Darell G. Slotton

Mercury Isotopes Link Mercury in San Francisco Bay Forage Fish to Surface Sediments

Identification of sources of biologically accessible Hg is necessary to fully evaluate Hg exposure in aquatic ecosystems. This study assesses the relationship between Hg in forage fish and Hg in surface sediments throughout San Francisco Bay (SF Bay) and evaluates processes influencing the incorporation of Hg into the aquatic food web. We measured the Hg stable isotope compositions of two nearshore fish species and compared them with previously reported analyses of colocated intertidal surface sediments. Fish δ(202)Hg values (mass-dependent fractionation) demonstrated a distinct spatial gradient within SF Bay that ranged from 0.60‰ in the south to -0.25‰ in the north. Fish δ(202)Hg values were consistently higher than sediment δ(202)Hg values by 0.73‰ (±0.16‰, 1SD). Fish and sediment δ(202)Hg values in SF Bay proper were well correlated (r(2) = 0.83), suggesting that sediment is a primary source of Hg to the nearshore aquatic food web. Fish Δ(199)Hg values (mass-independent fractionation) ranged from 0.46‰ to 1.55‰, did not correlate with sediment values, and yielded a Δ(199)Hg/Δ(201)Hg ratio of 1.26 (±0.01, 1SD; r(2) = 0.99). This mass-independent fractionation is consistent with photodegradation of MeHg to varying degrees at each site prior to incorporation into the food web.

REDISTRIBUTION OF MERCURY FROM CONTAMINATED LAKE SEDIMENTS OF CLEAR LAKE, CALIFORNIA

Mining operations conducted at the Sulphur Bank Mercury Mine at Clear Lake, California, from 1872–1957, together with acid mine drainage since abandonment, deposited ca. 100 metric tons of mercury (Hg) in the sediments of Clear Lake. In 1992 Hg in surficial sediments (up to 183 mg kg-1 total Hg and 15.9 μg kg-1 methyl Hg) exhibited a classic point source distribution with maximum concentrations adjacent to the mine. However, the ratio of methyl:total Hg in sediments increased with distance from the mine, suggesting either differential transport of methyl Hg or a non-linear relationship between sediment inorganic Hg concentrations and methylation. Water exhibited an even more gradual decline in total Hg concentrations with distance from the mine, in both unfiltered bottom water (max. ca. 70 ng L-1) and filtered surface water (max. ca. 7 ng L-1). In comparison with other studies, Clear Lake exhibits high total Hg in sediment and water, yet relatively low methyl Hg concentrations. Our findings indicate a non-linearity between total and methyl Hg concentrations in sediments. The ratio of methyl:inorganic Hg is approximately 2 orders of magnitude higher in the water column than in the sediments, making the methyl fraction much more available for down-gradient transport away from the mine. Particulate Hg comprises ca. 33–94% of the total Hg and ca. 25–78% of the methyl Hg in the water column. Geothermal springs do not appear to represent a significant source of Hg to Clear Lake. The present pattern of Hg distribution in Clear Lake shows that water column transport plays some role in the lake-wide contamination of methyl Hg, but high methylation at relatively low inorganic Hg concentrations cannot be ruled out. No quantitative estimate of the area of sediments requiring remediation is possible from these descriptive data alone.

THE LEGACY OF MERCURY CYCLING FROM MINING SOURCES IN AN AQUATIC ECOSYSTEM: FROM ORE TO ORGANISM

Clear Lake is the site of an abandoned mercury (Hg) mine (active intermittently from 1873 to 1957), now a U.S. Environmental Protection Agency Superfund Site. Mining activities, including bulldozing waste rock and tailings into the lake, resulted in approximately 100 Mg of Hg entering the lakes ecosystem. This series of papers represents the culmination of approximately 15 years of Hg-related studies on this ecosystem, following Hg from the ore body to the highest trophic levels. A series of physical, chemical, biological, and limnological studies elucidate how ongoing Hg loading to the lake is influenced by acid mine drainage and how wind-driven currents and baroclinic circulation patterns redistribute Hg throughout the lake. Methylmercury (MeHg) production in this system is controlled by both sulfate-reducing bacteria as well as newly identified iron-reducing bacteria. Sediment cores (dated with dichlorodiphenyldichlorethane [DDD], 210pb, and 14C) to approximately 250 cm depth (representing up to approximately 3000 years before present) elucidate a record of total Hg (TotHg) loading to the lake from natural sources and mining and demonstrate how MeHg remains stable at depth within the sediment column for decades to millenia. Core data also identify other stresses that have influenced the Clear Lake Basin especially over the past 150 years. Although Clear Lake is one of the most Hg-contaminated lakes in the world, biota do not exhibit MeHg concentrations as high as would be predicted based on the gross level of Hg loading. We compare Clear Lakes TotHg and MeHg concentrations with other sites worldwide and suggest several hypotheses to explain why this discrepancy exists. Based on our data, together with state and federal water and sediment quality criteria, we predict potential resulting environmental and human health effects and provide data that can assist remediation efforts.

