Experimental evidence for recovery of mercury-contaminated fish populations.

Anthropogenic releases of mercury (Hg)1-3 are a human health issue4 because the potent toxicant methylmercury (MeHg), formed primarily by microbial methylation of inorganic Hg in aquatic ecosystems, bioaccumulates to high concentrations in fish consumed by humans5,6. Predicting the efficacy of Hg pollution controls on fish MeHg concentrations is complex because many factors influence the production and bioaccumulation of MeHg7-9. Here we conducted a 15-year whole-ecosystem, single-factor experiment to determine the magnitude and timing of reductions in fish MeHg concentrations following reductions in Hg additions to a boreal lake and its watershed. During the seven-year addition phase, we applied enriched Hg isotopes to increase local Hg wet deposition rates fivefold. The Hg isotopes became increasingly incorporated into the food web as MeHg, predominantly from additions to the lake because most of those in the watershed remained there. Thereafter, isotopic additions were stopped, resulting in an approximately 100% reduction in Hg loading to the lake. The concentration of labelled MeHg quickly decreased by up to 91% in lower trophic level organisms, initiating rapid decreases of 38-76% of MeHg concentration in large-bodied fish populations in eight years. Although Hg loading from watersheds may not decline in step with lowering deposition rates, this experiment clearly demonstrates that any reduction in Hg loadings to lakes, whether from direct deposition or runoff, will have immediate benefits to fish consumers.

The effects of a stannous chloride-based water treatment system in a mercury contaminated stream.

We assessed the impacts of an innovative Hg water treatment system on a small, industrially-contaminated stream in the southeastern United States. The treatment system, installed in 2007, removes Hg from wastewater using tin (Sn) (II) chloride followed by air stripping. Mercury concentrations in the receiving stream, Tims Branch, decreased from >100 to ∼10 ng/L in the four years following treatment, and Hg body burdens in redfin pickerel (Esox americanus) decreased by 70% at the most contaminated site. Tin concentrations in water and fish increased significantly in the tributary leading to Tims Branch, but concentrations remain below levels of concern for human health or ecological risks. While other studies have shown that Sn may be environmentally methylated and methyltin can transfer its methyl group to Hg, results from our field studies and sediment incubation experiments suggest that the added Sn to the Tims Branch watershed is not contributing to methylmercury (MeHg) production or bioaccumulation in this system. The stannous chloride treatment system installed at Tims Branch was effective at removing Hg inputs and reducing Hg bioaccumulation in the stream, but future studies are needed to assess longer term impacts of Sn on the environment.

Sources of mercury in a contaminated stream--implications for the timescale of recovery.

Mercury contamination in East Fork Poplar Creek in Tennessee arises from dissolved mercury exiting a headwater industrial complex and residual mercury in the streambed and soil throughout the watershed downstream. The headwater inputs generate chronic base flow concentrations of total mercury of about 1,000 ng/L, but most of the annual export of mercury from the system appears to originate farther downstream. Effective targeting of remedial efforts requires determining how long downstream sources might continue to contaminate the system following elimination of the headwater mercury inputs. The authors calculations suggest that (1) contaminated soils and sediments account for >80% of the annual mercury export from the entire watershed, with most export occurring during wet weather events; (2) bank erosion and resuspension of streambed particulates are the major mercury sources maintaining high annual mercury export rates; and (3) the inventory of particle-associated mercury in the streambed was not large enough to sustain the estimated export rates for more than a few years. The authors findings imply that to prevent waterborne mercury contamination in this system from continuing for decades, remedial actions will have to control the headwater mercury source that sustains day-to-day base flow mercury concentrations and the riparian stream-bank sources that generate most of the mercury export from the system.

Decreasing aqueous mercury concentrations to meet the water quality criterion in fish: examining the water-fish relationship in two point-source contaminated streams.

