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Computer graphics for quality control in the INAA of geological samples

A data reduction system for the routine instrumental activation analysis of samples is described, with particular emphasis on interactive graphics capabilities for evaluating analytical quality. Graphics procedures have been developed to interactively control the analysis of selected photopeaks during spectral analysis, and to evaluate detector performance during a given counting cycle. Graphics algorithms are also used to compare the data on reference samples with accepted values, to prepare quality control charts to evaluate long term precision and to search for systematic variations in data on reference samples as a function of time. ?? 1987 Akade??miai Kiado??.

Journal of Radioanalytical and Nuclear Chemistry A

Application of epithermal neutron activation in multielement analysis of silicate rocks employing both coaxial Ge(Li) and low energy photon detector systems

The instrumental activation analysis of silicate rocks using epithermal neutrons has been studied using both high resolution coaxial Ge(Li) detectors and low energy photon detectors, and applied to the determination of 23 elements in eight new U.S.G.S. standard rocks. The analytical use X-ray peaks associated with electron capture or internal conversion processes has been evaluated. Of 28 elements which can be considered to be determinable by instrumental means, the epithermal activation approach is capable of giving improved sensitivity and precision in 16 cases, over the normal INAA procedure. In eleven cases the use of the low energy photon detector is thought to show advantages over convertional coaxial Ge(Li) spectroscopy. ?? 1977 Akade??miai Kiado??.

Journal of Radioanalytical Chemistry

Herbicides and nitrate in near-surface aquifers in the midcontinental United States, 1991

The occurrence and distribution of selected herbicides, atrazine metabolites, and nitrate were determined for near-surface aquifers (within 50 feet of land surface) in the corn- and soybean-producing region of the midcontinental United States. The study region included all or parts of Illinois, Indiana, Iowa, Kansas, Michigan, Minnesota, Missouri, Nebraska, North Dakota, Ohio, South Dakota, and Wisconsin. Water samples were collected during the spring and summer of 1991 from 303 wells completed in near-surface unconsolidated and near-surface bedrock aquifers. At least one herbicide or atrazine metabolite was detected in 24 percent of 579 water samples analyzed for herbicides, based on a reporting limit of 0.05 microgram per liter. However, no herbicide concentration exceeded the U.S. Environmental Protection Agency's maximum contaminant levels or health advisory levels for drinking water. The most frequently detected herbicide compound was desethylatrazine, an atrazine metabolite (18.1 percent), followed by atrazine (17.4 percent); deisopropylatrazine, an atrazine metabolite (5.7 percent); prometon (5.0 percent); metolachlor (2.7 percent); alachlor (1.7 percent); simazine (1.0 percent); metribuzin (1.0 percent); and cyanazine (0.7 percent). The herbicides ametryn, prometryn, propazine, and terbutryn were not detected during this study. Nitrate concentrations equal to or greater than 3.0 milligrams per liter (excess nitrate) were detected in 29 percent of the 599 nitrate analyses, and ammonium concentrations equal to or greater than 0.01 milligram per liter were detected in 78 percent of the 584 ammonium analyses. Nitrate concentrations equal to or greater than the U.S. Environmental Protection Agency's maximum contaminant level for drinking water of 10 milligrams per liter were found in 6 percent of the samples. The frequency of herbicide detection was, in part, affected by the analytical method's reporting limit. Results from this study show that the frequency of atrazine detection increases as the reporting limit decreases. Herbicide metabolite concentrations are critical to understanding the detection of herbicide residues. The frequency of detection of atrazine residue (atrazine + desethylatrazine + deisopropylatrazine) was 22.1 percent, which was more than the frequency of detection of atrazine alone (17.4 percent). Prometon was detected more frequently than every other herbicide except atrazine. The prometon appears to be derived from areas of nonagricultural land use, such as golf courses and residential areas. Herbicides and excess nitrate were both rarely detected in the eastern part of the study region, even though this is an area of intense herbicide and nitrogen-fertilizer use. Hydrogeologic factors, land use, agricultural practices, local features, and water chemistry were analyzed for possible relation to herbicide and excess-nitrate detections. Herbicides and excess nitrate were detected more frequently in near-surface unconsolidated aquifers than in nearsurface bedrock aquifers. The depth to the top of the aquifer was inversely related to the frequency of detection of herbicides and excess nitrate. The proximity of streams to sampled wells also affected the frequency of herbicide detection. Significant seasonal differences were determined for the frequency of herbicide detection, but not for the frequency of excess nitrate.

