Evaluation of Statistical Treatments of Left-Censored Environmental Data Using Coincident Uncensored Data Sets. II. Group Comparisons

The main classes of statistical treatments that have been used to determine if two groups of censored environmental data arise from the same distribution are substitution methods, maximum likelihood (MLE) techniques, and nonparametric methods. These treatments along with using all instrument-generated data (IN), even those less than the detection limit, were evaluated by examining 550 data sets in which the true values of the censored data were known, and therefore “true” probabilities could be calculated and used as a yardstick for comparison. It was found that technique “quality” was strongly dependent on the degree of censoring present in the groups. For low degrees of censoring (<25% in each group), the Generalized Wilcoxon (GW) technique and substitution of √2/2 times the detection limit gave overall the best results. For moderate degrees of censoring, MLE worked best, but only if the distribution could be estimated to be normal or log-normal prior to its application; otherwise, GW was a suitable alternative. For higher degrees of censoring (each group >40% censoring), no technique provided reliable estimates of the true probability. Group size did not appear to influence the quality of the result, and no technique appeared to become better or worse than other techniques relative to group size. Finally, IN appeared to do very well relative to the other techniques regardless of censoring or group size

Isotopic analyses of DSDP Hole 45-395A samples from veins containing gypsum (Table 1)

Gypsum and halite crystals, together with saponite and phillipsite, were found in a vein in a basalt sill 625 m below the sea floor at DSDP Site 395A, located 190 km west of the crest of the Mid-Atlantic Ridge. The delta34S value of the gypsum (+19.4‰) indicates a seawater source for the sulfate. The delta18O values of the saponite (+19.9‰) and phillipsite (+18.1‰) indicate either formation from normal seawater at about 55°C or formation from delta18O-depleted seawater at a lower temperature. The gypsum (which could be secondary after anhydrite) was formed by reaction between Ca[2+] released from basalt and SO4[2-] in circulating seawater. The halite could have formed when water was consumed by hydration of basalt under conditions of extremely restricted circulation. A more probable mechanism is that the gypsum was originally precipitated as anhydrite at temperatures above 60°C. As the temperature dropped the anhydrite converted to gypsum. The conversion would consume water, which could cause halite precipitation, and would cause an increase in the volume of solids, which would plug the vein and prevent subsequent dissolution of the halite

Metals Transport in the Sacramento River, California, 1996–1997 Volume 2: Interpretation of Metal Loads

Metals transport in the Sacramento River, northern California, from July 1996 to June 1997 was evaluated in terms of metal loads from sam-ples of water and suspended colloids that were collected on up to six occasions at 13 sites in the Sacramento River Basin. Four of the sampling periods (July, September, and November 1996; and May–June 1997) took place during relatively low-flow conditions and two sampling periods (December 1996 and January 1997) took place during high-flow and flooding conditions, respec-tively. This study focused primarily on loads of cadmium, copper, lead, and zinc, with secondary emphasis on loads of aluminum, iron, and mercury. Trace metals in acid mine drainage from abandoned and inactive base-metal mines, in the East and West Shasta mining districts, enter the Sacramento River system in predominantly dis-solved form into both Shasta Lake and Keswick Reservoir. The proportion of trace metals that was dissolved (as opposed to colloidal) in samples collected at Shasta and Keswick dams decreased in the order zinc ≈ cadmium \u3e copper \u3e lead. At four sampling sites on the Sacramento River—71, 256, 360, and 412 kilometers downstream of Keswick Dam—trace-metal loads were predomi-nantly colloidal during both high- and low-flow conditions. The proportion of total cadmium, copper, lead, and zinc loads transported to San Francisco Bay and the Sacramento–San Joaquin Delta estuary (referred to as the Bay–Delta) that is associated with mineralized areas was estimated by dividing loads at Keswick Dam by loads 412 kilometers downstream at Freeport and the Yolo Bypass. During moderately high flows in December 1996, mineralization-related total (dissolved + colloidal) trace-metal loads to the Bay–Delta (as a percentage of total loads meas-ured downstream) were cadmium, 87 percent; copper, 35 percent; lead, 10 percent; and zinc, 51 percent. During flood conditions in January 1997 loads were cadmium, 22 percent; copper, 11 percent; lead, 2 percent; and zinc, 15 percent. During irrigation drainage season from rice fields (May–June 1997) loads were cadmium, 53 percent; copper, 42 percent; lead, 20 percent; and zinc, 75 percent. These estimates must be qualified by the following factors: (1) metal loads at Colusa in December 1996 and at Verona in May–June 1997 generally exceeded those determined at Freeport during those sampling periods. Therefore, the above percentages represent maximum estimates of the apparent total proportion of metals from mineralized areas upstream of Keswick Dam; and (2) for logistics reasons, the Sacramento River was sampled at Tower Bridge instead of at Freeport during January 1997. Available data suggest that trace metal loads from agricultural drainage may be significant during certain flow conditions in areas where metals such as copper and zinc are added as agri-cultural amendments. Copper loads for sampling periods in July and September 1996 and in May– June 1997 show increases of dissolved and colloidal copper and in colloidal zinc between Colusa and Verona, the reach of the Sacramento River along which the Colusa Basin Drain, the Sacramento Slough, and other agricultural return flows are tributaries. Monthly sampling of these two agricultural drains by the USGS National Water-Quality Assessment Program shows seasonal variations in metal concentrations, reaching maximum concentrations of 4 to 6 micrograms per liter in “dissolved” (0.45-micrometer filtrate) copper concentrations in May 1996, December 1996, and June 1997. The total (dissolved plus colloidal) load of copper from the Colusa Basin Drain in June 1997 was 18 kilograms per day, whereas the copper load in Spring Creek, which drains the inactive mines on Iron Mountain, was 20 kilograms per day during the same sampling period. For comparison, during the January 1997 flood, the copper load in Spring Creek was about 1,100 kilograms per day and the copper load in the Yolo Bypass was about 7,300 kilograms per day. The data clearly indicate that most copper and zinc loads during the January 1997 flood entered the Sacramento River up-stream of Colusa, and upstream of the influence of the most intense agricultural drainage return flows in the Sacramento River watershed. This study has demonstrated that some trace metals of environmental significance (cadmium, copper, and zinc) in the Sacramento River are transported largely in dissolved form at upstream sites (below Shasta Dam, below Keswick Dam, and at Bend Bridge) proximal to the mineralized areas of the West Shasta and East Shasta mining districts. In contrast, these trace metals are transported largely in colloidal form at downstream sites (Colusa, Verona, Freeport, and Yolo Bypass). Aluminum, iron, and lead were observed to be transported predominantly in the colloidal phase at all mainstem Sacramento River sampling sites during all sampling periods in this study. Despite continuous water treatment, which has removed 85 to 90 percent of the cadmium, copper, and zinc from the mine drainage at Iron Mountain, Spring Creek remains a significant source of these metals to the Sacramento River system

