Diversity of dissimilatory sulfite reductase genes (dsrAB) in a salt marsh impacted by long-term acid mine drainage.

Sulfate-reducing bacteria (SRB) play a major role in the coupled biogeochemical cycling of sulfur and chalcophilic metal(loid)s. By implication, they can exert a strong influence on the speciation and mobility of multiple metal(loid) contaminants. In this study, we combined DsrAB gene sequencing and sulfur isotopic profiling to identify the phylogeny and distribution of SRB and to assess their metabolic activity in salt marsh sediments exposed to acid mine drainage (AMD) for over 100 years. Recovered dsrAB sequences from three sites sampled along an AMD flow path indicated the dominance of a single Desulfovibrio species. Other major sequence clades were related most closely to Desulfosarcina, Desulfococcus, Desulfobulbus, and Desulfosporosinus species. The presence of metal sulfides with low delta(34)S values relative to delta(34)S values of pore water sulfate showed that sediment SRB populations were actively reducing sulfate under ambient conditions (pH of approximately 2), although possibly within less acidic microenvironments. Interestingly, delta(34)S values for pore water sulfate were lower than those for sulfate delivered during tidal inundation of marsh sediments. 16S rRNA gene sequence data from sediments and sulfur isotope data confirmed that sulfur-oxidizing bacteria drove the reoxidation of biogenic sulfide coupled to oxygen or nitrate reduction over a timescale of hours. Collectively, these findings imply a highly dynamic microbially mediated cycling of sulfate and sulfide, and thus the speciation and mobility of chalcophilic contaminant metal(loid)s, in AMD-impacted marsh sediments.

Pathways of acid mine drainage to Clear Lake: implications for mercury cycling.

Pore fluids from Clear Lake sediments collected near the abandoned Sulphur Bank Mercury Mine have low pH (locally <4) and elevated sulfate (> or =197 mmol/L), aluminum (> or =52 mmol/L), and iron (> or =28 mmol/L) contents derived from oxidation of sulfide minerals at the mine site. Acid mine drainage (AMD) is entering Clear Lake by advective subsurface flow nearest the mine and by diffusion at greater distances. Oxygen and hydrogen isotope ratios, combined with pore fluid compositions, constrain the sources and pathways of contaminated fluids. Sediment cores taken nearest the mine have the highest concentrations of dissolved sulfate, aluminum, and iron, which are contributed by direct subsurface flow of AMD from sulfide-bearing waste rock. Sediment cores as far as 100 m west of the Clear Lake shoreline show the presence of AMD that originated in the acidic lake that occupies the abandoned Herman Pit at the mine site. High sulfate content in the AMD has the potential to promote the activity of sulfate-reducing bacteria in the organic-rich lake sediments, which leads to methylation of Hg+2, making it both more toxic and bioavailable. Quantitative depletion of pore water sulfate at depth and sulfur isotope values of diagenetic pyrite near 0 per thousand indicate that sulfate availability limits the extent of sulfate reduction in the lake sediments away from the mine. Profiles of pore water sulfate in the sediments near the mine show that excess sulfate is available to support the activity of sulfate-reducing bacteria near the mine site. Enriched isotope values of dissolved sulfate (as high as 17.1 per thousand) and highly depleted isotope values for diagenetic pyrite (as low as -22.6 per thousand) indicate active bacterial sulfate reduction in the AMD-contaminated sediments. Sulfate- and iron-rich acid mine drainage entering Clear Lake by shallow subsurface flow likely needs to be controlled in order to lower the environmental impacts of Hg in the Clear Lake ecosystem.

Clear Lake sediments: anthropogenic changes in physical sedimentology and magnetic response.

We analyzed the sedimentological characteristics and magnetic properties of cores from the three basins of Clear Lake, California, USA, to assess the depositional response to a series of land use changes that occurred in the watershed over the 20th century. Results indicate that distinct and abrupt shifts in particle size, magnetic concentration/mineralogy, and redox conditions occur concurrently with a variety of ecological and chemical changes in lake bed sediments. This coincidence of events occurred around 1927, a datum determined by an abrupt increase in total mercury (Hg) in Clear Lake cores and the known initiation of open-pit Hg mining at the Sulphur Bank Mercury Mine, confirmed by 210Pb dating. Ages below the 1927 horizon were determined by accelerator mass spectrometry on 14C of coarse organic debris. Calculated sedimentation rates below the 1927 datum are approximately 1 mm/yr, whereas rates from 1927 to 2000 are up to an order of magnitude higher, with averages of approximately 3.5-19 mm/yr. In both the Oaks and Upper Arms, the post-1927 co-occurrence of abrupt shifts in magnetic signatures with color differences indicative of changing redox conditions is interpreted to reflect a more oxygenated diagenetic regime and rapid burial of sediment below the depth of sulfate diffusion. Post-1927 in the Oaks Arm, grain size exhibits a gradual coarsening-upward pattern that we attribute to the input of mechanically deposited waste rock related to open-pit mining activities at the mine. In contrast, grain size in the Upper Arm exhibits a gradational fining-upward after 1927 that we interpret as human-induced erosion of fine-grained soils and chemically weathered rocks of the Franciscan Assemblage by heavy earthmoving equipment associated with a road- and home-building boom, exacerbated by stream channel mining and wetlands destruction. The flux of fine-grained sediment into the Upper Arm increased the nutrient load to the lake, and that in turn catalyzed profuse cyanobacterial blooms through the 20th century. The resulting organic biomass, in combination with the increased inorganic sediment supply, contributed to the abrupt increase in sedimentation rate after 1927.

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 lake's 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.

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 lake's 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.

Stable hydrogen and oxygen isotope ratios of bottled waters of the world.

Bottled and packaged waters are an increasingly significant component of the human diet. These products are regulated at the regional, national, and international levels, and determining the authenticity of marketing and labeling claims represents a challenge to regulatory agencies. Here, we present a dataset of stable isotope ratios for bottled waters sampled worldwide, and consider potential applications of such data for regulatory, forensic and geochemical standardization applications. The hydrogen and oxygen isotope ratios of 234 samples of bottled water range from -147 per thousand to +15 per thousand and from -19.1 per thousand to +3.0 per thousand, respectively. These values fall within and span most of the normal range for meteoric waters, indicating that these commercially available products represent a source of waters for use as laboratory working standards in applications requiring standardization over a large range of isotope ratios. The measured values of bottled water samples cluster along the global meteoric water line, suggesting that bottled water isotope ratios preserve information about the water sources from which they were derived. Using the dataset, we demonstrate how bottled water isotope ratios provide evidence for substantial evaporative enrichment of water sources prior to bottling and for the marketing of waters derived from mountain and lowland sources under the same name. Comparison of bottled water isotope ratios with natural environmental water isotope ratios demonstrates that on average the isotopic composition of bottled water tends to be similar to the composition of naturally available local water sources, suggesting that in many cases bottled water need not be considered as an isotopically distinct component of the human diet. Our findings suggest that stable isotope ratios of bottled water have the power to distinguish ultimate (e.g., recharge) and proximal (e.g., reservoir) sources of bottled water and constitute a potential tool for use in the regulatory monitoring of water products.