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Reactive solute transport in streams: A surface complexation approach for trace metal sorption

A model for trace metals that considers in-stream transport, metal oxide precipitation-dissolution, and pH-dependent sorption is presented. Linkage between a surface complexation submodel and the stream transport equations provides a framework for modeling sorption onto static and/or dynamic surfaces. A static surface (e.g., an iron- oxide-coated streambed) is defined as a surface with a temporally constant solid concentration. Limited contact between solutes in the water column and the static surface is considered using a pseudokinetic approach. A dynamic surface (e.g., freshly precipitated metal oxides) has a temporally variable solid concentration and is in equilibrium with the water column. Transport and deposition of solute mass sorbed to the dynamic surface is represented in the stream transport equations that include precipitate settling. The model is applied to a pH-modification experiment in an acid mine drainage stream. Dissolved copper concentrations were depressed for a 3 hour period in response to the experimentally elevated pH. After passage of the pH front, copper was desorbed, and dissolved concentrations returned to ambient levels. Copper sorption is modeled by considering sorption to aged hydrous ferric oxide (HFO) on the streambed (static surface) and freshly precipitated HFO in the water column (dynamic surface). Comparison of parameter estimates with reported values suggests that naturally formed iron oxides may be more effective in removing trace metals than synthetic oxides used in laboratory studies. The model's ability to simulate pH, metal oxide precipitation-dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between trace metal chemistry and hydrologic transport at the field scale.

Water Resources Research↗

Synthesis of new oligothiophene derivatives and their intercalation compounds: Orientation effects

The orientation dependence of intercalated oligothiophene derivatives in vermiculite and metal disulfides MS2 (M = Mo, Ti and Zr) on the pendant group on the thiophene ring and the host material was studied by X-ray diffraction (XRD) and solid state nuclear magnetic resonance spectroscopy. Amino and nitro derivatives of bi-, ter- and quarter-thiophenes were synthesized for the first time. The amino-oligothiophenes were intercalated into vermiculite by an exchange reaction with previously intercalated octadecylammonium vermiculite and into MS2 by the intercalation-exfoliation technique. Analysis of the XRD data indicates that a monolayer of amino-oligothiophene orients perpendicularly to the silicate surface in vermiculite and lies flat in the van der Waals gap of MS2.

Synthetic Metals↗

Yields of selected constituents in base flow and stormflow in urban watersheds of Jefferson County, Kentucky, 1988-92

Mean annual base-flow and stormflow yields of selected water-quality constituents from urban watersheds of Jefferson County, Kentucky, were estimated for 1988-92 to help describe the pro portions of constituent transport from point and nonpoint sources. Yield estimates were based on streamflow and water-quality data collected from a network of 25 stream sites in the county. Water- quality data for which estimates of base-flow and stormflow yields were computed include dissolved oxygen and oxygen demand, dissolved solids, suspended and volatile solids, nutrients, metals, and synthetic organic compounds. Transport of most constituents occurred primarily during stormflow. Chemical oxygen demand was related to the amount of industrial land use in each watershed, nitrite and phosphorus yields were inversely proportional to the amount of nonurban and commercial land use in each watershed, and zinc yields were inversely related to the degree of nonurban land use in each watershed.

Water-Resources Investigations Report↗

Ground-Water Quality in the Caguas-Juncos Valley, Puerto Rico, April to October 1990

Ground water from 48 wells and 1 spring in the Caguas-Juncos Valley was sampled and analyzed for major ions, nutrients, trace metals, and volatile synthetic organic chemicals from April to October 1990. This report presents the results of physical and chemical analyses made on these water samples. Dissolved-solids concentrations exceeded 500 milligrams per liter in 28 percent of the samples. Concentrations of trace metals were below the maximum contaminant levels set by Federal and Commonwealth agencies. Volatile synthetic organic chemicals were detected in water from five wells, four of which were located in urban and industrial areas. Concentrations of benzene, ethylbenzene, toluene, and xylene detected in samples from one observation well exceeded the maximum contaminant levels set be Federal and Commonwealth agencies.

