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John F. De Wild

Publications and source records attributed to John F. De Wild.

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Environmental factors affecting mercury in Camp Far West Reservoir, California, 2001-03

This report documents water quality in Camp Far West Reservoir from October 2001 through August 2003. The reservoir, located at approximately 300 feet above sea level in the foothills of the northwestern Sierra Nevada, California, is a monomictic lake characterized by extreme drawdown in the late summer and fall. Thermal stratification in summer and fall is coupled with anoxic conditions in the hypolimnion. Water-quality sampling was done at approximately 3-month intervals on eight occasions at several stations in the reservoir, including a group of three stations along a flow path in the reservoir: an upstream station in the Bear River arm (principal tributary), a mid-reservoir station in the thalweg (prereservoir river channel), and a station in the deepest part of the reservoir, in the thalweg near Camp Far West Dam. Stations in other tributary arms of the reservoir included those in the Rock Creek arm of the reservoir, a relatively low-flow tributary, and the Dairy Farm arm, a small tributary that receives acidic, metal-rich drainage seasonally from the inactive Dairy Farm Mine, which produced copper, zinc, and gold from underground workings and a surface pit. Several water-quality constituents varied significantly by season at all sampling stations, including major cations and anions, total mercury (filtered and unfiltered samples), nitrogen (ammonia plus organic), and total phosphorus. A strong seasonal signal also was observed for the sulfurisotope composition of aqueous sulfate from filtered water. Although there were some spatial differences in water quality, the seasonal variations were more profound. Concentrations of total mercury (filtered and unfiltered water) were highest during fall and winter; these concentrations decreased at most stations during spring and summer. Anoxic conditions developed in deep parts of the reservoir during summer and fall in association with thermal stratification. The highest concentrations of methylmercury in unfiltered water were observed in samples collected during summer from deepwater stations in the anoxic hypolimnion. In the shallow (less than 14 meters depth) oxic epilimnion, concentrations of methylmercury in unfiltered water were highest during the spring and lowest during the fall. The ratio of methylmercury to total mercury (MeHg/HgT) increased systematically from winter to spring to summer, largely in response to the progressive seasonal decrease in total mercury concentrations, but also to some extent because of increases in MeHg concentrations during summer. Water-quality data for Camp Far West Reservoir are used in conjunction with data from linked studies of sediment and biota to develop and refine a conceptual model for mercury methylation and bioaccumulation in the reservoir and the lower Bear River watershed. It is hypothesized that MeHg is produced by sulfate-reducing bacteria in the anoxic parts of the water column and in shallow bed sediment. Conditions were optimal for this process during late summer and fall. Previous work has indicated that Camp Far West Reservoir is a phosphate-limited system - molar ratios of inorganic nitrogen to inorganic phosphorus in filtered water were consistently greater than 16 (the Redfield ratio), sometimes by orders of magnitude. Therefore, concentrations of orthophosphate were expectedly very low or below detection at all stations during all seasons. It is further hypothesized that iron-reducing bacteria facilitate release of phosphorus from iron-rich sediments during summer and early fall, stimulating phytoplankton growth in the fall and winter, and that the MeHg produced in the hypolimnion and metalimnion is released to the entire water column in the late fall during reservoir destratification (vertical mixing). Mercury bioaccumulation factors (BAF) were computed using data from linked studies of biota spanning a range of trophic position: zooplankton, midge larvae, mayfly nymphs, crayfish, threadfin shad, bluegill,

California

Geochemical data for mercury, methylmercury, and other constituents in sediments from Englebright Lake, California, 2002

