Diel changes in water chemistry in an arsenic-rich stream and treatment-pond system

Arsenic concentrations are elevated in surface waters of the Warm Springs Ponds Operable Unit (WSPOU), located at the head of the upper Clark Fork River Superfund site, Montana, USA. Arsenic is derived from historical deposition of smelter emissions (Mill and Willow Creeks) and historical mining and milling wastes (Silver Bow Creek). Although long-term monitoring has characterized the general seasonal and flow-related trends in As concentrations in these streams and the pond system used to treat Silver Bow Creek water, little is known about solubility controls and sorption processes that influence diel cycles in As concentrations. Diel (24-h) sampling was conducted in July 2004 and August 2005 at the outlet of the treatment ponds, at two locations along a nearby reconstructed stream channel that diverts tributary water around the ponds, and at Silver Bow Creek 2 km below the ponds. Dissolved As concentration increased up to 51% during the day at most of the stream sites, whereas little or no diel change was displayed at the treatment-pond outlet. The strong cycle in streams is explained by pH- and temperature-dependent sorption of As onto hydrous metal oxides or biofilms on the streambed. Concentrations of dissolved Ca(2+) and HCO(3)(-) at the stream sites showed a diel temporal pattern opposite to that of As, and geochemical modeling supports the hypothesis that the concentrations of Ca(2+) and HCO(3)(-) were controlled by precipitation of calcite during the warm afternoon hours when pH rose above 9.0. Nightly increases in dissolved Mn and Fe(II) concentrations were out of phase with concentrations of other divalent cations and are more likely explained by redox phenomena.     

Mercury speciation and exchanges at the air-water interface of a tropical artificial reservoir, French Guiana

The distribution and speciation of mercury (Hg) in air, rain, and surface waters from the artificial tropical lake of Petit-Saut in French Guiana were investigated during the 2003/04 period. In the air, total gaseous mercury (TGM) at the dam station averaged 12+/-2 pmol m(-3) of which >98% was gaseous elemental mercury (GEM). GEM distribution depicted a day-night cycling with high concentrations (up to 15 pmol m(-3)) at dawn and low concentrations (down to 5 pmol m(-3)) at nightfall. Reactive gaseous mercury (RGM) represented <1% of the GEM with a mean concentration of 4+/-3 fmol m(-3). Diel RGM variations were negatively related to GEM. In the rain, the sum of all Hg species in the unfiltered (HgT(UNF)) averaged 16+/-12 pmol L(-1). Temporal distribution of HgT(UNF) exhibited a pattern of high concentrations during the late dry seasons (up to 57.5 pmol L(-1)) and low concentrations (down to 2.7 pmol L(-1)) in the course of the wet seasons. Unfiltered reactive (HgR(UNF)), dissolved gaseous (DGM) and monomethyl (MMHg(UNF)) Hg constituted 20, 5 and 5% of HgT(UNF), respectively. All measured Hg species were positively related and displayed negative relationships with the pH of the rain. In the reservoir surface waters, dissolved total mercury (HgT(D)) averaged 3.4+/-1.2 pmol L(-1) of which 10% consisted of DGM. DGM showed a trend of high concentrations during the dry seasons (480+/-270 fmol L(-1)) and lower (230+/-130 fmol L(-1)) in the course of the wet seasons. Diel variations included diurnal photo-induced DGM production (of about 60 fmol L(-1) h(-1)) coupled to minute to hour oxidation/reduction cycles (of >100 fmol L(-1) amplitude). Finally, calculated atmospheric Hg inputs to the Petit-Saut reservoir represented 14 mol yr(-1) whereas DGM evasion reached 23 mol yr(-1). Apportionment among forms of Hg deposition indicated that up to 75% of the total Hg invasive flux follows the rainfall pathway.     