Open-File Report↗

Quantification of manganese for ChemCam Mars and laboratory spectra using a multivariate model

We report a new calibration model for manganese using the laser-induced breakdown spectroscopy instrument that is part of the ChemCam instrument suite onboard the NASA Curiosity rover. The model has been trained using an expanded set of 523 manganese-bearing rock, mineral, metal ore, and synthetic standards. The optimal calibration model uses the Partial Least Squares (PLS) and Least Absolute Shrinkage and Selection Operator (LASSO) multivariate techniques, with a novel “double blending” technique. We determined the detection limit for manganese is 82 ppm using a method blank procedure and is possibly as low as 27 ppm based on visual inspection of the spectra. Based on a representative test set consisting of measurements on 93 standards, the double blended multivariate model shows a Root Mean Squared Error of Prediction (RMSEP) accuracy of 1.39 wt% MnO for the full blended model. Employing a local RMSEP estimate where the model performance is evaluated based on nearby test samples, the accuracy is 0.03 wt% at the quantification limit (0.05 wt% MnO), 0.4 wt% accuracy at 1.0 wt% MnO, and 4.4 wt% accuracy at 100 wt% MnO. Precision is estimated using the standard deviation of the test set measurements, and is ±0.01 wt% MnO at the quantification limit, ±0.09 wt% MnO at 1.0 wt% MnO, and ± 2.1 wt% MnO at 100 wt% MnO (all 1 standard deviation). This new calibration is important for understanding the variation of manganese in the bedrock with the Curiosity rover on Mars, which provides insight into past redox conditions on Mars.

Spectrochimica Acta B↗

National water summary 1986: Hydrologic events and ground-water quality

Ground water is one of the most important natural resources of the United States and degradation of its quality could have a major effect on the welfare of the Nation. Currently (1985), ground water is the source of drinking water for 53 percent of the Nation's population and for more than 97 percent of its rural population. It is the source of about 40 percent of the Nation's public water supply, 33 percent of water for irrigation, and 17 percent of freshwater for selfsupplied industries. Ground water also is the source of about 40 percent of the average annual streamflow in the United States, although during long periods of little or no precipitation, ground-water discharges provide nearly all of the base streamflow. This hydraulic connection between aquifers and streams implies that if a persistent pollutant gets into an aquifer, it eventually could discharge into a stream. Information presented in the 1986 National Water Summary clearly shows that the United States has very large amounts of potable ground water available for use. Although naturally occurring constituents, such as nitrate, and human-induced substances, such as synthetic organic chemicals, frequently are detected in ground water, their concentrations usually do not exceed existing Federal or State standards or guidelines for maximum concentrations in drinking water. Troublesome contamination of ground water falls into two basic categories related to the source or sources of the contamination. Locally, high concentrations of a variety of toxic metals, organic chemicals, and petroleum products have been detected in ground water associated with point sources such as wastedisposal sites, storage-tank leaks, and hazardous chemical spills. These types of local problems commonly occur in densely populated urban areas and industrialized areas. Larger, multicounty areas also have been identified where contamination frequently is found in shallow wells. These areas generally are associated with broad-scale, or nonpoint, sources of contamination such as agricultural activities or highdensity domestic waste disposal (septic systems) in urban centers. At present, only a very small percentage of the total volume of potable ground water in the United States is contaminated from both point and nonpoint sources; however, available data, especially data about the occurrence of synthetic organic and toxic substances, generally are inadequate to determine the full extent of ground-water contamination in the Nation's aquifers or to define trends in groundwater quality. Most information about the occurrence of these substances has come from the study of individual sites or areas where contamination had already been detected or suspected. Management and protection of ground water present a major challenge to the Nation. Current and projected costs of detection and cleanup of existing ground-water contamination are staggering and, even so, complete removal of pollutants from ground water in the vicinity of some waste sites might not be technically feasible. At all levels of government, the task of protecting the resource for its most beneficial uses is difficult and controversial. Despite increasing awareness that some of the Nation's ground water is contaminated with a variety of toxic metals, synthetic organic chemicals, radionuclides, pesticides, and other contaminants that might present a long-term risk to human health, public policy towards ground-water protection is still in the formative stages. Despite increasing efforts devoted to ground-water protection by State and Federal regulatory and resource-management agencies, the extent of ground-water contamination is likely to appear to increase over the next few years because more agencies will be searching for evidence of contamination, and they will be using increasingly sensitive analytical procedures. Increased technology and expanded monitoring activities probably will detect the effects of past contamination and land uses on water quality. The significant time lag between a waterquality change in one part of an aquifer system and the effects of that change at a downgradient site, such as a well, results from the generally slow movement of ground water. This lag between cause and observed effect needs to be considered in evaluating the effectiveness of current and future ground-water policies and remedial measures. Conclusive answers to questions about the location, extent, and severity of ground-water contamination, and about trends in ground-water quality, must await further collection and analysis of data from the Nation's aquifers. Generalizations, however, can be made, and the 1986 National Water Summary, which describes the natural quality of ground-water resources in each State and the major contamination problems that have been identified as of 1986, provides a national perspective of the ground-water-quality situation. The 1986 National Water Summary follows the format of previous volumes. It contains three parts, and the contents of each of these parts are highlighted below.