Illinois, Indiana, Iowa, Kansas, Michigan, Minneso

Global review reveals how disparate study motivations, analytical designs, and focal ions limit understanding of salinization effects on freshwater animals

Global salinization of freshwaters is adversely affecting biotic communities and ecosystem processes. We reviewed six decades (1960–2020) of literature published on animal responses to increased salinities across different taxonomic and ecological contexts and identified knowledge gaps. From 585 journal articles, we characterized 5924 responses of mollusks, crustaceans, zooplankton, non-arthropod invertebrates (NAI), insects, fishes, and amphibians to salinization. Insects and fishes were the most studied taxa; Na + and Cl − were the most studied ions − . Collectively, concentrations of the ions examined typically spanned five orders of magnitude. Species' invasiveness was a key motivation for studying mollusks, crustaceans, and fishes; threats of urbanization and road salts were key motivations for studying NAI, zooplankton, and amphibians. Laboratory studies were more common than field studies for most taxa. Focal life stages in laboratory studies varied widely but juveniles and adults were represented similarly in field studies. Studies of mollusks, NAI, and crustacean focused on adults; studies of zooplankton, insects, fishes, and amphibians focused on juveniles. Organismal- and population-level responses measuring solute uptake, internal chemistry, body condition, or ion concentrations predominated laboratory studies; population- and assemblage-level responses measuring abundance, spatial distribution, or assemblage composition predominated field studies. Negative responses to salinization predominated but positive and unimodal responses were apparent across all taxa and organizational levels. Key topics for further research include a) salinity responses by more taxa, b) responses to especially toxic ions (i.e., potassium, bicarbonate, sulfate, magnesium), c) mechanisms causing positive and unimodal responses, d) traits underpinning responses, e) effects transcending organizational levels, f) ion-specific response thresholds, and g) interactions between salinity and other stressors. Our review suggests inter-taxa variation in sensitivity to salinization reflects occurrence of certain biological traits, including gill-breathing, semi-permeable skin, multiple life stages, and limited mobility. We propose a traits-based framework to predict salinization sensitivity from shared traits. This evolutionary approach could inform management aimed at preventing or reducing adverse impacts of freshwater salinization.

Science of the Total Environment

Variations in pore-water quality, mineralogy, and sedimentary texture of clay-silts in the lower Miocene Kirkwood Formation, Atlantic City, New Jersey