Mercury and trace metal partitioning and fluxes in suburban Southwest Ohio watersheds

Many natural watersheds are increasingly affected by changes in land use associated with suburban sprawl and such alterations may influence concentrations, partitioning, and fluxes of toxic trace metals in fluvial ecosystems. We investigated the cycling of mercury (Hg), monomethylmercury, cadmium, copper, lead, nickel, and zinc in three watersheds at the urban fringe of Dayton, Ohio, over a 13-month period. Metal concentrations were related positively to discharge in each stream, with each metal having a high affinity for suspended particles and Hg also having a noticeable association with dissolved organic carbon. Although not observed for the other metals, levels of Hg in river water varied seasonally and among streams. Yields of Hg from two of the catchments were comparable to that predicted for runoff of atmospherically deposited Hg (∼25% of wet atmospheric flux), whereas the third watershed had a significantly greater annual flux associated with greater particle-specific and filtered water Hg concentrations, presumably from a point source. Fluxes of metals other than Hg were similar among each watershed and suggestive of a ubiquitous source, which could be either atmospheric deposition or weathering. Results of this study indicate that, with the exception of Hg being increased in one watershed, processes affecting metal partitioning and loadings are similar among southwest Ohio streams and comparable to other North American rivers that are equally or less impacted by urban development. Relative differences in land use, catchment area, and presence or absence of waste water treatment facilities had little or no detectable effect on most trace metal concentrations and fluxes. This suggests that suburban encroachment on agricultural and undeveloped lands has either similarly or not substantially impacted trace metal cycling in streams at the urban fringe of Dayton and, by extension, other comparable metropolitan areas.     

Importance of monsoon rainfall in mass fluxes of filtered and unfiltered mercury in Gwangyang Bay, Korea

We investigated the effects of the East Asian Summer Monsoon (EASM), which brings approximately half of Korea's annual rainfall in July, on the concentration and particle-water partitioning, and sources of Hg in coastal waters. Surface seawater samples were collected from eight sites in Gwangyang Bay, Korea, during the monsoon (July, 2009) and non-monsoon dry (April and November, 2009) seasons and the concentrations of suspended particulate matter, chlorophyll-a, and unfiltered and filtered Hg were determined. We found significant (p < 0.05) increases in filtered Hg in the monsoon season (1.8 ± 0.019 pM) compared to the dry season (0.62 ± 0.047 pM). In contrast, the Hg concentrations associated with particles showed no significant differences (p > 0.05) between the monsoon (459 ± 141 pmol g^− 1) and the dry season (346 ± 30 pmol g^− 1), which resulted in decreased particle-water partition coefficients of Hg in the monsoon season compared to the values in the dry season: 5.7 ± 0.1 in April, 5.3 ± 0.1 in July, and 5.8 ± 0.1 in November. The annual Hg input to Gwangyang Bay was estimated at 64 ± 6.6 mol yr^− 1 and 27 ± 1.9 mol yr^− 1 for unfiltered and filtered Hg, respectively. The Hg discharged from rivers was a major source of Hg in Gwangyang Bay: the river input contributed 83 ± 13% of total input of unfiltered and 73 ± 6.0% of filtered Hg. On a monthly basis, unfiltered Hg input was 17 ± 11 mol month^− 1 in the monsoon season and 3.2 ± 0.70 mol month^− 1 in the dry season, while filtered Hg input was 7.1 ± 4.1 mol month^− 1 in the monsoon and 1.3 ± 0.26 mol month^− 1 in the dry. Consequently, the EASM resulted in an unfiltered Hg input 5.3 times greater than the mean dry month input and a filtered Hg input 5.5 times greater than the mean dry month input, which is mainly attributable to enhanced river water discharge during the monsoon season.     

Methylmercury input to the Mississippi River from a large metropolitan wastewater treatment plant

Methylmercury (MeHg) and total mercury (THg) inputs to the Mississippi River from a large metropolitan wastewater treatment plant were measured to characterize the relative contribution of the treatment plant to in-stream loads of these contaminants. Concentrations of MeHg and THg were determined in filtered and unfiltered whole water samples collected weekly from the treatment plant effluent stream and from the river upstream of the plant discharge. Unfiltered MeHg concentrations in the plant effluent ranged from 0.034 to 0.062 ng L(-1) and were always less than those in the river (range: 0.083-0.227 ng L(-1)). The MeHg loading to the river from the treatment plant ranged from 0.026 to 0.051 g d(-1) and averaged 0.037 g d(-1) over the 13-week sampling period. The in-stream MeHg load in the river upstream varied widely depending on hydrologic conditions, ranging from 0.91 to 18.8 g d(-1) and averaging 4.79 g d(-1). The treatment plant discharge represented 1.6%, on average, of the in-stream MeHg load, ranging from 0.2 to 3.5% depending on flow conditions in the river. MeHg in treatment plant effluent was primarily in the filtered phase (mean: 57%, <0.2 microm), but in the river the filtered/unfiltered ratio (F/UF) was typically less than 30% except during a major precipitation runoff event, when F/UF increased to 78%. The MeHg/THg ratio in unfiltered treatment plant effluent varied little (range: 1.6-1.9%), suggesting that THg concentration can serve as a relatively accurate proxy for MeHg concentration in this effluent stream. Supplemental sampling of the treatment plant influent stream showed that removals of MeHg and THg across the treatment process averaged 97% and 99%, respectively. These results show the treatment plant to be effective in removing MeHg and THg from wastewater and in minimizing its impact on Hg levels in the receiving water.     