Water Supply Paper↗

Contaminants in fishes from Great Lakes-influenced sections and above dams of three Michigan rivers. I: Concentrations of organo chlorine insecticides, polychlorinated biphenyls, dioxin equivalents, and mercury

Fishes of the Great Lakes contain hazardous chemicals such as synthetic halogenated hydrocarbons and metals. These fish can move from the lakes into the Great Lakes tributaries of Michigan. In doing so, they transport concentrationsof contaminants which may represent a risk to wildlife. Concentrations of mercury (Hg), total polychlorinated biphenyls (PCBs), 2,3,7,8-tetrachlorodibenzo- p -dioxin equivalents (TCDD-EQ), total DDT complex, aldrin, endrin, dieldrin, heptachlor, heptachlor epoxide, lindane, hexachlorobenzene, cis -chlordane, oxychlordane, endosulfan-I, methoxychlor, trans -chlordane, and trans -nonachlor were determined in composite samples of fishes from above and below Michigan hydroelectric dams, which separate the fishes which have access to the Great Lakes from fishes that do not. Mean concentrations of total PCBs, TCDD-EQ, DDT, and most of the other pesticides were greater in composite samples of six species of fishes from below than above the dams on the Au Sable, Manistee, and Muskegon Rivers. Concentrations of mercury, were the same or greater above the dams than below. However, this difference was statistically significant only on the Au Sable. Mercury concentrations ranged from less than 0.05 mg/kg to 0.73 mg Hg/kg, ww. Total concentrations of PCBs ranged from 0.02 to 1.7 mg/kg, ww. Concentrations of 2,3,7,8-tetrachlordibenzo- p -dioxin equivalents varied among fishes and locations. The concentrations of TCDD-EQ ranged from 2.4 to 71 μg/kg, ww, with concentrations in carp being the greatest. Concentrations of TCDD-EQ were greater than the concentrations which would be expected to occur, due solely to the presence of polychlorinated dibenzo- p -dioxins (PCDD), polychlorinated dibenzofurans (PCDF), and technical mixtures of PCBs.

Michigan↗

Water-quality trends for streams and reservoirs in the Research Triangle area of North Carolina, 1983-95

