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Toxic substances in surface waters and sediments: A study to assess the effects of arsenic-contaminated alluvial sediment in Whitewood Creek, South Dakota

Field measurements and bioassay experiments were done to investigate the effects of arsenic and phosphorus interactions on sorption of these solutes by the benthic flora (periphyton and submerged macrophytes) in Whitewood Creek, a stream in western South Dakota. Short-term (24-hour) sorption experiments were used to determine arsenic transport characteristics for algae (first-order rate constants for solute sorption, biomass, and accumulation factors) collected in the creek along a transect beginning upstream from a mine discharge point and downgradient through a 57-kilometer reach. Temporal changes in biomass differed significantly between and within sampling sites. Arsenic concentrations in plant tissue increased with distance downstream, but temporal changes in concentrations in tissues differed considerably from site to site. Cultures of Achnanthes minutissima (Bacillariophyceae) and Stichococcus sp. (Chlorophyceae) were isolated from four sites along a longitudinal concentration gradient of dissolved arsenic within the study reach and were maintained at ambient solute concentrations. Arsenic accumulation factors and sorption-rate constants for these isolates were determined as a function of dissolved arsenate and orthophosphate. Cell surfaces of algal isolates exhibited preferential orthophosphate sorption over arsenate. Initial sorption of both arsenate and orthophosphate followed first-order mass transfer for each culturing condition. Although sorption-rate constants increased slightly with increased dissolved-arsenate concentration, algae, isolated from a site with elevated dissolved arsenic in the stream channel, had a significantly slower rate of arsenic sorption compared with the same species isolated from an uncontaminated site upstream. In diel studies, amplitudes of the pH cycles increased with measured biomass except at a site immediately downstream from water-treatment-plant discharge. Inorganic pentavalent arsenic dominated arsenic speciation at all sites?not a surprising result for the well-oxygenated water column along this reach. Concentration fluctuations in dissolved-arsenic species lagged pH fluctuations by approximately 3 hours at the most downstream site, but no discernible lag was observed at an artificially pooled area with an order of magnitude higher biomass. Furthermore, the amplitudes of diel fluctuations in arsenic species were greater at the pooled area than at the most downstream site. Lack of correspondence between changes in dissolved-orthophosphate concentrations and arsenic species may have resulted from preferential sorption of orthophosphate over arsenate by the biomass. Based on carbon-fixation estimates, the phosphorus demand from photosynthetic activity required water-column concentrations to be supplemented by another source such as phosphate regeneration within the benthic community or desorption of particle-bound phosphate.

South Dakota↗

Ground-water contamination by crude oil at the Bemidji, Minnesota, research site- An introduction: Chapter A in Ground-water contamination by crude oil at the Bemidji, Minnesota, research site; US Geological Survey Toxic Waste--ground-water contamination study

The U.S. Geological Survey has begun a research project to improve understanding of the mobilization, transport, and fate of petroleum contaminants in the shallow subsurface and to use this understanding to develop predictive models of contaminant behavior. The project site is near Bemidji in northern Minnesota where an accidental spill of 10,500 barrels of crude oil occurred when a pipeline broke on August 20, 1979. Regulatory and remedial actions have been completed. The site is in a remote area with neither man-made hydraulic stresses nor other anthropogenic sources of the compounds of interest. The spill is in the recharge area of a local flow system that discharges to a small closed lake approximately 1,000 feet down the hydraulic gradient. The aquifer is pitted outwash dissected by younger glacial channels and is underlain by poorly permeable till at a depth of about 80 feet. Ground water dissolves oil floating on the water table under the spill site and moves toward the lake. At the water table, ground water enters the lake through lacustrine sediments; at depth, flow may be underneath the lake through the outwash. Contaminant transport has been as rapid as 4 feet per day based on the rate of movement of contaminants monitored through wells installed within a few days of the spill, but average rates are undoubtedly much less.

Minnesota↗

Determination of hydraulic conductivity in three dimensions and its relation to dispersivity: Chapter D in Ground-water contamination by crude oil at the Bemidji, Minnesota, research site; US Geological Survey Toxic Waste--ground-water contamination study