Properties of and pore-water solute chemistry in confining units in the New Jersey Coastal Plain were studied to determine whether leakage of solute-enriched pore water from confining units affects regional aquifer-water chemistry, which ultimately may result in aquifer waters with high sodium and bicarbonate concentrations. Pore-water samples collected from a continuously cored borehole in the lower Miocene Kirkwood Formation at Atlantic City, NJ, were analyzed: 15 samples were obtained from clay-silt confining-unit sediments, and four samples were from silt interbeds in the sand of the major confined aquifer in the region, the Atlantic City 800-ft sand. The samples were analyzed to assess interrelations among mineralogy, texture, fluidretention properties, sediment chemistry, and pore-water chemistry, and to document the scale of variation in these properties. Linear regressions were developed to describe the relations of constituents dissolved in 14 pore-water samples collected from the lower confining unit overlying the Atlantic City 800-ft sand and from the silt interbeds in the upper sand unit of the Atlantic City 800-ft sand. The regressions were for concentrations of magnesium and calcium (m = 0.27, R2 = 0.99); concentrations of sodium and the sum of calcium and magnesium (m = 0.17, R 2 = 0.92); concentrations of sulfate and the sum of calcium and magnesium (m = 1.14, R 2 = 0.99); and concentrations of sodium and sulfate (m = 0.14, R 2 = 0.89). The percentage of fine sand was greatest in the shallowest sampled interval, where pore-water concentrations of calcium, magnesium, and sulfate were greatest. The pore-water samples were of three distinct water-quality types (hydrogeochemical facies): a calcium-sulfate type, a mixed calcium-sodium-sulfate-chloride-bicarbonate type, and a sodium-sulfate-bicarbonate-chloride type. The first two types were found only in the lower confining unit; the third type was found only in the composite confining unit underlying the Atlantic City 800-ft sand. Each of these hydrogeochemical facies generally is found within distinct intervals over a range of tens of feet in the core. Krige estimates of pore-water–constituent variations with depth were made by using only the analytical results for the 14 samples from the lower confining unit overlying the Atlantic City 800-ft sand and the silt interbeds in the upper sand unit of the Atlantic City 800-ft sand. Geostatistical analysis of the pore-water–quality data generally resulted in two types of semivariograms. One semivariogram type best fits concentration trends with depth for calcium, magnesium, strontium, sodium, sulfate, and specific conductance; lithium and chloride may also fit this semivariogram type. The other semivariogram type best fits concentration trends with depth for silica, cation exchange capacity, and dissolved inorganic carbon. The scale of variation of the concentrations and properties is indicated by the maximum lag autocorrelation distance of the theoretical semivariograms (the range) and ranged from 44 to 110 ft (13.4–33.5 m). The scale of variation of pore-water major-ion concentrations of sulfate, chloride, calcium, and magnesium alone is on the order of 65–70 ft (19.8–21.3 m). The semivariograms for all pore-water constituents except silica have significant variance at the smallest lag distance, indicating that the constituent concentration varied over a larger scale than the sampling interval. The dominant exchangeable cation in the sediment is calcium. Cation exchange reactions do not appear to be the dominant process in the sediments of the lower confining unit above the Atlantic City 800-ft sand, because a linear correlation exists between the concentration of sodium and the sum of calcium and magnesium concentrations in the pore water; concentrations of all these constituents increase in the upward flow direction, and the ratio of sodium to chloride in the pore water is about 1.0. Two significant principal components explained 82.5% of the total variation in pore-water solute chemistry. Principal component 1 represents about 53% of the variation in pore-water quality and includes calcium, magnesium, sulfate, strontium, and lithium. Coupled chemical processes in the confining units, such as incongruent dissolution of carbonate and other mineral phases or redox transformations of sulfur, likely explain the covariance of these constituents. Principal component 2 represents about 30% of the variation and includes sodium, dissolved inorganic carbon, and chloride. Covariance of sodium and chloride probably is caused by the presence of residual seawater.

New Jersey

Experimental studies in stream-aquifer interaction along the Arkansas River in Central Kansas - Field testing and analysis

During the last several years, streamflows of a number of Kansas streams have been reduced as a result of groundwater declines. In order to better understand and quantify stream-aquifer interrelationships, an eight-day comprehensive stream-aquifer pumping test, followed by recovery monitoring, was conducted along the Arkansas River near Great Bend, Kansas. In addition to water level monitoring in numerous observation wells, streamflow data, streambed hydraulic gradients, neutron probe-based water content of dewatered sediments, water chemistry and other data were collected. The alluvial aquifer is shown to be highly transmissive ( T = 1803 m 2 d −1 ) with the pumping stress (9538 m 3 d −1 ) having a radius of influence larger than 1.77 km, impacting both the aquifer levels and the streamflow in the nearby Arkansas River. Drawdown and recharge boundary effects were observed in all observation wells, including those on the opposite side of the river. The alluvial aquifer did not exhibit a water table behavior and responded as a leaky confined aquifer. A semiconfining clay layer less than 3 m thick and an additional recharge source from a nearby stream-alluvial system were the probable causes of the observed phenomena. Actual streamflow depletion is shown to be appreciably less than the computed depletion based on analytical solutions.

Kansas

Contaminants in stream sediments from seven U.S. metropolitan areas: Data summary of a National Pilot Study