Water-quality and streamflow monitoring data, collected from 1983 to 1995, were analyzed for 34 stream and reservoir sites in a seven-county region within the upper Neuse and upper Cape Fear River Basins. Early data (1983-88) were compiled from U.S. Geological Survey water-quality studies and from the ambient water-quality monitoring network of the North Carolina Department of Environment, Health, and Natural Resources. Analyses of major ions, nutrients, metals, trace elements, and synthetic organic compounds were compiled from samples collected by the U.S. Geological Survey from 1988 to 1995 as part of a continuing project to monitor the water quality of surface-water supplies in the Research Triangle area of North Carolina, and from the North Carolina Department of Environment, Health, and Natural Resources ambient water-quality monitoring network. This report presents the results of analysis of consistently increasing or decreasing trends in concentrations of nitrogen and phosphorus species, suspended sediment, suspended solids, sodium, chloride, iron, manganese, zinc, and chlorophyll a from seasonal Kendall trend analysis on flow-adjusted concentrations for streams and concentrations in lakes. Total phosphorus concentrations also were tested for a step decrease in concentration (step trend) associated with the North Carolina phosphate-detergent ban of 1988. For some other constituents, insufficient data or values below laboratory detection limits precluded trend analysis. A regionwide decrease in total phosphorus, ranging from 25 to 81 percent, was observed that coincided with increased phosphorus removal efforts at municipal wastewater-treatment facilities in the region and the statewide phosphate-detergent ban. Most sites had stable or decreasing trends in nitrogen concentrations; however, increasing trends occurred in the Neuse River near Clayton and at Smithfield, both of which are downstream from the developing Raleigh-Durham area. Chlorophyll a concentrations have increased by 17 to 52 percent per year at monitored reservoirs, except at Cane Creek Reservoir and Lake Michie where there was no trend. No significant trends in suspended-sediment concentrations were observed. Long-term sodium concentrations were available for only a few sites. Of these, decreasing concentrations were observed in the Neuse River at Smithfield and Cane Creek near Orange Grove, and an increasing concentration was observed in University Lake. At most sites, concentrations of manganese, iron, and zinc were stable. Decreasing iron trends were observed in Little River and Cane Creek Reservoirs and Lake Michie. Cane Creek Reservoir also had a decreasing manganese trend. Seven sites, all downstream from wastewater-treatment facilities, were analyzed for zinc trends. A decreasing trend was observed in two of these--Knap of Reeds Creek and Little Lick Creek.

North Carolina↗

Water-quality characteristics of selected public recreational lakes and ponds in Connecticut

Reconnaissance limnological and lakebed-sediment surveys were conducted in Connecticut during 1989-91 by the U.S. Geological Survey, in cooperation with the Connecticut Department of Environmental Protec- tion, to evaluate water-quality characteristics of selected public recreational lakes and ponds in the State. Limnological surveys were conducted on 49 lakes and ponds selected from a list of 105 publicly owned waterbodies that qualified for water- quality assessments under Section 314 of the Federal Clean Water Act. Lakebed-sediment surveys were conducted in 9 river impoundments and 1 riverine lake below industrial areas and 2 headwater lakes in relatively pristine areas. The limnological surveys consisted of two sampling events--during spring turnover and during the summer stratifi- cation. Each sampling event included depth profiles of water temperature, specific conductance, hydrogen-ion activity, and dissolved oxygen concen- trations; measurements of Secchi disc transparency; and the collection of samples for the analyses of alkalinity, chlorophyll, phosphorus, and nitrogen concentrations. Areal extent and population density of the dominant aquatic macrophytes were qualita- tively noted during the summer sampling event. These water-quality data were used to determine the trophic classification and acidification status of the 49 lakes. The trophic classification yielded the following results: 2 oligotrophic, 8 early mesotrophic, 13 mesotrophic, 5 late mesotrophic, 10 eutrophic, and 11 highly eutrophic lakes. In terms of acidification status, 7 lakes were classified as acid threatened and 42 as not threatened. A Wilcoxon two-tailed signed rank test was used to compare data for 13 lakes and ponds from the present survey with data from the 1973-75 or 1978-79 surveys conducted by the Connecticut Agricultural Experiment Station and Connecticut Department of Environmental Protection. The test showed no significant difference at the 90 percent confidence level for spring nitrogen and summer chlorophyll-a concen- trations, a significant increase at the 90 percent confidence level in summer phosphorus concentra- tions, and a significant decrease at the 95 percent confidence level in summer transparency. For the lakebed-sediment surveys, composite-grab samples were collected from the deepest part of each lake. Samples were analyzed for arsenic, cyanide, organic and inorganic carbon, selected metals, and methylene-extractable, synthetic organic compounds classified by the U.S. Environmental Protection Agency as semi-volatile priority pollutants. Hanover Pond, Eagleville Lake, and West Thompson Lake had three of the four highest concentrations of cadmium, chromium, copper, lead, nickel, zinc, and cyanide. The four lakes with the highest concentrations of arsenic (Aspinook Pond, Fitchville Pond, Mashapaug Pond, and West Thompson Lake) are located in the eastern part of Connecticut. The three samples with the highest mercury concentrations were from Lake Lillinonah and Lake Zoar. There appears to be a positive correlation between the concentrations of cadmium, chromium, copper, lead, nickel, zinc, and cyanide. Only 15 of the 54 synthetic organic compounds analyzed for were detected in 9 of the 12 lakes sampled. Of these 15 compounds, 14 are polycyclic aromatic hydrocarbons and the 15th is a phthalate ester. Hanover Pond had the most compounds detected (9), and phenanthrene was the compound detected in the most lakes (8).