East Fork Poplar Creek (EF) and White Oak Creek (WC) are two mercury-contaminated streams located on the United States (U.S.) Department of Energy Oak Ridge Reservation in East Tennessee. East Fork Poplar Creek is the larger and more contaminated of the two, with average aqueous mercury (Hg) concentrations exceeding those in reference streams by several hundred-fold. Remedial actions over the past 20 years have decreased aqueous Hg concentrations in EF by 85% (from >1600 ng/L to <400 ng/L). Fish fillet concentrations, however, have not responded to this decrease in aqueous Hg and remain above the U.S. Environmental Protection Agency National Recommended Water Quality Criteria (NRWQC) of 0.3 mg/kg. The lack of correlation between aqueous and fish tissue Hg concentrations in this creek has led to questions regarding the usefulness of target aqueous Hg concentrations and strategies for future remediation efforts. White Oak Creek has a similar contamination history but aqueous Hg concentrations in WC are an order of magnitude lower than in EF. Despite the lower aqueous Hg concentrations (<100 ng/L), fish fillet concentrations in WC have also been above the NRWQC, making the aqueous Hg remediation goal of 200 ng/L in EF seem unlikely to result in an effective decrease in fillet Hg concentrations. Recent monitoring efforts in WC, however, suggest an aqueous total Hg threshold above which Hg bioaccumulation in fish may not respond. This new information could be useful in guiding remedial actions in EF and in other point-source contaminated streams.

Monitoring fish contaminant responses to abatement actions: factors that affect recovery.

Monitoring of contaminant accumulation in fish has been conducted in East Fork Poplar Creek (EFPC) in Oak Ridge, Tennessee since 1985. Bioaccumulation trends are examined over a twenty year period coinciding with major pollution abatement actions by a Department of Energy facility at the stream's headwaters. Although EFPC is enriched in many contaminants relative to other local streams, only polychlorinated biphenyls (PCBs) and mercury (Hg) were found to accumulate in the edible portions of fish to levels of human health concern. Mercury concentrations in redbreast sunfish were found to vary with season of collection, sex and size of individual fish. Over the course of the monitoring, waterborne Hg concentrations were reduced >80%; however, this did not translate into a comparable decrease in Hg bioaccumulation at most sites. Mercury bioaccumulation in fish did respond to decreased inputs in the industrialized headwater reach, but paradoxically increased in the lowermost reach of EFPC. As a result, the downstream pattern of Hg concentration in fish changed from one resembling dilution of a headwater point source in the 1980s to a uniform distribution in the 2000s. The reason for this remains unknown, but is hypothesized to involve changes in the chemical form and reactivity of waterborne Hg associated with the removal of residual chlorine and the addition of suspended particulates to the streamflow. PCB concentrations in fish varied greatly from year-to-year, but always exhibited a pronounced downstream decrease, and appeared to respond to management practices that limited episodic inputs from legacy sources within the facility.

History of mercury use and environmental contamination at the Oak Ridge Y-12 Plant.

Between 1950 and 1963 approximately 11 million kilograms of mercury (Hg) were used at the Oak Ridge Y-12 National Security Complex (Y-12 NSC) for lithium isotope separation processes. About 3% of the Hg was lost to the air, soil and rock under facilities, and East Fork Poplar Creek (EFPC) which originates in the plant site. Smaller amounts of Hg were used at other Oak Ridge facilities with similar results. Although the primary Hg discharges from Y-12 NSC stopped in 1963, small amounts of Hg continue to be released into the creek from point sources and diffuse contaminated soil and groundwater sources within Y-12 NSC. Mercury concentration in EFPC has decreased 85% from ∼2000 ng/L in the 1980s. In general, methylmercury concentrations in water and in fish have not declined in response to improvements in water quality and exhibit trends of increasing concentration in some cases.

Mercury and other heavy metals influence bacterial community structure in contaminated Tennessee streams.