This report presents geochemical data from two 2002 sampling campaigns conducted in Englebright Lake on the Yuba River in northern California. A deep coring campaign was done in May-June 2002 and a shallow sampling campaign was completed in October 2002. This work assessed the chemical composition of material deposited in the reservoir between 1940, the year Englebright Dam was completed, and 2002 as part of the Upper Yuba River Studies Program, an effort designed to evaluate the feasibility of introducing anadromous fish, including steelhead and spring-run Chinook salmon, upstream from Englebright Dam. Results of analyses of total mercury (HgT) in 444 subsamples, methylmercury (MeHg) in 243 subsamples, and other trace and major elements in 202 subsamples are presented. Data quality was evaluated on the basis of analyses of replicate pairs of subsamples, standard reference materials, blanks, and spike additions.Deep coring penetrated the full thickness of material deposited after 1940 at six locations in the reservoir; the cores reached a maximum depth of 32.8 meters below the reservoir floor. At the three deep coring sites closest to Englebright Dam, concentrations of HgT (dry basis) were consistently in the range of 100 to 500 ng/g (nanogram per gram), in sediment dominantly of silt size (median grain size of 0.004 to 0.063 mm [millimeter]). At the deep coring sites located farther upstream, the upper parts of the profile had lower concentrations of HgT, generally ranging from 2 to 100 ng/g, in sediment dominantly of sand size (median grain size from 0.063 to 2 mm). The lower part of the vertical profiles at three upstream coring sites had higher concentrations of HgT than the upper and middle parts of these profiles, and had finer median grain size. The highest median concentration of MeHg (1.1 ng/g) was in the top 2 cm (centimeter) of the shallow box cores. This vertical interval also had the highest value of the ratio of MeHg to HgT, 0.41 percent. Median concentrations of MeHg and median values of MeHg/HgT decreased systematically with depth from 0-4 to 4-8 to 8-12 cm in the shallow cores. However, similar systematic decreases were not observed at the meter scale in the deep cores of the MEM (MEthylMercury) series. The overall median of the ratio MeHg/HgT in the deep cores was 0.25 percent, not much less than the overall median value for the shallow cores (0.33 percent). Mercury-203 radiotracer divalent inorganic mercury (203Hg(II)) was used to determine microbial mercury-methylation potential rates for 11 samples collected from three reservoir locations and various depths in the sediment profile. For the five shallow mercury-methylation subsamples, ancillary geochemical parameters were assayed, including microbial sulfate reduction rates, sulfur speciation (sediment acid volatile sulfide, total reduced sulfur, and pore-water sulfate), iron speciation (sediment acid extractable iron(II), amorphous iron(III), crystalline iron(III) and pore-water iron(II)), pore-water chloride and dissolved organic carbon, and pH, oxidation-reduction potential (Eh) and whole-sediment organic content. The highest potential rates of microbial mercury methylation were measured in shallow (0 to 8 cm depth) sediments (5 to 30 nanograms of mercury per gram dry sediment per day), whereas potential rates for subsamples collected from depths greater than 500 cm were consistently below the detection limit of the radiotracer method (< 0.02 nanogram of mercury per gram dry sediment per day). Chemical analyses of trace and major elements in bed sediment are presented for 202 samples from deep cores from five locations in Englebright Lake. The mean values and standard deviations for selected trace elements were as follows (in micrograms per gram): antimony, 2.4 &plusmn; 1.6; arsenic, 69 &plusmn; 48; chromium, 134 &plusmn; 23; lead, 33 &plusmn; 25; and nickel, 87 &plusmn; 24. Concentrated samples of heavy-mineral grains, prepared using nine large-volume composite samples from

California

Geochemical characterization of water, sediment, and biota affected by mercury contamination and acidic drainage from historical gold mining, Greenhorn Creek, Nevada County, California, 1999-2001