MINE-DERIVED MERCURY: EFFECTS ON LOWER TROPHIC SPECIES IN CLEAR LAKE, CALIFORNIA

Considerable ecological research on mercury (Hg) has focused on higher trophic level species (e.g., fishes and birds), but less on lower trophic species. Clear Lake, site of the abandoned Sulphur Bank Mercury Mine, provides a unique opportunity to study a system influenced by mine-derived Hg. An exponentially decreasing gradient of total Hg (TotHg) away from the mine allowed us to evaluate Hg bioaccumulation in planktonic and benthic invertebrates and evaluate population- and community-level parameters that might be influenced by Hg. Studies from 1992-1998 demonstrated that TotHg in lower trophic species typically decreased exponentially away from the mine, similar to trends observed in water and sediments. However, a significant amount of invertebrate TotHg (approximately 60% for sediment-dwelling chironomid insect larvae) likely derives from Hg-laden particles in their guts. Spatially, whole-body methylmercury (MeHg) did not typically exhibit a significant decrease with increasing distance from the mine. Temporally, TotHg concentrations in plankton and chironomids did not exhibit any short-term (seasonal or annual) or long-term (multiyear) trends. Methylmercury, however, was elevated during late summer/fall in both plankton and chironomids, but it exhibited no long-term increase or decrease during this study. Although data from a 50-yr monitoring program for benthic chaoborid and chironomid larvae documented significant population fluctuations, they did not demonstrate population-level trends with respect to Hg concentrations. Littoral invertebrates also exhibited no detectable population- or community-level trends associated with the steep Hg gradient. Although sediment TotHg concentrations (1-1200 mg/kg dry mass) exceed sediment quality guidelines by up to 7000 times, it is notable that no population- or community-level effects were detected for benthic and planktonic taxa. In comparison with other sites worldwide, Clear Lakes lower trophic species typically have significantly higher TotHg concentrations, but comparable or lower MeHg concentrations, which may be responsible for the discrepancy between highly elevated TotHg concentrations and the general lack of observed population- or community-level effects. These data suggest that MeHg, as well as TotHg, should be used when establishing sediment quality guidelines. In addition, site-specific criteria should be established using the observed relationship between MeHg and observed ecological responses.

SPATIOTEMPORAL TRENDS IN FISH MERCURY FROM A MINE-DOMINATED ECOSYSTEM: CLEAR LAKE, CALIFORNIA

Clear Lake, California, USA, receives acid mine drainage and mercury (Hg) from the Sulphur Bank Mercury Mine, a U.S. Environmental Protection Agency (U.S. EPA) Superfund Site that was active intermittently from 1873 to 1957 and partially remediated in 1992. Mercury concentrations were analyzed primarily in four species of Clear Lake fishes: inland silversides (Menidia beryllina, planktivore), common carp (Cyprinus carpio, benthic scavenger/omnivore), channel catfish (Ictalurus punctatus, benthic omnivorous predator), and largemouth bass (Micropterus salmoides, piscivorous top predator). These data represent one of the largest fish Hg data sets for a single site, especially in California. Spatially, total Hg (TotHg) in silversides and bass declined with distance from the mine, indicating that the mine site represents a point source for Hg loading to Clear Lake. Temporally, fish Hg has not declined significantly over 12 years since mine site remediation. Mercury concentrations were variable throughout the study period, with no monotonic trends of increase or decrease, except those correlated with boom and bust cycles of an introduced fish, threadfin shad (Dorosoma petenense). However, stochastic events such as storms also influence juvenile largemouth bass Hg as evidenced during an acid mine drainage overflow event in 1995. Compared to other sites regionally and nationally, most fish in Clear Lake exhibit Hg concentrations similar to other Hg-contaminated sites, up to approximately 2.0 mg/kg wet mass (WM) TotHg in largemouth bass. However, even these elevated concentrations are less than would be anticipated from such high inorganic Hg loading to the lake. Mercury in some Clear Lake largemouth bass exceeded all human health fish consumption guidelines established over the past 25 years by the U.S. Food and Drug Administration (1.0 mg/kg WM), the National Academy of Sciences (0.5 mg/kg WM), and the U.S. EPA (0.3 mg/kg WM). Mercury in higher trophic level fishes exceeds ecotoxicological risk assessment estimates for concentrations that would be safe for wildlife, specifically the nonlisted Common Merganser and the recently delisted Bald Eagle. Fish populations of 11 out of 18 species surveyed exhibited a significant decrease in abundance with increasing proximity to the mine; this decrease is correlated with increasing water and sediment Hg. These trends may be related to Hg or other lake-wide gradients such as distribution of submerged aquatic vegetation.