Concentration of mercury, methylmercury, cadmium, lead, arsenic, and selenium in the rain and stream water of two contrasting watersheds in western Maryland.

Weekly wet deposition and throughfall rain samples were collected in the Blacklick Run (BLK) and Herrington Creek Tributary (HCRT), two streams in western Maryland (MD). Samples were analyzed for total mercury (Hg), methylmercury (MMHg). arsenic (As), selenium (Se), cadmium (Cd), and Icad (Pb). Hg concentrations generally fell between 50 and 100 pM. comparable to concentrations in wet deposition measured at other MD sites. While Hg concentrations decreased with rainfall amount, a similar washout trend was not seen for MMHg. Cd, Pb, As, and Se concentrations were comparable overall to those measured in the region. Concentrations of Hg, Cd, and Pb in throughfall were similar between sites and equivalent or higher than wet deposition concentrations. As and Se concentrations were similar in throughfall at the two sites, though throughfall at BLK seemed to be punctuated with slightly higher concentrations of these two metals. Concentrations of Hg, MMHg, Cd, Pb, As, Se, and SPM were measured in monthly stream collections and compared with concentrations found in other MD rivers. In addition to the monthly collections, four storm events were sampled. These measurements demonstrate the importance of storm events in trace metal transport, especially for Hg, Pb and MMHg. For these metals, a strong correlation between metal and suspended particulate concentration was evident. Retention efficiencies of the watersheds for the metals were calculated for each watershed. Of all the metals, Hg is the most and As is the least strongly retained in the watershed.     

Distribution, speciation, and transport of mercury in stream-sediment, stream-water, and fish collected near abandoned mercury mines in southwestern Alaska, USA

Concentrations of total Hg, Hg (II), and methylmercury were measured in stream-sediment, stream-water, and fish collected downstream from abandoned mercury mines in southwestern Alaska to evaluate environmental effects to surrounding ecosystems. These mines are found in a broad belt covering several tens of thousands of square kilometers, primarily in the Kuskokwim River basin. Mercury ore is dominantly cinnabar (HgS), but elemental mercury (Hg degrees) is present in ore at one mine and near retorts and in streams at several mine sites. Approximately 1400 t of mercury have been produced from the region, which is approximately 99% of all mercury produced from Alaska. These mines are not presently operating because of low prices and low demand for mercury. Stream-sediment samples collected downstream from the mines contain as much as 5500 microg/g Hg. Such high Hg concentrations are related to the abundance of cinnabar, which is highly resistant to physical and chemical weathering, and is visible in streams below mine sites. Although total Hg concentrations in the stream-sediment samples collected near mines are high, Hg speciation data indicate that concentrations of Hg (II) are generally less than 5%, and methylmercury concentrations are less than 1% of the total Hg. Stream waters below the mines are neutral to slightly alkaline (pH 6.8-8.4), which is a result of the insolubility of cinnabar and the lack of acid-generating minerals such as pyrite in the deposits. Unfiltered stream-water samples collected below the mines generally contain 500-2500 ng/l Hg; whereas, corresponding stream-water samples filtered through a 0.45-microm membrane contain less than 50 ng/l Hg. These stream-water results indicate that most of the Hg transported downstream from the mines is as finely-suspended material rather than dissolved Hg. Mercury speciation data show that concentrations of Hg (II) and methylmercury in stream-water samples are typically less than 22 ng/l, and generally less than 5% of the total Hg. Muscle samples of fish collected downstream from mines contain as much as 620 ng/g Hg (wet wt.), of which 90-100% is methylmercury. Although these Hg concentrations are several times higher than that in fish collected from regional baseline sites, the concentration of Hg in fish is below the 1000 ng/g action level for edible fish established by the US Food and Drug Administration (FDA). Salmon contain less than 100 ng/g Hg, which are among the lowest Hg contents observed for fish in the study, and well below the FDA action level.     