Continuous Lake-Sediment Records of Glaciation in the Sierra Nevada between 52,600 and 12,500 14C yr B.P.

The chemistry of the carbonate-free clay-size fraction of Owens Lake sediments supports the use of total organic carbon and magnetic susceptibility as indicators of stadial-interstadial oscillations, Owens Lake records of total organic carbon, magnetic susceptibility, and chemical composition of the carbonate-free, clay-size fraction indicate that Tioga glaciation began ~24,500 and ended by ~13,600 14C yr B.P. Many of the components of glacial rock flour (e.g., TiO2 , MnO, BaO) found in Owens Lake sediments achieved maximum values during the Tioga glaciation when valley glaciers reached their greatest extent. Total organic carbon and Si02 (amorphous) concentrations reached minimum values during Tioga glaciation, resulting from decreases in productivity that accompanied the introduction of rock flour into the surface waters of Owens Lake. At least 20 stadial-interstadial oscillations occurred in the Sierra Nevada between 52,600 and 14,000 14C yr B.P. Total organic carbon data from a Pyramid Lake sediment core also indicate oscillations in glacier activity between \u3e39,500 and ~13,600 14C yr B.P. Alpine glacier oscillations occurred on a frequency ofbasins, suggesting that millennial-scale oscillations occurred in California and Nevada during most of the past 52,600 yr

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, standardreference 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)), porewater 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 (\u3c 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 ± 1.6; arsenic, 69 ± 48; chromium, 134 ± 23; lead, 33 ± 25; and nickel, 87 ± 24. Concentrated samples of heavy-mineral grains, prepared using nine large-volume composite samples from deep cores, were examined using optical and scanning-electron microscopy. Estimated gold concentrations in the composite sediment samples ranged from 38 to 840 milligrams per cubic meter. Grains of gold-mercury amalgam and grains of electrum (native gold), with and without mercury staining, were observed in the heavy-mineral concentrates. Results of this study will be used to evaluate potential effects on fish habitat and trace-element transport in relation to various scenarios regarding efforts to improve fish passage at Englebright Lake. The scenarios include dredging or release of sediments to downstream environments in association withdam modification or removal

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 the 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 part 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. In total, 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

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 (pre-reservoir 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 sulfur-isotope 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 deep-water 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, and spotted bass. Significant increases in total mercury in tissue with increasing organism size were observed for all three fish species and for crayfish. The BAF values were computed using the average methylmercury concentration (wet) in biota divided by the arithmetic mean concentration of methylmercury in filtered water (0.04 nanograms per liter). As expected, the BAF values increased systematically with increasing trophic position. Values of BAF were 190,000 for zooplankton; 470,000 to 930,000 for three taxa of invertebrates; 2.7 million for threadfin shad (whole body); 4.2 million for bluegill (fillet); and 10 million for spotted bass (fillet). The BAF values are high compared with those for biota in other reservoirs in northern California and elsewhere, indicating relatively efficient biomagnification of mercury in Camp Far West Reservoir