Methylmercury degradation and exposure pathways in streams and wetlands impacted by historical mining

The authors acknowledge financial support from the National Science Foundation: EAR-1226741 (to M.B.S.) and EAR-1225630 (to J.D.B.).Monomethyl mercury (MMHg) and total mercury (THg) concentrations and Hg stable isotope ratios (δ202Hg and Δ199Hg) were measured in sediment and aquatic organisms from Cache Creek (California Coast Range) and Yolo Bypass (Sacramento Valley). Cache Creek sediment had a large range in THg (87 to 3870 ng/g) and δ202Hg (− 1.69 to − 0.20‰) reflecting the heterogeneity of Hg mining sources in sediment. The δ202Hg of Yolo Bypass wetland sediment suggests a mixture of high and low THg sediment sources. Relationships between %MMHg (the percent ratio of MMHg to THg) and Hg isotope values (δ202Hg and Δ199Hg) in fish and macroinvertebrates were used to identify and estimate the isotopic composition of MMHg. Deviation from linear relationships was found between %MMHg and Hg isotope values, which is indicative of the bioaccumulation of isotopically distinct pools of MMHg. The isotopic composition of pre-photodegraded MMHg (i.e., subtracting fractionation from photochemical reactions) was estimated and contrasting relationships were observed between the estimated δ202Hg of pre-photodegraded MMHg and sediment IHg. Cache Creek had mass dependent fractionation (MDF; δ202Hg) of at least − 0.4‰ whereas Yolo Bypass had MDF of + 0.2 to + 0.5‰. This result supports the hypothesis that Hg isotope fractionation between IHg and MMHg observed in rivers (− MDF) is unique compared to + MDF observed in non-flowing water environments such as wetlands, lakes, and the coastal ocean.PostprintPeer reviewe

Spatial patterns of mercury in biota of Adirondack, New York lakes

We studied the spatial distribution patterns of mercury (Hg) in lake water, littoral sediments, zooplankton, crayfish, fish, and common loons in 44 lakes of the Adirondacks of New York State, USA, a region that has been characterized as a “biological Hg hotspot”. Our study confirmed this pattern, finding that a substantial fraction of the lakes studied had fish and loon samples exceeding established criteria for human and wildlife health. Factors accounting for the spatial variability of Hg in lake water and biota were lake chemistry (pH, acid neutralizing capacity (ANC), percent carbon in sediments), biology (taxa presence, trophic status) and landscape characteristics (land cover class, lake elevation). Hg concentrations in zooplankton, fish and common loons were negatively associated with the lake water acid-base status (pH, ANC). Bioaccumulation factors (BAF) for methyl Hg (MeHg) increased from crayfish (mean log10 BAF = 5.7), to zooplankton (5.9), to prey fish (6.2), to larger fish (6.3), to common loons (7.2). MeHg BAF values in zooplankton, crayfish, and fish (yellow perch equivalent) all increased with increasing lake elevation. Our findings support the hypothesis that bioaccumulation of MeHg at the base of the food chain is an important controller of Hg concentrations in taxa at higher trophic levels. The characteristics of Adirondack lake-watersheds (sensitivity to acidic deposition; significant forest and wetland land cover; and low nutrient inputs) contribute to elevated Hg concentrations in aquatic biota

Mercury and methylmercury concentrations and loads in the Cache Creek watershed, California

Concentrations and loads of total mercury and methylmercury were measured in streams draining abandoned mercury mines and in the proximity of geothermal discharge in the Cache Creek watershed of California during a 17-month period from January 2000 through May 2001. Rainfall and runoff were lower than long-term averages during the study period. The greatest loading of mercury and methylmercury from upstream sources to downstream receiving waters, such as San Francisco Bay, generally occurred during or after winter rainfall events. During the study period, loads of mercury and methylmercury from geothermal sources tended to be greater than those from abandoned mining areas, a pattern attributable to the lack of large precipitation events capable of mobilizing significant amounts of either mercury-laden sediment or dissolved mercury and methylmercury from mine waste. Streambed sediments of Cache Creek are a significant source of mercury and methylmercury to downstream receiving bodies of water. Much of the mercury in these sediments is the result of deposition over the last 100–150 years by either storm-water runoff, from abandoned mines, or continuous discharges from geothermal areas. Several geochemical constituents were useful as natural tracers for mining and geothermal areas, including the aqueous concentrations of boron, chloride, lithium and sulfate, and the stable isotopes of hydrogen and oxygen in water. Stable isotopes of water in areas draining geothermal discharges showed a distinct trend toward enrichment of 18O compared with meteoric waters, whereas much of the runoff from abandoned mines indicated a stable isotopic pattern more consistent with local meteoric water