Atmospheric mercury depletion event study in Ny-Alesund (Svalbard) in spring 2005. Deposition and transformation of Hg in surface snow during springtime

A field campaign was conducted in Ny-Alesund (78 degrees 54'N, 11 degrees 53'E), Svalbard (Norway) during April and May 2005. An Atmospheric Mercury (Hg) Depletion Event (AMDE) was observed from the morning of April 24 until the evening of April 27. Transport of already Hg and ozone (O3) depleted air masses could explain this observed depletion. Due to a snowfall event during the AMDE, surface snow Hg concentrations increased two fold. Hg deposition took place over a short period of time corresponding to 3-4 days. More than 80% of the deposited Hg was estimated to be reemitted back to the atmosphere in the days following the event. During the campaign, we observed night and day variations in surface snow Hg concentrations, which may be the result of gaseous elemental mercury (GEM) oxidation to divalent Hg at the snow/air interface by daylight surface snow chemistry. Finally, a decrease in the reactive Hg (HgR) fraction of total Hg (HgT) in the surface snow was observed during spring. We postulate that the transformation of HgR to a more stable form may occur in Arctic snow during spring.     

Mercury in the bivalves Anadara (Senilia) senilis,Perna perna and Crassostrea tulipa from Ghana

Three bivalves: Anadara (Senilia) senilis (n=220), Crassostrea tulipa (n=260) from two 'open' lagoons (Benya and Ningo) and a 'closed' lagoon (Sakumo), and Perna perna (n=170) from rocky shores adjacent to Benya and Sakumo, were analyzed for their total and organic Hg concentrations and total body burden. Median concentrations for cockles were 0.20 micro/gdw for the wet season and 0.36 microg/gdw for the dry season. Total mercury concentration for both mussels and oysters ranged from 0.04 to 0.84 microg/gdw. Seasonal variations and age effect were detected in all the species but no significant spatial variation was found along the coast. Organic (methyl) mercury concentration ranged from 0.03 to 0.55 microg/gdw was stable without age effect. The median relative organic mercury varied between 30 and 80% depending on the season, location, species and the type of lagoon. The lower concentrations in the wet season were due to primary production and dilution effect. Log-transformed regression relationships between body burden and size were used to compare the species.     

Mercury in ground water, septage, leach-field effluent, and soils in residential areas, New Jersey coastal plain

Water samples were collected from domestic wells at an unsewered residential area in Gloucester County, New Jersey where mercury (Hg) concentrations in well water were known to exceed the USEPA maximum contaminant level (MCL) of 2,000 ng/L. This residential area (the CSL site) is representative of more than 70 such areas in southern New Jersey where about 600 domestic wells, sampled previously by State and county agencies, yielded water containing Hg at concentrations that exceed the MCL. Recent studies indicate that background concentrations of Hg in water from this unconfined sand and gravel aquifer system are <10 ng/L. Additional sampling was conducted at the CSL site in order to better understand sources of Hg and potential Hg transport mechanisms in the areas with Hg-contaminated ground water. At the CSL site, concentrations of Hg were substantially lower (although still exceeding the MCL in some cases) in filtered water samples than in the unfiltered water samples collected previously from the same wells. Surfactants and elevated concentrations of sodium, chloride, nitrate, ammonium, and phosphate in water from domestic and observation wells indicated septic-system effects on water quality; detections of sulfide indicated localized reducing conditions. Hg concentrations in septage and leach-field effluent sampled at several other households in the region were low relative to the contaminant-level Hg concentrations in water from domestic wells. Relations of Hg concentrations in leach-field effluent to iron concentrations indicate that reductive dissolution of iron hydroxides in soils may release Hg to the percolating effluent.     