Water-Resources Investigations Report↗

Water-quality assessment of part of the Upper Mississippi River basin, Minnesota and Wisconsin: Environmental setting and study design

The Upper Mississippi River Basin is diverse in ways that can control the areal distribution and flow of water and the distribution and concentration of constituents that affect water quality. A review of the environmental setting of the Upper Mississippi River Basin study unit of the National Water-Quality Assessment Program is intended to put water quality in perspective with the geology, soils, climate, hydrology, ecology and historical uses of the land and provides a basis for the sampling design of the study. The Upper Mississippi River Basin study unit encompasses about 47,000 square miles and includes all of the basin upstream from Lake Pepin. The climate of the study unit is subhumid continental with cold dry winters and warm, moist summers. Average annual precipitation ranges from 22 inches in the western part of the study unit to 32 inches in the east. Annual runoff ranges from less than 2 inches in the west to 14 inches in the northeast. The physiography of the study unit includes the Superior Upland and the Central Lowland Provinces. The Wisconsin Driftless Area and the Dissected Till Plains are unique physiographic sections of the Central Lowland Province. Hydrogeologic units in glacial deposits include surficial and buried sand and gravel aquifers and confining units. Bedrock aquifers and confining units are part of a thick sequence of sedimentary rocks that can be divided into major aquifers separated by confining units. The population of the study unit was about 3,640,000 as of 1990 and increased 16 percent between 1970 and 1990. Seventy-five percent of the population lives in the Twin Cities metropolitan area. An average of 413 million gallons of water per day was used 59 percent from ground water and 41 percent from surface water. Land use and land cover in the study unit consists of forested, agricultural, and urban areas. About 63 percent of the land area is agricultural. The quality of water in streams and ground water are affected by both natural and anthropogenic factors. The quality of water is generally satisfactory for most domestic, public, industrial, and irrigation uses. Most water is of the calcium-magnesium-bicarbonate type. The initial six-year phase of the Upper Mississippi River Basin National Water-Quality Assessment, lasting from 1994 to 1999, focuses on data collection and analysis in a 19,500 square-mile area in Minnesota and Wisconsin that includes the Twin Cities metropolitan area. The study design focuses on factors that have an influence on or a potential influence on the water quality in that area. The most significant contaminants include nutrients, pesticides, synthetic-organic compounds, and trace metals. Environmental stratification consists of dividing the study unit into subareas with homogeneous characteristics to assess natural and anthropogenic factors affecting water quality. The assessment of water quality in streams and in aquifers is based on the sampling design that compares water quality within homogeneous subareas defined by subbasins or aquifer boundaries. The study unit is stratified at four levels for the surface-water component: glacial deposit composition, surficial geology, general land use and land cover, and secondary land use. Ground-water studies emphasize shallow ground water where quality is most likely influenced by overlying land use and land cover. Stratification for ground-water sampling is superimposed on the distribution of shallow aquifers. For each aquifer and surface-water basin this stratification forms the basis for the proposed sampling design used in the Upper Mississippi River Basin National Water-Quality Assessment.

Minnesota, Wisconsin↗

National water summary 1983: Hydrologic events and issues

The United States as a Nation possesses abundant water resources and has developed and used those resources extensively. The national renewable supply of water is about 1,400 billion gallons per day (for the conterminous 48 States). Approximately 380 billion gallons per day of freshwater is withdrawn for use by the Nation's homes, farms, and industries, and about 280 billion gallons per day is returned to streams. Although a large percentage of the Nation's waste is carried in this return flow, the quality of water in streams has improved in many respects as a result of the pollution-control pro- grams of recent years. However, much remains to be learned about water quality particularly the extent of contamination by synthetic organic chemicals and heavy metals, and the effects of these contaminants on human health.