MERCURY IN ABIOTIC MATRICES OF CLEAR LAKE, CALIFORNIA: HUMAN HEALTH AND ECOTOXICOLOGICAL IMPLICATIONS

Mercury (Hg) from Hg mining at Clear Lake, California, USA, has contaminated water and sediments for over 130 years and has the potential to affect human and environmental health. With total mercury (TotHg) concentrations up to 438 mg/kg (dry mass) in surficial sediments and up to 399 ng/L in lake water, Clear Lake is one of the most Hg-contaminated lakes worldwide. Particulate Hg in surface water near the mine ranges from 10,000 to 64,000 ng/g; TotHg declines exponentially with distance from the Sulphur Bank Mercury Mine. From 1992 to 1998, no significant long-term trends for TotHg or methylmercury (MeHg) in sediments or water were observed, but peaks of both TotHg and MeHg occurred following a 1995 flooding event. Sediments and water exhibit summer/fall maxima and winter/spring minima for MeHg, but not TotHg. Sediment TotHg has not declined significantly a decade after remediation in 1992. At the mine site, aqueous TotHg reached 374,000 ng/L in unfiltered groundwater. Pore water sulfate in sediments varies seasonally from 112 mg/L in summer/fall (when Hg methylation is highest) to 3300 mg/L in winter. While TotHg is exceptionally high in both sediments and water, MeHg is substantially lower than would be expected based on the bulk Hg loading to the lake and in comparison with other sites worldwide. Total mercury in Clear Lake water does not exceed the Safe Drinking Water Act criteria, but it sometimes greatly exceeds human health criteria established by the Great Lakes Initiative, U.S. Environmental Protection Agency water quality guidelines, and the California Toxics Rule criterion. Methylmercury concentrations exceed the Great Lakes Initiative criterion for MeHg in water at some sites only during summer/fall. Relative to ecological health, Clear Lake sediments greatly exceed the National Oceanic and Atmospheric Administrations benthic fauna Sediment Quality Guidelines for toxic effects, as well as the more concensus-based Threshold Effects Concentration criteria. Based on these criteria, Hg-contaminated sediments and water from Clear Lake are predicted to have some lethal and sublethal effects on specific resident aquatic species. However, based on unique physical and chemical characteristics of the Clear Lake environment, MeHg toxicity may be significantly less than anticipated from the large inorganic Hg loading.

Seasonal and annual trends in forage fish mercury concentrations, San Francisco Bay.

San Francisco Bay is contaminated by mercury (Hg) due to historic and ongoing sources, and has elevated Hg concentrations throughout the aquatic food web. We monitored Hg in forage fish to indicate seasonal and interannual variations and trends. Interannual variation and long-term trends were determined by monitoring Hg bioaccumulation during September-November, for topsmelt (Atherinops affinis) and Mississippi silverside (Menidia audens) at six sites, over six years (2005 to 2010). Seasonal variation was characterized for arrow goby (Clevelandia ios) at one site, topsmelt at six sites, and Mississippi silverside at nine sites. Arrow goby exhibited a consistent seasonal pattern from 2008 to 2010, with lowest concentrations observed in late spring, and highest concentrations in late summer or early fall. In contrast, topsmelt concentrations tended to peak in late winter or early spring and silverside seasonal fluctuations varied among sites. The seasonal patterns may relate to seasonal shifts in net MeHg production in the contrasting habitats of the species. Topsmelt exhibited an increase in Alviso Slough from 2005 to 2010, possibly related to recent hypoxia in that site. Otherwise, directional trends for Hg in forage fish were not observed. For topsmelt and silverside, the variability explained by year was relatively low compared to sampling station, suggesting that interannual variation is not a strong influence on Hg concentrations. Although fish Hg has shown long-term declines in some ecosystems around the world, San Francisco Bay forage fish did not decline over the six-year monitoring period examined.