High concentrations of uranium, inorganic mercury [Hg(II)], and methylmercury (MeHg) have been detected in streams located in the Department of Energy reservation in Oak Ridge, TN. To determine the potential effects of the surface water contamination on the microbial community composition, surface stream sediments were collected 7 times during the year, from 5 contaminated locations and 1 control stream. Fifty-nine samples were analyzed for bacterial community composition and geochemistry. Community characterization was based on GS 454 FLX pyrosequencing with 235 Mb of 16S rRNA gene sequence targeting the V4 region. Sorting and filtering of the raw reads resulted in 588,699 high-quality sequences with lengths of >200 bp. The bacterial community consisted of 23 phyla, including Proteobacteria (ranging from 22.9 to 58.5% per sample), Cyanobacteria (0.2 to 32.0%), Acidobacteria (1.6 to 30.6%), Verrucomicrobia (3.4 to 31.0%), and unclassified bacteria. Redundancy analysis indicated no significant differences in the bacterial community structure between midchannel and near-bank samples. Significant correlations were found between the bacterial community and seasonal as well as geochemical factors. Furthermore, several community members within the Proteobacteria group that includes sulfate-reducing bacteria and within the Verrucomicrobia group appeared to be associated positively with Hg and MeHg. This study is the first to indicate an influence of MeHg on the in situ microbial community and suggests possible roles of these bacteria in the Hg/MeHg cycle.

Kinetic controls on the complexation between mercury and dissolved organic matter in a contaminated environment.

The interaction of mercury (Hg) with dissolved natural organic matter (NOM) under equilibrium conditions is the focus of many studies but the kinetic controls on Hg-NOM complexation in aquatic systems have often been overlooked. We examined the rates of Hg-NOM complexation both in a contaminated Upper East Fork Poplar Creek (UEFPC) in Oak Ridge, Tennessee, and in controlled laboratory experiments using reducible Hg (Hg(R)) measurements and C(18) solid phase extraction techniques. Of the filterable Hg at the headwaters of UEFPC, >90% was present as Hg(R) and this fraction decreased downstream but remained >29% of the filterable Hg at all sites. The presence of higher Hg(R) concentrations than would be predicted under equilibrium conditions in UEFPC and in experiments with a NOM isolate suggests that kinetic reactions are controlling the complexation between Hg and NOM. The slow formation of Hg-NOM complexes is attributed to competitive ligand exchange among various moieties and functional groups in NOM with a range of binding strengths and configurations. This study demonstrates the need to consider the effects of Hg-NOM complexation kinetics on processes such as Hg methylation and solid phase partitioning.

Whole-ecosystem study shows rapid fish-mercury response to changes in mercury deposition.

Methylmercury contamination of fisheries from centuries of industrial atmospheric emissions negatively impacts humans and wildlife worldwide. The response of fish methylmercury concentrations to changes in mercury deposition has been difficult to establish because sediments/soils contain large pools of historical contamination, and many factors in addition to deposition affect fish mercury. To test directly the response of fish contamination to changing mercury deposition, we conducted a whole-ecosystem experiment, increasing the mercury load to a lake and its watershed by the addition of enriched stable mercury isotopes. The isotopes allowed us to distinguish between experimentally applied mercury and mercury already present in the ecosystem and to examine bioaccumulation of mercury deposited to different parts of the watershed. Fish methylmercury concentrations responded rapidly to changes in mercury deposition over the first 3 years of study. Essentially all of the increase in fish methylmercury concentrations came from mercury deposited directly to the lake surface. In contrast, <1% of the mercury isotope deposited to the watershed was exported to the lake. Steady state was not reached within 3 years. Lake mercury isotope concentrations were still rising in lake biota, and watershed mercury isotope exports to the lake were increasing slowly. Therefore, we predict that mercury emissions reductions will yield rapid (years) reductions in fish methylmercury concentrations and will yield concomitant reductions in risk. However, a full response will be delayed by the gradual export of mercury stored in watersheds. The rate of response will vary among lakes depending on the relative surface areas of water and watershed.