Mercury and methylmercury in the Gulf of Trieste (northern Adriatic Sea)

The distribution, sources and fate of mercury (Hg) in the water column of the Gulf of Trieste (northern Adriatic Sea), affected by the Hg polluted river Soca/Isonzo for centuries draining the cinnabar-rich deposits of the Idrija mining district (NW Slovenia), were studied in terms of total and dissolved Hg, reactive Hg, total and dissolved methylmercury (MeHg), mesozooplankton Hg and MeHg, and sedimentation rates of particulate Hg. Higher total Hg concentrations in the surface layer were restricted to the area of the Gulf in front of the river plume expanding in a westerly direction. Higher concentrations in bottom water layers were the consequence of sediment resuspension. Dissolved Hg exhibited higher concentrations in the surface layer in the area in front of the river plume. Higher bottom concentrations of dissolved Hg observed at some stations were probably due to remobilization from sediments, including resuspension and benthic recycling. The relationship between dissolved Hg in the surface layer and salinity showed nonconservative mixing in June 1995 during higher riverine inflow and nearly conservative mixing in September 1995 during lower riverine inflow. Both mixing curves confirm the river Soca/Isonzo to be the most important source of total and dissolved Hg, which are significantly correlated, in the Gulf. Reactive Hg is significantly correlated with dissolved Hg, indicating that the majority of dissolved Hg is reactive and potentially involved in biogeochemical transformations. The higher total MeHg in the bottom layer is the result of remobilization of MeHg from sediments including benthic fluxes. Strong seasonal variation of sedimentation rates of particulate Hg was found during a 2-year study in the central part of the Gulf. These variations followed those of total sedimented matter, indicating that sedimented Hg is mostly associated with inorganic matter. About a 2.5-fold higher fluxes of particulate Hg were observed at the depth of 20 m relative to 10 m which is attributed to bottom sediment resuspension. Temporal variability of mesozooplankton Hg and MeHg is the consequence of biomass and species variations, and grazing behaviour. From the preliminary Hg mass balance it appears that the Gulf is an efficient trap for total Hg and a net source of MeHg.     

The influence of humic substances on the speciation and bioavailability of dissolved mercury and methylmercury, measured as uptake by Chaoborus larvae and loss by volatilization

The influence of dissolved humic substances (HS) on the bioavailability of dissolved inorganic and methyl mercury (Hg) was quantified by measuring the direct uptake of 203Hg in Chaoborus larvae using laboratory microcosms containing artificial freshwater. The animals were exposed individually in triplicate aquaria at 10 different concentrations of HS covering the whole range found in natural freshwaters (0-110 mg C l(-1)). Mercury-203 concentrations were monitored repeatedly in the same individuals and in their ambient water during up to 10 days. Near-steady state Hg concentrations in Chaoborus were usually reached within 5 days. The bioconcentration factor (BCF, direct uptake only) for the larvae in the absence of HS was 0.55+/-0.09 (S.E.) ml individual(-1) for inorganic Hg and 5.3+/-0.7 ml individual(-1) for methyl Hg, thus showing a 10-fold difference. Normalizing to the organic carbon content of the larvae yields a BCF(OC) in the absence of HS of 2.8+/-0.4 x 10(3) ml (gC)(-1) for inorganic Hg and 2.7+/-0.3 x 10(4) ml (gC)(-1) for methyl Hg. The uptake of both inorganic and methyl Hg decreased markedly with increasing concentration of HS. For inorganic Hg, the decrease in uptake was most pronounced at HS concentrations below 0.2 mg C l(-1). For methyl Hg, the relationship between uptake and log([HS]) was sigmoid, showing a reduction by > 90% when increasing HS concentrations from 1 to 50 mg C l(-1). Similar patterns were observed for losses of Hg from the water phase, mainly through volatilization. These results have implications for both the biouptake and the abiotic cycling of Hg in natural ecosystems and suggest that most dissolved inorganic Hg is bound to dissolved organic matter in most natural freshwaters, whereas dissolved methyl Hg is bound only in humic waters. Assuming that only free aqueous Hg is taken up by the organisms, the rather simple methodology employed here can be used for estimating distribution coefficients (K(OC)) for Hg between HS and water. In this study, the K(OC) values were 2.5+/-0.7 (S.E.) x 10(7) ml (gC)(-1) for inorganic Hg and 1.5+/-0.6 x 10(5) ml (gC)(-1) for methyl Hg. Values of similar magnitude were derived from observed losses of Hg from the water phase, supporting the assumption of an immobilization of both inorganic and methyl Hg by HS. The strong negative influence of dissolved HS on the bioavailability of both inorganic and methyl Hg in freshwater suggests that the high Hg levels often found in fish from humic lakes in the boreal forest zone cannot be explained alone by direct uptake of methyl Hg from the water phase into biota at low trophic levels.     