This report presents data collected as a part of a synoptic survey of stream sediment contaminants, associated watershed characteristics and invertebrate responses in laboratory sediment toxicity tests from 98 streams (sites) in seven metropolitan study areas across the continental United States. The report presents methods, data, and sediment-quality guidelines, including the derivation of a new sediment pyrethroid probable effects concentration, for the purposes of relating measured contaminants to land use and toxicity evaluation. The study evaluated sites that ranged in their degree of relative urbanization within the study areas of Atlanta, Boston, Dallas-Fort Worth, Denver, Milwaukee-Green Bay, Salt Lake City, and Seattle-Tacoma. In all, 108 chemical analytes quantified in the study are presented, by class and number of individual compounds, as follows: polyaromatic hydrocarbons (PAHs) (28), organochlorine pesticides (OCs) (18), polychlorinated biphenyls (Aroclors) (3), pyrethroid insecticides (14), fipronil compounds (4), priority trace and other major elements (41). The potential of these sediments to cause toxicity to sediment-dwelling invertebrates was evaluated using two standard sediment toxicity tests: a 28-day growth and survival toxicity test with the amphipod Hyalella azteca, and a 10-day growth and survival toxicity test with the midge Chironomus dilutus. Further, approximately 95 relevant watershed and reach-level characteristics were generated and are presented to aid in interpretation and explanation of contaminant and toxicity patterns. Interpretation of the findings of this study, including the relationships with urbanization and other factors, the relationship between sediment toxicity and sediment chemistry in the seven study areas, and the sources and occurrence of pyrethroid insecticides, are discussed in detail in a forthcoming series of journal articles.

Boston;Atlanta;Milwaukee;Green Bay;Dallas;Fort Wor

Analytical Results for Agricultural Soils Samples from a Monitoring Program Near Deer Trail, Colorado (USA)

Since late 1993, Metro Wastewater Reclamation District of Denver (Metro District, MWRD), a large wastewater treatment plant in Denver, Colorado, has applied Grade I, Class B biosolids to about 52,000 acres of nonirrigated farmland and rangeland near Deer Trail, Colorado, USA. In cooperation with the Metro District in 1993, the U.S. Geological Survey (USGS) began monitoring groundwater at part of this site. In 1999, the USGS began a more comprehensive monitoring study of the entire site to address stakeholder concerns about the potential chemical effects of biosolids applications to water, soil, and vegetation. This more comprehensive monitoring program has recently been extended through 2010. Monitoring components of the more comprehensive study include biosolids collected at the wastewater treatment plant, soil, crops, dust, alluvial and bedrock groundwater, and stream bed sediment. Soils for this study were defined as the plow zone of the dry land agricultural fields - the top twelve inches of the soil column. This report presents analytical results for the soil samples collected at the Metro District farm land near Deer Trail, Colorado, during three separate sampling events during 1999, 2000, and 2002. Soil samples taken in 1999 were to be a representation of the original baseline of the agricultural soils prior to any biosolids application. The soil samples taken in 2000 represent the soils after one application of biosolids to the middle field at each site and those taken in 2002 represent the soils after two applications. There have been no biosolids applied to any of the four control fields. The next soil sampling is scheduled for the spring of 2010. Priority parameters for biosolids identified by the stakeholders and also regulated by Colorado when used as an agricultural soil amendment include the total concentrations of nine trace elements (arsenic, cadmium, copper, lead, mercury, molybdenum, nickel, selenium, and zinc), plutonium isotopes, and gross alpha and beta activity (Colorado Department of Public Health and Environment, Hazardous Materials and Waste Management Division, 1997; Colorado Department of Public Health and Environment,1998; U.S. Environmental Protection Agency, 1993). Since these were the identified priority parameters for the biosolids, the soils have the same set of priority parameters. Although the composite soils' priority analytes have been reported earlier to Metro District, the remaining elemental datasets for both the composite soils samples and selected fields' individual subsamples' data are presented here for the first time. More information about the other monitoring components is presented elsewhere in the literature (http://co.water.usgs.gov/projects/CO406/CO406.html). In general, the objective of each component of the study was to determine whether concentrations of priority parameters (1) were higher than regulatory limits, (2) were increasing with time, and(or) (3) were significantly higher in biosolids-applied areas than in a similar farmed area where biosolids were not applied. The method chosen for sampling the soils proved to be an efficient and reliable representation of the average composition of each field. This was shown by analyzing individual subsamples, averaging the resulting values, and then comparing the values to the composited samples' values. The soil chemistry shows distinct differences between the two sites, most likely due to the different underlying parent material. Biosolids data were used to compile an inorganic-chemical biosolids signature that can be contrasted with the geochemical signature of the agricultural soils for this site. The biosolids signature and an understanding of the geology and hydrology of the site can be used to separate biosolids effects from natural geochemical effects. Elements of particular interest for a biosolids signature after application in the soils include bismuth, copper, silver, mercury, and phosphorus. This signat