Evasion of added isotopic mercury from a northern temperate lake.

Isotopically enriched Hg (90% 202Hg) was added to a small lake in Ontario, Canada, at a rate equivalent to approximately threefold the annual direct atmospheric deposition rate that is typical of the northeastern United States. The Hg spike was thoroughly mixed into the epilimnion in nine separate events at two-week intervals throughout the summer growing season for three consecutive years. We measured concentrations of spike and ambient dissolved gaseous Hg (DGM) concentrations in surface water and the rate of volatilization of Hg from the lake on four separate, week-long sampling periods using floating dynamic flux chambers. The relationship between empirically measured rates of spike-Hg evasion were evaluated as functions of DGM concentration, wind velocity, and solar illumination. No individual environmental variable proved to be a strong predictor of the evasion flux. The DGM-normalized flux (expressed as the mass transfer coefficient, k) varied with wind velocity in a manner consistent with existing models of evasion of volatile solutes from natural waters but was higher than model estimates at low wind velocity. The empirical data were used to construct a description of evasion flux as a function of total dissolved Hg, wind, and solar illumination. That model was then applied to data for three summers for the experiment to generate estimates of Hg re-emission from the lake surface to the atmosphere. Based on ratios of spike Hg to ambient Hg in DGM and dissolved total Hg pools, ratios of DGM to total Hg in spike and ambient Hg pools, and flux estimates of spike and ambient Hg, we concluded that the added Hg spike was chemically indistinguishable from the ambient Hg in its behavior. Approximately 45% of Hg added to the lake over the summer was lost via volatilization.

Relationship between the loading rate of inorganic mercury to aquatic ecosystems and dissolved gaseous mercury production and evasion.

The purpose of our study was to test the hypothesis that dissolved gaseous mercury (DGM) production and evasion is directly proportional to the loading rate of inorganic mercury [Hg(II)] to aquatic ecosystems. We simulated different rates of atmospheric mercury deposition in 10-m diameter mesocosms in a boreal lake by adding multiple additions of Hg(II) enriched with a stable mercury isotope ((202)Hg). We measured DGM concentrations in surface waters and estimated evasion rates using the thin-film gas exchange model and mass transfer coefficients derived from sulfur hexafluoride (SF(6)) additions. The additions of Hg(II) stimulated DGM production, indicating that newly added Hg(II) was highly reactive. Concentrations of DGM derived from the experimental Hg(II) additions ("spike DGM") were directly proportional to the rate of Hg(II) loading to the mesocosms. Spike DGM concentrations averaged 0.15, 0.48 and 0.94 ng l(-1) in mesocosms loaded at 7.1, 14.2, and 35.5 microg Hg m(-2) yr(-1), respectively. The evasion rates of spike DGM from these mesocosms averaged 4.2, 17.2, and 22.3 ng m(-2)h(-1), respectively. The percentage of Hg(II) added to the mesocosms that was lost to the atmosphere was substantial (33-59% over 8 weeks) and was unrelated to the rate of Hg(II) loading. We conclude that changes in atmospheric mercury deposition to aquatic ecosystems will not change the relative proportion of mercury recycled to the atmosphere.

Airborne emissions of mercury from municipal solid waste. I: new measurements from six operating landfills in Florida.