Experimental evidence against diffusion control of Hg evasion from soils

Elemental Hg (Hg(0)) evolution from soils can be an important process and needs to be measured in more ecosystems. The diffusion model for soil gaseous efflux has been applied to modeling the fluxes of several gases in soils and deserves testing with regard to Hg(0). As an initial test of this model, we examined soil gaseous Hg(0) and CO(2) concentrations at two depths (20 and 40 cm) over the course of a controlled environment study conducted in the EcoCELLs at the Desert Research Institute in Reno, Nevada. We also compared small, spatially distributed gas wells against the more commonly used large gas wells. In this study, two EcoCELLs were first watered (June 2000) and then planted (July 2000) with trembling aspen (Populus tremuloides). Following that, trees were harvested (October 2000) and one EcoCELL (EcoCELL 2) was replanted with aspen (25 April 2001). During most of the experiment, there was a strong vertical gradient of CO(2) (increasing with depth, as is typical of a diffusion-driven process), but no vertical gradient of soil gaseous Hg(0). Strong diel variations in soil gas Hg(0) concentration were noted, whereas diel variations in CO(2) were small and not statistically significant. Initial watering and planting caused increases in both soil gas CO(2) and Hg(0). Replanting in EcoCELL 2 caused a statistically significant increase in soil gas CO(2) but not Hg(0). Calculated Hg(0) effluxes using the diffusion model produced values two orders of magnitude lower than those measured using field chambers placed directly on the soil or whole-cell fluxes. Neither soil gas Hg(0) concentrations nor calculated fluxes were correlated with measured Hg(0) efflux from soil or from whole EcoCELLs. We conclude that (1) soil gas Hg(0) flux is not diffusion-driven and thus soil gas Hg(0) concentrations cannot be used to calculated soil Hg(0) efflux; (2) soil gas Hg(0) concentrations are increased by watering dry soil, probably because of displacement/desorption processes; (3) soil gas Hg(0) concentrations were unaffected by plants, suggesting that roots and rhizosphere processes are unimportant in controlling Hg(0) evasion from the soil surface. We recommend the use of the small wells in all future studies because they are much easier to install and provide more resolution of spatial and temporal patterns in soil gaseous Hg(0).     

Mercury distribution and speciation in Lake Balaton, Hungary

The distribution and speciation of mercury in air, rain, lake water, sediment, and zooplankton in Lake Balaton (Hungary) were investigated between 1999 and 2002. In air, total gaseous mercury (TGM) ranged from 0.4 to 5.9 ng m(-3) and particulate phase mercury (PPM) from 0.01 to 0.39 ng m(-3). Higher concentrations of both TGM and PPM occurred during daytime. Higher concentrations of PPM occurred in winter. In rain and snow, total mercury ranged from 10.8 to 36.7 ng L(-1) in summer but levels up to 191 ng L(-1) in winter. Monomethylmercury (MMHg) concentrations ranged from 0.09 to 1.26 ng L(-1) and showed no seasonal variations. Total Hg in the unfiltered lake water varied spatially, with concentrations ranging from 1.4 to 6.5 ng L(-1). Approximately 70% of the total Hg is dissolved. MMHg levels ranged from 0.08 to 0.44 ng L(-1) as total and from 0.05 to 0.37 ng L(-1) in the dissolved form. Lower Hg concentrations in the water column occurred in winter. In suspended particulate matter and in sediment, total mercury ranged from 9 to 160 ng g(-1) dw, and MMHg ranged from 0.07 to 0.84 ng g(-1) dw. In zooplankton, an average mercury level of 31.0+/-6.8 ng g(-1) dw occurred, with MMHg accounting for approximately 17%. In sediments, suspended-matter- and zooplankton-high Hg and MMHg levels occurred at the mouth of the River Zala, but, in the lake, higher concentrations occurred on the Northern side, and an increasing trend from north-west to north-east was observed. In general, regarding Hg, Lake Balaton can be considered as a relatively uncontaminated site. The high-pH and well-oxygenated water as well as the low organic matter content of the sediment does not favour the methylation of Hg. In addition, bioconcentration and bioaccumulation factors are relatively low compared to other aquatic systems.     