ANTHROPOGENIC STRESSORS AND CHANGES IN THE CLEAR LAKE ECOSYSTEM AS RECORDED IN SEDIMENT CORES

Sediment cores were collected to investigate multiple stresses on Clear Lake, California, USA, through the period of European occupation to the present day. Earlier workers suggested the hypothesis that the use of mechanized earthmoving equipment, starting in the 1920s and 1930s, was responsible for erosion, mercury (Hg) contamination, and habitat loss stresses. Cores (approximately 2.5 m in depth) were collected in 1996 and 2000 from each of the three arms of the lake. Carbon-14 dating suggests that these cores represent as much as 3000 years of the lakes history, beginning long before European settlement. Total mercury (TotHg) and methylmercury (MeHg), dry matter, water, carbon, nitrogen, phosphorus, sulfur, and the stable isotopes 13C and 15N were measured at 5-cm intervals. Nearly all parameters show major changes at depths of 58-135 cm, beginning at ca. 1927 (dated with 210Pb). Accepting this date for concomitant major changes in seven cores yields an estimated 8.6 mm/yr average sedimentation rate after 1927. Pre-1927 sedimentation rates were approximately 1 mm/yr. Total mercury and MeHg, dry matter, phosphorus, and 15N increase significantly, whereas nitrogen, sulfur, carbon, and water content decrease significantly above the 1927 horizon. Both TotHg and MeHg show extremely large increases (roughly 10-fold) above the 1927 horizon. A peak in inorganic deposition rate and minimum values for percentage of water is present at depths corresponding to ca. 1970. Interestingly, the first 75 years of European settlement in the Clear Lake basin (including the most productive years of the Sulphur Bank Mercury Mine) appeared to have had undetectable effects on lake cores. Changes since 1927 were dramatic. The large increase in Hg beginning about 1927 corresponds to the use of heavy equipment to exploit the ore deposit at the mine using open-pit methods. Increases in sediment deposition from increased earthmoving in the basin and sulfate loading from the mine are the most likely explanations for the dramatic changes seen in the post-1927 sections of the cores.

Mercury Contamination of Skin Whiteners in Cambodia

ABSTRACT Eleven of 41 brands of skin whiteners that were collected in Phnom Penh, Cambodia, and processed with a screening kit contained more than 2000 μg/g mercury. Risk analysis indicates that these 11 brands were toxic. Nine of 19 of these skin whiteners analyzed with cold vapor atomic absorption (CVAA) spectrophotometry exceeded Association of Southeast Asian Nations (ASEAN) guidelines for cosmetic good manufacturing practice limit on mercury of 1 μg/g. The most contaminated whitener analyzed by CVAA had 12,590 μg/g mercury. The mercury-containing products were labeled as produced in Thailand, China, Taiwan, Vietnam, the United States, and an unidentified country. Eight other products (antifungal, steroids, and antibiotics) were sold as additives to be mixed into whitener concoctions. In the 19 samples analyzed with CVAA, there was a significant association between the mercury content and a label “for export only.” Labeling of sampled products varied from detailed to slight, with none containing Khmer instructions. Variability in mercury content of some products appeared to reflect copying of brand names with very similar packaging.

VERTICAL STABILITY OF MERCURY IN HISTORIC AND PREHISTORIC SEDIMENTS FROM CLEAR LAKE, CALIFORNIA

Clear Lake, California, USA, is the site of the Sulphur Bank Mercury Mine, now a U.S. Environmental Protection Agency Superfund Site. Intermittent mining from 1873 to 1957 resulted in approximately 100 Mg of mercury (Hg) being deposited into the lakes ecosystem. Sediment cores to approximately 2.5 m depth (dated using 210Pb and 14C) represent approximately 3000 years of sedimentation. Clear Lake sediments have experienced Hg deposition from anthropogenic sources (mining) during historic times (to the mid-1900s) and geologic sources during prehistoric times (prior to the mid-1800s). This provides a unique opportunity to evaluate hypotheses relating to (1) the influence of the mine on Hg loading to the lake and (2) the potential upward mobilization of Hg by diagenetic processes proposed by some as an alternative explanation for increased Hg concentrations at the surface of the sediment column believed to be caused by increased global atmospheric deposition. Although Hg mining began in 1873, no significant evidence of anthropogenic Hg loading was detected in cores prior to open-pit mining ca. 1927, which also involved bulldozing mine waste rock and tailings into the lake. Exponential increases in total Hg (TotHg) and methylmercury (MeHg) were observed above the 1927 horizon, where estimated sedimentation rates were 2.2-20.4 mm/yr and peaks of both forms of Hg maintained vertical stability within the sediment column. Below the 1927 horizon, a slow increase in both TotHg and MeHg with depth was observed from approximately 1000 to 3000 years before present, where sedimentation rates ranged from approximately 0.6 to 2.0 mm/yr and elevated Hg profiles appear stable. Vertical stability of Hg in the shallow and deep sediment column suggests that both TotHg and MeHg do not undergo diagenetic upward mobilization within the sediment column under rapid or slow sedimentation rates. Because (1) these data were collected at a site with known anthropogenic and geologic sources and (2) regions of elevated Hg concentrations from both sources remain stable within the sediment column under very different sedimentation regimes, these results also support the hypothesis that elevated Hg at the surface of cores in other worldwide locations likely represents global atmospheric deposition rather than upward diagenetic mobilization.