Recent investigations suggest that dispersion in aquifers is scale dependent and a function of the heterogeneity of aquifer materials. Theoretical stochastic studies indicate that determining hydraulic-conductivity variability in three dimensions is important in analyzing the dispersion process. Even though field methods are available to approximate hydraulic conductivity in three dimensions, the methods are not generally used because of high cost of field equipment and because measurement and analysis techniques are cumbersome and time consuming. The hypothesis of this study is that field-determined values of dispersivity are scale dependent and that they may be described as a function of hydraulic conductivity in three dimensions. The objectives of the study at the Bemidji research site are to (1) determine hydraulic conductivity of the porous media in three dimensions, (2) determine field values of dispersivity and its scale dependence on hydraulic conductivity, and (3) develop and apply a computerized data-collection, storage, and analysis system for field use in comprehensive determination of hydraulic conductivity and dispersivity. Plans for this investigation involve a variety of methods of analysis. Hydraulic conductivity will be determined separately in the horizontal and vertical planes of the hydraulic-conductivity ellipsoid. Field values of dispersivity will be determined by single-well and doublet-well injection or withdrawal tests with tracers. A computerized data-collection, storage, and analysis system to measure pressure, flow rate, tracer concentrations, and temperature will be designed for field testing. Real-time computer programs will be used to analyze field data. The initial methods of analysis will be utilized to meet the objectives of the study. Preliminary field data indicate the aquifer underlying the Bemidji site is vertically heterogeneous, cross-bedded outwash. Preliminary analysis of the flow field around a hypothetical doublet-well tracer test indicates that the location of the wells can affect the field value of dispersivity. Preliminary analysis also indicates that different values of dispersivity may result from anisotropic conditions in tests in which observation wells are located at equal radial distances from either the injection or withdrawal well.

Water-Resources Investigations Report↗

Effects of land use on ground-water quality in central Florida — Preliminary results: U.S. Geological Survey Toxic Waste — Ground-water Contamination Program

Groundwater is the principal source of drinking water in central Florida. The most important hydrogeologic unit is the Floridan aquifer system, consisting of fractured limestone and dolomite limestone. Activities of man in areas of recharge to the Floridian aquifer system that may be affecting groundwater quality include: (1) the use of drainage wells for stormwater disposal in urban areas, (2) the use of pesticides and fertilizers in citrus groves, and (3) the mining and processing of phosphate ore in mining areas. Preliminary findings about the impacts of these land uses on ground-water quality by comparison with a fourth land use representing the absence of human activity in another area of recharge are presented. Drainage wells convey excess urban stormwater directly to the Upper Floridian aquifer. The volatile organic compounds are the most common contaminants in ground water. Trace elements such as chromium and lead are entering the aquifer but their movement is apparently attenuated by precipitation reactions associated with high pH or by cation-exchange reactions. Among the trace elements and organic chemicals, most ground-water contamination in citrus production areas is caused by pesticides, which include the organic compounds simazine, ametryne, chlordane, DDE , bromacil, aldicarb, EDB, trifluralin, and diazinon, and the trace elements zinc and copper; other contaminants include benzene, toluene, napthalene, and indene compounds. In the phosphate mining area, constituents of concern are arsenic, selenium, and mercury, and secondarily lead, chromium, cadmium, and others. Organic compounds such as fluorene, naphthalene, di-n-butyl phthalate, alkylated benzenes and naphthalenes, and indene compounds also are entering groundwater. (Author 's abstract)

Florida↗

US Geological Survey Toxic Substances Hydrology Program: Proceedings of the technical meeting, Phoenix, Arizona, September 26-30, 1988

Crude oil floating at the surface of a shallow aquifer of glacial outwash, near Bemidji, Minnesota, is altered by geochemical processes. Hydrocarbons from the oil are attenuated by several reactions that include aerobic and anaerobic microbial degradation. These degradation reactions result in the development of geochemical facies in the shallow groundwater system. Groundwater most affected by the presence of organic compounds is anoxic, and concentrations of methane, dissolved organic carbon, and total inorganic are high--0.76 millimole/L, 2.9 millimole/L, and 12.3 millimole/L, respectively. The concentrations of chemical species and delta-(13)C isotope values indicate that the plume near the oil lens has become progressively more reducing. Over a 4-year period (1984 through 1987), the concentrations of methane and iron have increased by a factor of > 25. The data suggest that sequential degradation occurs, as predicted by thermo-dynamics: manganese is reduced before iron is reduced, which occurs before methanogenesis. These data provide field evidence that reduction of iron and manganese is an important mechanism of decomposition of organic matter in aquifers. The delta-(13)C values of inorganic carbon of the native groundwater range from -12 ppt to -15 ppt as a result of mixing of soil CO2 with CO2 from the dissolution of carbonates. Non methanogenic biodegradation of oil constituents adds isotopically light CO2 to the groundwater because the oil has a delta-(13)C value of 28 ppt. The delta-(13)C value of inorganic carbon in the reducing zone have become progressively heavier from 1985 through 1987. The maximum change occurs 15 m downgradient from the oil lens, where the delta-(13)C values increased from -21.6 ppt to -5.35 ppt. This change indicates that the plume has become more reducing and methanogenic over time.

Water-Resources Investigations Report↗