Open-File Report

Early developments in petroleum geochemistry

Petroleum geochemistry is the outgrowth of the application of the principles and methods of organic chemistry to petroleum refining and petroleum geology . This paper reviews 120 years of petroleum geochemistry, from about 1860 to 1980, and includes a discussion of the formal recognition of petroleum geochemistry as an earth-science discipline starting in 1959 when a general petroleum geochemistry symposium was first organized at Fordham University, New York. A chronology of significant events, including concepts, techniques, and textbook publications, is presented. Because petroleum geochemistry has been a tool for petroleum exploration from the beginning, the early developments of surface prospecting, source-rock identification, and oil/oil and oil/source correlation are discussed, along with the application of geochemistry to petroleum migration, accumulation, and alteration. In addition the paper deals with the biomarker revolution, which began in earnest about 1964, and with early models of geothermal history. Concepts in petroleum geochemistry have continually evolved, enhanced by the development of new analytical techniques, leading to new discoveries concerning the origin and occurrence of petroleum.

Organic Geochemistry

Methods of analysis—Determination of pesticides in filtered water and suspended sediment using liquid chromatography- and gas chromatography-tandem mass spectrometry

The widespread application of pesticides in agricultural and urban areas leads to their presence in surface waters. Presence of these biologically active chemicals in environmental waters potentially has adverse effects on nontarget organisms. To better understand the environmental fate of these contaminants, a robust method to capture chemicals with wide-ranging physicochemical properties has been developed. The method was developed by the U.S. Geological Survey’s Organic Chemistry Research Laboratory to monitor pesticides, pesticide degradates, and other agrochemicals in environmental surface waters throughout the country. The analysis involves a multiresidue method to determine 183 pesticides and pesticide degradates in filtered water samples and 178 pesticides and pesticide degradates in paired suspended sediment samples. After the filtration of whole water, contaminants are individually measured in the filtered water and the collected suspended sediment. Filtered water is extracted via solid-phase extraction, whereas suspended sediment is extracted using an ultrasonication, solid-liquid extraction. Samples are analyzed by liquid chromatography-tandem mass spectrometry using an electrospray ionization source in positive and negative modes and analyzed by gas chromatography-tandem mass spectrometry using an advanced electron ionization source in positive mode. Instrument parameters were optimized for the highest sensitivity, and at least two transitions (quantifier and qualifier) were monitored for each analyte. Recoveries in test filtered water ( n =9; 183 analytes) from the American River, California, and suspended sediment ( n =9; 178 analytes) samples fortified at 15 nanograms per liter (ng/L) ranged from 70.1 to 121.0 and 71.1 to 117.0 percent in water and suspended sediment filter samples, respectively. Method detection limits of pesticides and pesticide degradates ranged from 0.5 to 10.6 ng/L in water and 0.7 to 11.8 ng/L in suspended sediment filters. Reporting limits were 1.1–21.1 ng/L and 1.5–23.7 ng/L in water and filter samples, respectively. The developed method is applied to surface-water samples for the analysis of pesticides, pesticide degradates, and other agrochemicals.