Mercury-bearing material enters municipal landfills from a wide array of sources, including fluorescent lights, batteries, electrical switches, thermometers, and general waste; however, the fate of mercury (Hg) in landfills has not been widely studied. Using automated flux chambers and downwind atmospheric sampling, we quantified the primary pathways of Hg vapor releases to the atmosphere at six municipal landfill operations in Florida. These pathways included landfill gas (LFG) releases from active vent systems, passive emissions from landfill surface covers, and emissions from daily activities at each working face (WF). We spiked the WF at two sites with known Hg sources; these were readily detected downwind, and were used to test our emission modeling approaches. Gaseous elemental mercury (Hg(O)) was released to the atmosphere at readily detectable rates from all sources measured; rates ranged from approximately 1-10 ng m(-2) hr(-1) over aged landfill cover, from approximately 8-20 mg/hr from LFG flares (LFG included Hg(O) at microg/m3 concentrations), and from approximately 200-400 mg/hr at the WF. These fluxes exceed our earlier published estimates. Attempts to identify specific Hg sources in excavated and sorted waste indicated few readily identifiable sources; because of effective mixing and diffusion of Hg(O), the entire waste mass acts as a source. We estimate that atmospheric Hg releases from municipal landfill operations in the state of Florida are on the order of 10-50 kg/yr, substantially larger than our original estimates, but still a small fraction of current overall anthropogenic losses.

Airborne emissions of mercury from municipal solid waste. II: potential losses of airborne mercury before landfill.

Waste distribution and compaction at the working face of municipal waste landfills releases mercury vapor (Hg(o)) to the atmosphere, as does the flaring of landfill gas. Waste storage and processing before its addition to the landfill also has the potential to release Hg(o) to the air if it is initially present or formed by chemical reduction of Hg(II) to Hg(o) within collected waste. We measured the release of Hg vapor to the atmosphere during dumpster and transfer station activities and waste storage before landfilling at a municipal landfill operation in central Florida. We also quantified the potential contribution of specific Hg-bearing wastes, including mercury (Hg) thermometers and fluorescent bulbs, and searched for primary Hg sources in sorted wastes at three different landfills. Surprisingly large fluxes were estimated for Hg losses at transfer facilities (approximately 100 mg/hr) and from dumpsters in the field (approximately 30 mg/hr for 1000 dumpsters), suggesting that Hg emissions occurring before landfilling may constitute a significant fraction of the total emission from the disposal/landfill cycle and a need for more measurements on these sources. Reducing conditions of landfill burial were obviously not needed to generate strong Hg(o) signals, indicating that much of the Hg was already present in a metallic (Hg(o)) form. Attempts to identify specific Hg sources in excavated and sorted waste indicated few readily identifiable sources; because of effective mixing and diffusion of Hg(o), the entire waste mass acts as a source. Broken fluorescent bulbs and thermometers in dumpsters emitted Hg(o) at 10 to >100 microg/hr and continued to act as near constant sources for several days.

Effect of point source removal on mercury bioaccumulation in an industrial pond.

A one hectare pond on the headwaters of a mercury-contaminated creek in Oak Ridge, Tennessee acted as a biochemical reactor for the production of methylmercury, increasing waterborne methylmercury concentrations in the stream below the pond discharge. The flow of the creek was diverted around the pond in order to eliminate this input. Waterborne total mercury, methylmercury, and mercury in fish, were monitored in the pond and stream before and after bypass. Waterborne methylmercury concentration in the creek downstream from the pond decreased over 800% following diversion of streamflow around the pond, but mercury in redbreast sunfish in the pond tailwater did not decline similarly. Within the pond, now isolated from fresh waterborne mercury inputs from the stream, methylmercury concentrations in the water column remained similar to levels present before bypass. However, mercury concentrations in sunfish in the pond decreased approximately 75% following bypass, despite the continued presence of highly contaminated sediments (approximately 50 mg Hg/kg dry weight). We concluded that a decrease in the fraction of 'dissolved methylmercury' in the isolated pond relative to pre-bypass conditions explained the decrease in mercury in fish within the pond. That observation also indicates that mercury associated with pond sediments was relatively unavailable for eventual bioaccumulation when compared to 'fresh' mercury contributed by upstream sources. The lack of a post-bypass decrease in mercury concentrations in tailwater fish was also likely to be associated with the particle-associated nature of waterborne methylmercury exported from the pond.