Methylmercury in rivers draining cultivated watersheds

Total mercury (THg) concentrations in streams draining cultivated watersheds in Minnesota, USA are strongly correlated with total suspended sediment (TSS) concentrations, varying widely in response to precipitation-driven inputs of soil-derived suspended sediments. Methylmercury (MeHg) concentrations in these waterways have not been studied, and little is known about mercury uptake mechanisms in resident fish populations. To begin to identify factors influencing MeHg concentrations and loadings in these streams, we measured THg and MeHg concentrations in unfiltered whole water samples from the Minnesota River and two of its major tributaries, the Blue Earth and Le Sueur Rivers. Land use in the watersheds of these rivers is over 90% row-crop agriculture, and extensive artificial drainage systems deliver runoff and associated solids quickly to local streams and rivers. THg concentrations were elevated (>10 ng/l) during much of Spring 2000 and part of the summer when runoff from precipitation events increased stream discharge and carried soil materials into the streams. Reduced precipitation resulted in low flow conditions from August through October, and THg concentrations decreased to <4.0 ng/l in all three rivers. MeHg concentrations in the Le Sueur River ranged from 0.07 to 0.42 ng/l between June and December. Higher MeHg concentrations (>0.2 ng/l) were measured during summer months when THg and TSS concentrations were high after precipitation events. Elevated MeHg concentrations were also observed in late October after leaf litter inputs. Conditions on the Blue Earth River were different, with elevated MeHg concentrations (>0.5 ng/l) observed during low flow in August and September. These higher concentrations coincided with a period of enhanced microbial growth stimulated by high late-summer temperatures. A late-October increase in MeHg concentration attributed to leaf litter inputs was also observed in this river. MeHg concentration trends in the Minnesota River were similar to those in the Blue Earth River. Indicators of biological productivity (chlorophyll a, volatile suspended solids, and total Kjeldahl nitrogen) were higher in the Blue Earth and Minnesota Rivers compared to the Le Sueur River, which may signal a connection between higher biological activity and increased MeHg concentrations.     

Mercury storage in surface soils in a central Washington forest and estimated release during the 2001 Rex Creek Fire

Recent investigations indicate that wildfires provide a significant flux of mercury (Hg) from terrestrial ecosystems to the atmosphere. However, little is known about how geographic location, climate, stand age, and tree species affect Hg accumulation prior to burning and loss during burning. Soil cores collected in sites burned during the summer 2001 Rex Creek Fire in the eastern Cascade Mountains (Washington State, USA) and in adjacent unburned control sites indicate that Hg loss from soils during the Rex Creek Fire averaged 6.7 (+/-2.5) g Hg ha(-1). This soil profile-based estimate of Hg release is higher than a previous estimate for the same fire based on airborne measurements of Hg and CO concentrations in smoke. This study has implications for global estimates of Hg storage in forests and release to the atmosphere during wildfires.     

Diurnal variation of dissolved gaseous mercury (DGM) levels in a southern reservoir lake (Tennessee, USA) in relation to solar radiation

Variations of dissolved gaseous mercury (DGM) concentrations in a southern reservoir lake (Cane Creek Lake, Cookeville, TN, USA) in relation to solar radiation were investigated consecutively from June 2003 to May 2004. The daytime DGM levels in the lake exhibited a two-phase diurnal trend; the DGM concentrations rose in the morning, peaked around noontime and then fell in the afternoon through the evening; these trends followed the general pattern of diurnal solar radiation variations. The morning and afternoon phases appeared to be asymmetrical with the former relatively steep and the latter gradual. A variety of daytime DGM level variations other than the typical two-phase diurnal patterns were also observed. For the time spans studied, the daytime mean DGM concentrations of the lake ranged from 12 to 68 pg L(-1) (60-340 fM). The daytime mean DGM levels in the summertime (June, July, August) showed values above 30 pg L(-1) (150 fM) in most cases and a large number of peak DGM concentrations above 50 pg L(-1) (250 fM). The summer DGM levels in the lake appear to be comparable to those observed in the large northern lakes for the summertime. The daytime DGM levels in the lake were found to correlate with solar radiation to various degrees (cases of r values above 0.8: approximately 12% and approximately 18% of the total sampling days for correlation with global solar radiation and UVA radiation, respectively). Correlating trends are recognizable between the daytime mean DGM concentration and the corresponding mean global solar radiation (r = 0.66, p < 0.0005) and between the daytime mean DGM concentration and the corresponding mean UVA radiation (r = 0.62, p < 0.0005).     