Techniques and Methods

Environmental presence and persistence of pharmaceuticals: An overview

Emerging contaminants (ECs) in the environment – that is, chemicals with domestic, municipal, industrial, or agricultural sources that are not commonly monitored but may have the potential for adverse environmental effects – is a rapidly growing field of research. The use of “emerging” is not intended to infer that the presence of these compounds in the environment is new. These chemicals have been released into the environment as long as they have been in production or, in the case of hormones and other endogenous compounds, since the rise of animal life. What is emerging is the interest by the scientific and lay communities in the presence of these chemicals in the environment, the analytical capabilities required for detection, and the subtle effects that very small concentrations of these chemicals appear to have on aquatic biota. In December 2006, Environmental Science & Technology devoted an entire special issue (volume 40, number 23) to the topic of ECs, illustrating the increased interest in the subject. Within the EGs, one particular class that has seen a substantial increase in research over the past 10 years is pharmaceuticals and personal-care products (PPCPs). This increased research interest can be demonstrated by several means, including requests for proposals from funding agencies, but the clearest indication of a focused effort to understand the introduction, transformation, and potential health and environmental effects of PPCPs and ECs, in general, is the number of published reports. This increase can be shown by examining six environmental journals that regularly publish PPCP-related papers – Chemosphere , Environmental Science & Technology , Environmental Toxicology and Chemistry , Science of the Total Environment , Water Research , and Water Science and Technology . In 1998 there were 22 papers published on pharmaceuticals, antibiotics, or drugs in these 6 journals; by 2006, this number increased sixfold to 132 papers (Figure 1.1). This growth can be attributed to a number of factors. The presence of pharmaceuticals in surface-water samples from Europe and the United States was documented in several sentinel papers. These ground-breaking works encouraged other scientists to examine the rivers, streams, lakes, and reservoirs in their regions for such chemicals. In addition, the intense public attention paid to news reports on the environmental detections of these chemicals and possible effects of aquatic life has made this issue visible to the wastewater-treatment, drinking-water treatment, and regulatory communities. This has driven the funding bodies associated with these communities to fund studies or request proposals that address the presence, fate, and effects of PPCPs in aquatic systems. The release of the first comprehensive reconnaissance of pharmaceuticals and other wastewater contaminants in the United States provides an example of the intense media interest in this topic. Within 6 days on online publication of this study, 72 newspapers across the United States had published articles describing the results, either locally written or based on international media syndicate reports. There also was substantial concurrent coverage by local and national radio and television outlets, including the Cable News Network, ABC World News Tonight , and National Public Radio. A substantial fraction of these news stories may be attributable to press releases and media briefings prior to publication. However, the interest by television and print journalists in reporting the results of a peer-reviewed journal article to the general public was motivated by the recognition that describing the presence of PPCPs in water supplies would be of interest to the public. To better convey the results of the study published by Koplin et al. to the public, a separate general-interest fact sheet was published to summarize the important points of the study. Because PPCPs are commonly and widely used by individuals, there is likely a preexisting, personal identification with these compounds that does not occur for the wide range of other organic and inorganic contaminants whose presence in the environment has previously been described. This greater public “name recognition” makes itself known through the media to the regulatory and technical community and has prompted interest in sponsoring research that defines the composition and concentrations of PPCPs in potential sources and their fate and effects following relase into the environment. Independent of the drivers that potentially fuel the interest in studies of PPCPs, it is clear that PPCP research has grown beyond surface-water studies to examine issues such as: • Presence in other matrices, such as groundwater, landfill leachates, sediments, and biosolids. • Environmental transport and fate in surface water, groundwater, and soils amended with reclaimed water or biosolids. • PPCP source elucidation, such as wastewater treatment plant (WWTP) effluents, confined animal feeding operations (CAFOs), and aquaculture. • Removal during wastewater and drinking-water treatment. • Effects on aquatic ecosystems, terrestrial ecosystems, and human health. The chapters in this book provide an extensive examination of current environmental pharmaceutical research and are divided into three sections: “Occurrence and Analysis of Pharmaceuticals in the Environment,” “Environment Fate and Transformations of Veterinary Pharmaceuticals,” and “treatment of Pharmaceuticals in Drinking Water and Wastewater.” The purpose of this introductory overview chapter is to outline current (2004-2006) knowledge about the presence and concentration of PPCPs as described in the published literature. Previous reviews should be consulted for discussions on pre-2004 publications. Those reviews will provide the reader with a comprehensive introduction to the topic of PPCPs in the environment. This chapter describes the sources of PPCPs and other organic contaminants often associated with human wastewater into the environment, the range of concentrations present in various environmental compartments, and the potential routes of removal/sequestration. An overview of the sources and fate of veterinary pharmaceuticals will be discussed in Chapter 5, “Fate and Transport of Veterinary Medicines in the Soil Environment.”

Book chapter

Geochemistry and mineralogy of metallurgical slag

Slag is a waste product from the pyrometallurgical processing of natural ores or the recycling of man-made materials. This chapter provides an overview of the geochemical and mineralogical characteristics of different types of slag. A review of the analytical methods used to determine these characteristics is also provided. Ferrous slags include blast furnace, steelmaking, and ferroalloy slags; the compositions of these slags are generally dominated by Ca and Si, some with significant Al, Fe, and/or Mg. Whereas, the composition of non-ferrous slags, mostly from base-metal production, are generally dominated by Fe and Si with significant but lesser amounts of Al and Ca. As for primary mineralogical phases, olivine-group phases, spinels, and glass are common among all types of slag. Other silicates such as melilite, pyroxene, feldspars, and oxides also occur. Sulfides are more common in non-ferrous slags and metals and intermetallic compounds can be found in both base-metal and ferrous slags. Carbonates are generally exclusive of ferrous slags. The chemical composition of slag depends on the furnace feed, fluxes, fuel source, and furnace conditions and efficiency of metal extraction. The chemistry and texture of mineralogical phases found in slag reflect melt composition and cooling rates. Overall, the mineralogy and chemistry of slags will determine its fate as an environmental liability or a valuable resource.