Water Supply Paper↗

Fractionation of Cu and Zn isotopes during adsorption onto amorphous Fe(III) oxyhydroxide: Experimental mixing of acid rock drainage and ambient river water

Fractionation of Cu and Zn isotopes during adsorption onto amorphous ferric oxyhydroxide is examined in experimental mixtures of metal-rich acid rock drainage and relatively pure river water and during batch adsorption experiments using synthetic ferrihydrite. A diverse set of Cu- and Zn-bearing solutions was examined, including natural waters, complex synthetic acid rock drainage, and simple NaNO 3 electrolyte. Metal adsorption data are combined with isotopic measurements of dissolved Cu ( 65 Cu/ 63 Cu) and Zn ( 66 Zn/ 64 Zn) in each of the experiments. Fractionation of Cu and Zn isotopes occurs during adsorption of the metal onto amorphous ferric oxyhydroxide. The adsorption data are modeled successfully using the diffuse double layer model in PHREEQC. The isotopic data are best described by a closed system, equilibrium exchange model. The fractionation factors ( α soln–solid ) are 0.99927 ± 0.00008 for Cu and 0.99948 ± 0.00004 for Zn or, alternately, the separation factors ( Δ soln–solid ) are −0.73 ± 0.08‰ for Cu and −0.52 ± 0.04‰ for Zn. These factors indicate that the heavier isotope preferentially adsorbs onto the oxyhydroxide surface, which is consistent with shorter metal–oxygen bonds and lower coordination number for the metal at the surface relative to the aqueous ion. Fractionation of Cu isotopes also is greater than that for Zn isotopes. Limited isotopic data for adsorption of Cu, Fe(II), and Zn onto amorphous ferric oxyhydroxide suggest that isotopic fractionation is related to the intrinsic equilibrium constants that define aqueous metal interactions with oxyhydroxide surface sites. Greater isotopic fractionation occurs with stronger metal binding by the oxyhydroxide with Cu > Zn > Fe(II).

Geochimica et Cosmochimica Acta↗

Mechanism of molybdenum removal from the sea and its concentration in black shales: EXAFS evidence

Molybdenum K-edge EXAFS (extended X-ray absorption fine structure) spectra yield new structural information about the chemical environment of Mo in high-Mo black shales and sediments. Two spectral types are found. The less common one, associated with Mo ores developed in shale in China, is that of a MoS2 phase, possibly X-ray amorphous jordisite. The other, associated with Cretaceous deep sea sediments and with other black shales, is characterized by short Mo-O distances (1.69-1.71 A??), by Mo-S distances of 2.30-2.38 A??, and in some cases by second shell Mo and Fe interactions, which suggests that some Mo resides in transition metal-rich phases. EXAFS spectra of synthetic amorphous materials, prepared by scavenging Mo from HS solutions with Fe(II), FeOOH, and humic acid, suggest that the second spectral type arises from Mo present chiefly in two forms. One is a compact, Mo-Fe-S "cubane" type compound with Mo-S distances of ???2.36 A?? and Mo-Fe distances of ???2.66 A??, while the other is probably an organic form containing some Mo-O double bonds (???1.69 A??). Laboratory products, that were prepared by scavenging dissolved Mo from sulfidic solutions with humic acid, yield spectra quite similar to the second spectral type observed in shales and sediments, including unexpected indications of Mo-Fe interactions. Molybdenum L-edge spectra indicate that the mean oxidation state in the sediments and shales lies between IV and VI. This work demonstrates the merit of EXAFS for obtaining structural information on natural materials containing X-ray amorphous components which defeat conventional mineralogical characterization. The implications of these findings regarding Mo scavenging from sulfidic natural waters are considered. We introduce the concept of a geochemical switch, in which HS- transforms the marine behavior of Mo from that of a conservative element to that of a particle reactive element. The action point of the HS- switch is calculated to be, aHS- = 10-3.6 - 10-4.3. When aHS- approaches the action point, Mo becomes reactive to particles containing transition metals (e.g., Fe). We conjecture that thiols, including humic-bound thiol groups, also switch Mo behavior. In contrast to previous ideas, our model for Mo scavenging deemphasizes the role of reduction from Mo(VI) to Mo(V) as the initial step in scavenging; instead, we emphasize the ease with which Mo forms covalent bonds to transition metals and organic molecules via S bridges.