In 1999, the U.S. Geological Survey (USGS) initiated studies of mercury and methylmercury occurrence, transformation, and transport in the Bear River and Yuba River watersheds of the northwestern Sierra Nevada. Because these watersheds were affected by large-scale, historical gold extraction using mercury amalgamation beginning in the 1850s, they were selected for a pilot study of mercury transport by the USGS and other cooperating agencies. This report presents data on methylmercury (MeHg) and total mercury (THg) concentrations in water, bed sediment, invertebrates, and frogs collected at 40 stations during 1999-2001 in the Greenhorn Creek drainage, a major tributary to Bear River. Results document several mercury contamination “hot spots” that represent potential targets for ongoing and future remediation efforts at abandoned mine sites in the study area. Water-quality samples were collected one or more times at each of 29 stations. The concentrations of total mercury in 45 unfiltered water samples ranged from 0.80 to 153,000 nanograms per liter (ng/L); the median was 9.6 ng/L. Total mercury concentrations in filtered water (41 samples) ranged from less than 0.3 to 8,000 ng/L; the median was 2.7 ng/L. Concentrations of methylmercury in the unfiltered water (40 samples) ranged from less than 0.04 to 9.1 ng/L; the median was 0.07 ng/L. Methylmercury in filtered water (13 samples) ranged from less than 0.04 to 0.27 ng/L; the median was 0.04 ng/L. Acidic drainage with pH values as low as 3.4 was encountered in some of the mined areas. Elevated concentrations of aluminum, cadmium, copper, iron, manganese, nickel, and zinc were found at several stations, especially in the more acidic water samples. Total mercury concentrations in sediment were determined by laboratory and field methods. Total mercury concentrations (determined by laboratory methods) in ten samples from eight stations ranged from about 0.0044 to 12 µg/g (microgram per gram, equivalent to parts per million). Methylmercury concentrations in these samples ranged from less than 0.00011 to 0.0095 µg/g. A field panning method was used to determine the concentration of liquid elemental mercury in 22 samples from 14 stations. Measured quantities of elemental mercury recovered by panning ranged from a trace amount estimated at 100 milligrams per kilogram (equivalent to parts per million) to 45,000 milligrams per kilogram (equivalent to 4.5 per cent, by weight). In total, 194 invertebrate samples were collected at 31 stations; 78 of the samples were analyzed for concentrations of THg and MeHg and used to calculate MeHg to THg ratios. A total of 69 frog samples were collected at 19 stations, and all were analyzed only for THg. Ranges of MeHg concentrations (µg/g, wet weight) in invertebrate samples and number of samples (n) were 0.0012-0.048 for banana slugs (Arionidae, n = 27), 0.027-0.39 for dobsonflies (Corydalidae, n = 14), 0.029-0.50 for predaceous diving beetles (Dytiscidae, n = 31), 0.026-0.52 for predaceous stoneflies (Perlidae, n = 18), 0.011-1.6 for dragonflies (Odonata, n = 46), and 0.061-0.55 for water striders (Gerridae, n = 56). The ratio of MeHg to THg in invertebrates was greater than 50 percent for 74 of 78 samples. The data from this reconnaissance sampling effort have been used by land-management agencies in selecting abandoned mine sites for remediation. The Forest Service has remediated the Sailor Flat site, and the Bureau of Land Management has initiated plans to remediate the Boston Mine drainage tunnel.

California

Determination of methyl mercury by aqueous phase ethylation, followed by gas chromatographic separation with cold vapor atomic fluorescence detection

A recent national sampling of streams in the United States revealed low methyl mercury concentrations in surface waters. The resulting median and mean concentrations, calculated from 104 samples, were 0.06 nanograms per liter (ng/L) and 0.15 ng/L, respectively. This level of methyl mercury in surface water in the United States has created a need for analytical techniques capable of detecting sub-nanogram per liter concentrations. In an attempt to create a U.S. Geological Survey approved method, the Wisconsin District Mercury Laboratory has adapted a distillation/ethylation/ gas-phase separation method with cold vapor atomic fluorescence spectroscopy detection for the determination of methyl mercury in filtered and unfiltered waters. This method is described in this report. Based on multiple analyses of surface water and ground-water samples, a method detection limit of 0.04 ng/L was established. Precision and accuracy were evaluated for the method using both spiked and unspiked ground-water and surface-water samples. The percent relative standard deviations ranged from 10.2 to 15.6 for all analyses at all concentrations. Average recoveries obtained for the spiked matrices ranged from 88.8 to 117 percent. The precision and accuracy ranges are within the acceptable method-performance limits. Considering the demonstrated detection limit, precision, and accuracy, the method is an effective means to quantify methyl mercury in waters at or below environmentally relevant concentrations

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