Influence of filtration on concentrations of 62 elements analysed on crystalline bedrock groundwater samples by ICP-MS.

Analyses of unfiltered and filtered (< 0.45 micron and < 0.10 micron) groundwater samples from 15 selected wells in crystalline bedrock aquifers of the Oslo area, Norway, have been studied for 62 chemical elements. While concentrations of almost all elements vary over several orders of magnitude between the individual wells, the discrepancy between filtered and unfiltered samples from the same well are rather small, not exceeding one order of magnitude. Many elements show no influence of filtration at all, while one element (Sn) suggests that filtration may actually introduce contamination to the samples. Correlation between unfiltered and filtered samples is high for most elements. The study shows that: (1) even unfiltered samples will satisfactorily reflect general water chemistry as long as drinking water (i.e. by definition rather 'clean' water, with low particulates) is collected; (2) filtered samples do not necessarily reflect 'true' solution chemistry (an elusive concept); and (3) the differences between samples filtered at < 0.45 micron and < 0.10 micron are so minimal for most elements, that the additional effort invested in ultra-filtration may not be justified for bedrock groundwater samples.     

Temporal and spatial distributions of phosphine in Taihu Lake, China

Phosphine is a natural gaseous carrier of phosphorus in its geochemical cycles, and it might be of importance to the phosphorus balance of eutrophic lakes. Phosphine concentration levels in Taihu Lake, a typical shallow eutrophic lake in China, were intensely investigated in this work. Results show that in the period of 2002 the variation of phosphine concentration in the atmosphere near Taihu Lake is significant, with a maximum value 2.85 pg/l. Concurrent sampling of phosphine in surface and bottom water of the lake had no distinct change. The mean concentration of phosphine in the water ranged from 1.92 to 3.01 pg/l. Approximately 84-90% of the phosphine was removed from lake water during passage of the sample through a 0.45 microm pore size filter, i.e. the average phosphine concentrations of filtered lake water in all sampling locations were from 0.37 to 0.40 pg/l with the highest value 0.73 pg/l and the lowest 0.08 pg/l, whereas phosphine concentrations in unfiltered samples were 5-9 times higher. Phosphine levels in lake sediments were positively correlated with different contamination of the samples. The concentration levels of phosphine were also higher in severe polluted sites. The local average values of the phosphine concentrations were from 21550 to 563,100 pg/kg. Its highest value was 919,238 pg/kg at 6# site (Zhihu harbor), a severely polluted sampling site.     

Distribution of total and methyl mercury in sediments along Steamboat Creek (Nevada, USA)

In the late 1800s, mills in the Washoe Lake area, Nevada, used elemental mercury to remove gold and silver from the ores of the Comstock deposit. Since that time, mercury contaminated waste has been distributed from Washoe Lake, down Steamboat Creek, and to the Truckee River. The creek has high mercury concentrations in both water and sediments, and continues to be a constant source of mercury to the Truckee River. The objective of this study was to determine concentrations of total and methyl mercury (MeHg) in surface sediments and characterize their spatial distribution in the Steamboat Creek watershed. Total mercury concentrations measured in channel and bank sediments did not decrease downstream, indicating that mercury contamination has been distributed along the creek's length. Total mercury concentrations in sediments (0.01-21.43 microg/g) were one to two orders of magnitude higher than those in pristine systems. At 14 out of 17 sites, MeHg concentrations in streambank sediments were higher than the concentrations in the channel, suggesting that low banks with wet sediments might be important sites of mercury methylation in this system. Both pond/wetland and channel sites exhibited high potential for mercury methylation (6.4-30.0 ng g(-1) day(-1)). Potential methylation rates were positively correlated with sulfate reduction rates, and decreased as a function of reduced sulfur and MeHg concentration in the sediments. Potential demethylation rate appeared not to be influenced by MeHg concentration, sulfur chemistry, DOC, sediment grain size or other parameters, and showed little variation across the sites (3.7-7.4 ng g(-1) day(-1)).