Geochimica et Cosmochimica Acta↗

Assessment of water quality in the South Indian River Water Control District, Palm Beach County, Florida, 1989-94

The South Indian River Water Control District is located in an area of northern Palm Beach County, Fla., where many residents must rely on private wells for domestic water supplies and individual septic tanks for waste disposal. As a result, contamination of the surficial aquifer system and availability of a potable water supply have become of increasing concern. To address this concern, the U.S. Geological Survey, in cooperation with the South Indian River Water Control District, conducted a study to assess ground-water and surface-water quality in the District from 1989 to 1994. The study consisted of water-quality monitoring at 11 wells and 14 surface-water sites located within the District. Water samples were analyzed for major inorganic constituents and physical characteristics, trace metals, nitrogen and phosphorus species, and synthetic organic compounds. The predominant water type within the South Indian River Water Control District is calcium bicarbonate; however, mixed-ion type water and sodium bicarbonate type water also exist in varying amounts. Sodium chloride type water is present in the western areas of the District due to incompletely flushed residual sea water. Results of the study indicated that concentrations of most constituents were within State drinking-water standards as established by the Florida Department of Environmental Protection, but concentrations of certain constituents occasionally exceeded drinking-water standards in some ground-water and surface-water samples. Sodium and chloride concentrations exceeded the standards in ground water at two wells, dissolved-solids concentrations at five ground-water wells and one surface-water site, and color values at all 11 ground-water wells and all 14 surface-water sites. Other constituents also exhibited concentrations that exceeded drinking-water standards. Cadmium and zinc concentrations exceeded the standards in ground water at one well, and lead concentrations exceeded the standard in ground water at five wells. Nitrogen and phosphorus specie concentrations did not exceed respective drinking-water standards in any ground-water or surface-water samples. Additionally, organic compounds were not detected at four surface-water sites monitored for National Pollutant Discharge Elimination System constituents. Several synthetic organic compounds were detected at or above 50 micrograms per liter in water samples collected from six ground-water wells and three surface-water sites.

Florida↗

Surface-water-quality assessment of the lower Kansas River basin, Kansas and Nebraska: Project data November 1986 through April 1990

Surface-water-quality data were collected from the lower Kansas River Basin in Kansas and Nebraska. The data are presented in 17 tables consisting of physical properties, concentrations of dissolved solids and major ions, dissolved and total nutrients, dissolved and total major metals and trace elements, radioactivity, organic carbon, pesticides and other synthetic-organic compounds, bacteria and chlorophyll-a, in water; particle-size distributions and concentrations of major metals and trace elements in suspended and streambed sediment; and concentrations of synthetic-organic compounds in streambed sediment. The data are grouped within each table by sampling sites, arranged in downstream order. Ninety-one sites were sampled in the study area. These sampling sites are classified in three, non-exclusive categories (fixed, synoptic, and miscellaneous sites) on the basis of sampling frequency and location. Sampling sites are presented on a plate and in 3 tables, cross-referenced by downstream order, alphabetical order, U.S. Geological Survey identification number, sampling-site classification category, and types of analyses performed at each site. The methods used to collect, analyze, and verify the accuracy of the data also are presented.

Kansas, Nebraska↗

Metal interferences and their removal prior to the determination of As(T) and As(III) in acid mine waters by hydride generation atomic absorption spectrometry

