in Minnesota rivers and streams

Patterns of mercury (Hg) speciation were examined in four Minnesota streams ranging from the main-stem Mississippi River to small tributaries in the basin. Filtered phase concentrations of methylmercury (MeHg), inorganic Hg (IHg), and dissolved organic carbon (DOC) were higher in all streams during a major summertime runoff event, and DOC was enriched with MeHg but not with IHg. Particulate-phase MeHg and IHg concentrations generally increased with total suspended solids (TSS) concentrations but the event data did not diverge greatly from the non-event data, suggesting that sources of suspended sediments in these streams did not vary significantly between event and non-event samplings. The dissolved fractions (filtered concentration/unfiltered concentration) of both MeHg and IHg increased with increasing DOC concentrations, but varied inversely with TSS concentrations. While MeHg typically constitutes only a minor portion of the total Hg (THg) in these streams, this contribution is not constant and can vary greatly over time in response to watershed inputs.     

Mercury species of sediment and fish in freshwater fish ponds around the Pearl River Delta, PR China: human health risk assessment

This study investigated total mercury (THg) and methylmercury (MeHg) concentrations in five species of freshwater fish and their associated fish pond sediments collected from 18 freshwater fish ponds around the Pearl River Delta (PRD). The concentrations of THg and MeHg in fish pond surface sediments were 33.1-386 ng g(-1) dry wt and 0.18-1.25 ng g(-1) dry wt, respectively. The age of ponds affected the surface sediment MeHg concentration. The vertical distribution of MeHg in sediment cores showed that MeHg concentrations decreased with increasing depth in the top 10 cm. In addition, a significant correlation was observed between %MeHg and DNA from Desulfovibrionacaea or Desulfobulbus (p<0.05) in sediment cores. Concentrations of THg and MeHg in fish muscles ranged from 7.43-76.7 to 5.93-76.1 ng g(-1) wet wt, respectively, with significant linear relationships (r=0.97, p<0.01, n=122) observed between THg and MeHg levels in fish. A significant correlation between THg concentrations in fish (herbivorous: r=0.71, p<0.05, n=7; carnivorous: r=0.77, p<0.05, n=11) and corresponding sediments was also obtained. Risk assessment indicated that the consumption of largemouth bass and mandarin fish would result in higher estimated daily intakes (EDIs) of MeHg than reference dose (RfD) for both adults and children.     

Mercury transport between sediments and the overlying water of the St. Lawrence River area of concern near Cornwall, Ontario

Contaminated sediments in the St. Lawrence River remain a difficult problem despite decreases in emissions. Here, sediment and pore water phases were analyzed for total mercury (THg) and methyl mercury (MeHg) and diffusion from the sediment to the overlying water was 17.5 ± 10.6 SE ng cm⁻² yr⁻¹ for THg and 3.8 ± 1.7 SE ng cm⁻² yr⁻¹ for MeHg. These fluxes were very small when compared to the particle-bound mercury flux accumulating in the sediment (183 ± 30 SE ng cm⁻² yr⁻¹). Studies have reported that fish from the westernmost site have higher Hg concentrations than fish collected from the other two sites of the Cornwall Area of Concern, which could not be explained by differences in the Hg flux or THg concentrations in sediments, but the highest concentrations of sediment MeHg, and the greatest proportions of MeHg to THg in both sediment and pore water were observed where fish had highest MeHg concentrations.     

Methylmercury speciation in the dissolved phase of a stratified lake using the diffusive gradient in thin film technique

The diffusive gradient in thin film (DGT) technique was successfully used to monitor methylmercury (MeHg) speciation in the dissolved phase of a stratified boreal lake, Lake 658 of the Experimental Lakes Area (ELA) in Ontario, Canada. Water samples were conventionally analysed for MeHg, sulfides, and dissolved organic matter (DOM). MeHg accumulated by DGT devices was compared to MeHg concentration measured conventionally in water samples to establish MeHg speciation. In the epilimnion, MeHg was almost entirely bound to DOM. In the top of the hypolimnion an additional labile fraction was identified, and at the bottom of the lake a significant fraction of MeHg was potentially associated to colloidal material. As part of the METAALICUS project, isotope enriched inorganic mercury was applied to Lake 658 and its watershed for several years to establish the relationship between atmospheric Hg deposition and Hg in fish. Little or no difference in MeHg speciation in the dissolved phase was detected between ambient and spike MeHg.     

Manipulation of precipitation in small headwater catchments at Storgama, Norway: effects on leaching of organic carbon and nitrogen species

Projected changes in climate in Southern Norway include increases in summer and autumn precipitation. This may affect leaching of dissolved organic matter (DOM) from soils. Effects of experimentally added extra precipitation (10 mm week) during the growing season of 3 years (2004-2006) to small headwater catchments at Storgama (59 degrees 0'N, 550-600 m a.s.l.) on leaching of total organic carbon (TOC) and total organic nitrogen (TON) were assessed. Extra precipitation did not have a significant effect on average TOC and TON concentrations in runoff. Thus, fluxes of TOC and TON increased nearly proportionally with water fluxes. This suggests that a store of adsorbed and potentially mobile TOC and TON in catchment soils buffers the concentration of DOM in runoff. The size and dynamics of the pool of TOC and TON depends on the balance between production and leaching rates. Infrequent short droughts had only small effects on TOC and TON fluxes in runoff from the reference catchments.     

Spatial trend and pollution assessment of total mercury and methylmercury pollution in the Pearl River Delta soil, South China

Total mercury (THg) and methylmercury (MeHg) were measured in large number of soil samples collected from areas with different types of land use, different depth in the Pearl River Delta (PRD) of South China. THg and MeHg concentrations ranged from 16.7 to 3320 ng g⁻¹ and 0.01 to 1.34 ng g⁻¹, respectively. THg levels are highest in the top 0-20 cm soil layer, and decrease from the surface to bottom layer soil. Spatial variation was observed with different types of land use. Urban parks had the highest concentrations and the other areas tended to decrease in the order of residential areas, industrial areas, vegetable fields, cereal fields, and woodlands. Temporal variation was also noted, and two relatively high THg contamination zones located in the northwestern part of the PRD have significantly expanded over the last two decades. Both THg and MeHg concentrations were correlated significantly with soil organic matter (OM), but not with soil pH. THg pollution status was evaluated using two assessment methods.     

Behaviour of arsenic in forested catchments following a high-pollution period

Due to high availability of adsorption sites, forested catchments could be net sinks for pollutant arsenic both during the period of increasing and decreasing pollution. We tested this hypothesis along a north-south pollution gradient in spruce die-back affected areas of Central Europe. For two water years (2007-2008), we monitored As fluxes via spruce-canopy throughfall, open-area precipitation, and runoff in four headwater catchments (Czech Republic). Since 1980, atmospheric As inputs decreased 26 times in the north, and 13 times in the south. Arsenic export by runoff was similar to atmospheric inputs at three sites, resulting in a near-zero As mass balance. One site exhibited a net export of As (2.2 g ha⁻¹ yr⁻¹). In contrast, the preceding period (1995-2006) showed much higher As fluxes, and higher As export. Czech catchments do not serve as net sinks of atmospheric As. A considerable proportion of old industrial arsenic is flushed out of the soil.     

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.