Mercury and Methylmercury Concentrations and Loads in the Cache Creek Basin, California, January 2000 through May 2001

Concentrations and mass loads of total mercury and methylmercury in streams draining abandoned mercury mines and near geothermal discharge in the Cache Creek Basin, California, were measured during a 17-month period from January 2000 through May 2001. Rainfall and runoff averages during the study period were lower than long-term averages. Mass loads of mercury and methylmercury from upstream sources to downstream receiving waters, such as San Francisco Bay, were generally the highest during or after winter rainfall events. During the study period, mass loads of mercury and methylmercury from geothermal sources tended to be greater than those from abandoned mining areas because of a lack of large precipitation events capable of mobilizing significant amounts of either mercury-laden sediment or dissolved mercury and methylmercury from mine waste. Streambed sediments of Cache Creek are a source of mercury and methylmercury to downstream receiving bodies of water such as the Delta of the San Joaquin and Sacramento Rivers. Much of the mercury in these sediments was deposited over the last 150 years by erosion and stream discharge from abandoned mines or by continuous discharges from geothermal areas. Several geochemical constituents were useful as natural tracers for mining and geothermal areas. These constituents included aqueous concentrations of boron, chloride, lithium, and sulfate, and the stable isotopes of hydrogen and oxygen in water. Stable isotopes of water in areas draining geothermal discharges were enriched with more oxygen-18 relative to oxygen-16 than meteoric waters, whereas the stable isotopes of water from much of the runoff from abandoned mines were similar to that of meteoric water. Geochemical signatures from stable isotopes and trace-element concentrations may be useful as tracers of total mercury or methylmercury from specific locations; however, mercury and methylmercury are not conservatively transported. A distinct mixing trend of trace elements and stable isotopes of hydrogen and oxygen from geothermal waters was apparent in Sulphur Creek and lower Bear Creek (tributaries to Cache Creek), but the signals are lost upon mixing with Cache Creek because of dilutio

Sacramento-San Joaquin Delta Regional Ecosystem Restoration Implementation Plan

Mercury has been identified as an important contaminant in the Delta, based on elevated concentrations of methylmercury (a toxic, organic form that readily bioaccumulates) in fish and wildlife. There are health risks associated with human exposure to methylmercury by consumption of sport fish, particularly top predators such as bass species. Original mercury sources were upstream tributaries where historical mining of mercury in the Coast Ranges and gold in the Sierra Nevada and Klamath-Trinity Mountains caused contamination of water and sediment on a regional scale. Remediation of abandoned mine sites may reduce local sources in these watersheds, but much of the mercury contamination occurs in sediments stored in the riverbeds, floodplains, and the Bay- Delta, where scouring of Gold-Rush-era sediment represents an ongoing source. Conversion of inorganic mercury to toxic methylmercury occurs in anaerobic environments including some wetlands. Wetland restoration managers must be cognizant of potential effects on mercury cycling so that the problem is not exacerbated. Recent research suggests that wettingdrying cycles can contribute to mercury methylation. For example, high marshes (inundated only during the highest tides for several days per month) tend to have higher methylmercury concentrations in water, sediment, and biota compared with low marshes, which do not dry out completely during the tidal cycle. Seasonally inundated flood plains are another environment experiencing wetting and drying where methylmercury concentrations are typically elevated. Stream restoration efforts using gravel injection or other reworking of coarse sediment in most watersheds of the Central Valley involve tailings from historical gold mining that are likely to contain elevated mercury in associated fines. Habitat restoration projects, particularly those involving wetlands, may cause increases in methylmercury exposure in the watershed. This possibility should be evaluated. The DRERIP mercury conceptual model and its four submodels (1. Methylation, 2. Bioaccumulation, 3. Human Health Effects, and 4. Wildlife Heath Effects) can be used to understand the general relationships among drivers and outcomes associated with mercury cycling in the Delta. Several linkages between important drivers and outcomes have been identified as important but highly uncertain (i.e. poorly understood). For example, there may be significant wildlife health effect of mercury on mammals and reptiles in the Delta, but there is currently very little or no information about it. The characteristics of such linkages are important when prioritizing and funding restoration projects and associated monitoring in the Delta and its tributaries