Hydride generation atomic absorption spectrometry (HGAAS) is a sensitive and selective method for the determination of total arsenic (arsenic(III) plus arsenic(V)) and arsenic(III); however, it is subject to metal interferences for acid mine waters. Sodium borohydride is used to produce arsine gas, but high metal concentrations can suppress arsine production. This report investigates interferences of sixteen metal species including aluminum, antimony(III), antimony(V), cadmium, chromium(III), chromium(IV), cobalt, copper(II), iron(III), iron(II), lead, manganese, nickel, selenium(IV), selenium(VI), and zinc ranging in concentration from 0 to 1,000 milligrams per liter and offers a method for removing interfering metal cations with cation exchange resin. The degree of interference for each metal without cation-exchange on the determination of total arsenic and arsenic(III) was evaluated by spiking synthetic samples containing arsenic(III) and arsenic(V) with the potential interfering metal. Total arsenic recoveries ranged from 92 to 102 percent for all metals tested except antimony(III) and antimony(V) which suppressed arsine formation when the antimony(III)/total arsenic molar ratio exceeded 4 or the antimony(V)/total arsenic molar ratio exceeded 2. Arsenic(III) recoveries for samples spiked with aluminum, chromium(III), cobalt, iron(II), lead, manganese, nickel, selenium(VI), and zinc ranged from 84 to 107 percent over the entire concentration range tested. Low arsenic(III) recoveries occurred when the molar ratios of metals to arsenic(III) were copper greater than 120, iron(III) greater than 70, chromium(VI) greater than 2, cadmium greater than 800, antimony(III) greater than 3, antimony(V) greater than 12, or selenium(IV) greater than 1. Low recoveries result when interfering metals compete for available sodium borohydride, causing incomplete arsine production, or when the interfering metal oxidizes arsenic(III). Separation of interfering metal cations using cation-exchange prior to hydridegeneration permits accurate arsenic(III) determinations in acid mine waters containing high concentrations of interfering metals. Stabilization of the arsenic redox species for as many as 15 months is demonstrated for samples that have been properly filtered and acidified with HCl in the field. The detection limits for the method described in this report are 0.1 micrograms per liter for total arsenic and 0.8 micrograms per liter for arsenic(III).

Water-Resources Investigations Report↗

Stanford-USGS shrimp-RG ion microprobe: A new approach to determining the distribution of trace elements in coal

The distribution of Cr and other trace metals of environmental interest in a range of widely used U.S. coals was investigated using the Stanford-USGS SHRIMP-RG ion microprobe . Using the oxygen ion source, concentrations of Cr (11 to 176 ppm), V (23 to 248 ppm), Mn (2 to 149 ppm), Ni (2 to 30 ppm), and 13 other elements were determined in illite/smectite, a group of clay minerals commonly present in coal. The results confirm previous indirect or semi-quantitative determinations indicating illite/smectite to be an important host of these metals. Calibration was achieved using doped aluminosilicate-glass synthetic standards and glasses prepared from USGS rock standards. Grains for analysis were identified optically, and confirmed by 1) precursory electron microprobe analysis and wavelength-dispersive compositional mapping, and 2) SHRIMP-RG major element data obtained concurrently with trace element results. Follow-up investigations will focus on the distribution of As and other elements that are more effectively ionized with the cesium primary beam currently being tested.

ACS Division of Fuel Chemistry, Preprints↗

Triangle area water supply monitoring project, October 1988 through September 2001, North Carolina -- description of the water-quality network, sampling and analysis methods, and quality-assurance practices

The Triangle Area Water Supply Monitoring Project was initiated in October 1988 to provide long-term water-quality data for six area water-supply reservoirs and their tributaries. In addition, the project provides data that can be used to determine the effectiveness of large-scale changes in water-resource management practices, document differences in water quality among water-supply types (large multiuse reservoir, small reservoir, run-of-river), and tributary-loading and in-lake data for water-quality modeling of Falls and Jordan Lakes. By September 2001, the project had progressed in four phases and included as many as 34 sites (in 1991). Most sites were sampled and analyzed by the U.S. Geological Survey. Some sites were already a part of the North Carolina Division of Water Quality statewide ambient water-quality monitoring network and were sampled by the Division of Water Quality. The network has provided data on streamflow, physical properties, and concentrations of nutrients, major ions, metals, trace elements, chlorophyll, total organic carbon, suspended sediment, and selected synthetic organic compounds. Project quality-assurance activities include written procedures for sample collection, record management and archive, collection of field quality-control samples (blank samples and replicate samples), and monitoring the quality of field supplies. In addition to project quality-assurance activities, the quality of laboratory analyses was assessed through laboratory quality-assurance practices and an independent laboratory quality-control assessment provided by the U.S. Geological Survey Branch of Quality Systems through the Blind Inorganic Sample Project and the Organic Blind Sample Project.

North Carolina↗