Book chapter

Comparison of precipitation chemistry measurements obtained by the Canadian Air and Precipitation Monitoring Network and National Atmospheric Deposition Program for the period 1995-2004

Precipitation chemistry and depth measurements obtained by the Canadian Air and Precipitation Monitoring Network (CAPMoN) and the US National Atmospheric Deposition Program/National Trends Network (NADP/NTN) were compared for the 10-year period 1995–2004. Colocated sets of CAPMoN and NADP instrumentation, consisting of precipitation collectors and rain gages, were operated simultaneously per standard protocols for each network at Sutton, Ontario and Frelighsburg, Ontario, Canada and at State College, PA, USA. CAPMoN samples were collected daily, and NADP samples were collected weekly, and samples were analyzed exclusively by each network’s laboratory for pH, H + , Ca 2+ , Mg 2+ , Na + , K + , NH + 4 , Cl − , NO − 3 , and SO 2− 4 . Weekly and annual precipitation-weighted mean concentrations for each network were compared. This study is a follow-up to an earlier internetwork comparison for the period 1986–1993, published by Alain Sirois, Robert Vet, and Dennis Lamb in 2000. Median weekly internetwork differences for 1995–2004 data were the same to slightly lower than for data for the previous study period (1986–1993) for all analytes except NO − 3 , SO 2− 4 , and sample depth. A 1994 NADP sampling protocol change and a 1998 change in the types of filters used to process NADP samples reversed the previously identified negative bias in NADP data for hydrogen-ion and sodium concentrations. Statistically significant biases (α = 0.10) for sodium and hydrogen-ion concentrations observed in the 1986–1993 data were not significant for 1995–2004. Weekly CAPMoN measurements generally are higher than weekly NADP measurements due to differences in sample filtration and field instrumentation, not sample evaporation, contamination, or analytical laboratory differences.

Environmental Monitoring and Assessment

Ground-Water Quality Data in the Santa Clara River Valley Study Unit, 2007: Results from the California GAMA Program

Ground-water quality in the approximately 460-square-mile Santa Clara River Valley study unit (SCRV) was investigated from April to June 2007 as part of the statewide Priority Basin project of the Ground-Water Ambient Monitoring and Assessment (GAMA) Program. The GAMA Priority Basin project was developed in response to the Groundwater Quality Monitoring Act of 2001 and is being conducted by the U.S. Geological Survey (USGS) in cooperation with the California State Water Resources Control Board (SWRCB). The study was designed to provide a spatially unbiased assessment of the quality of raw ground water used for public water supplies within SCRV, and to facilitate a statistically consistent basis for comparing water quality throughout California. Fifty-seven ground-water samples were collected from 53 wells in Ventura and Los Angeles Counties. Forty-two wells were selected using a randomized grid-based method to provide statistical representation of the study area (grid wells). Eleven wells (understanding wells) were selected to further evaluate water chemistry in particular parts of the study area, and four depth-dependent ground-water samples were collected from one of the eleven understanding wells to help understand the relation between water chemistry and depth. The ground-water samples were analyzed for a large number of synthetic organic constituents (volatile organic compounds [VOC], pesticides and pesticide degradates, potential wastewater-indicator compounds, and pharmaceutical compounds), a constituent of special interest (perchlorate), naturally occurring inorganic constituents (nutrients, major and minor ions, and trace elements), radioactive constituents, and microbial constituents. Naturally occurring isotopes (tritium, carbon-13, carbon-14 [abundance], stable isotopes of hydrogen and oxygen in water, stable isotopes of nitrogen and oxygen in nitrate, chlorine-37, and bromine-81), and dissolved noble gases also were measured to help identify the source and age of the sampled ground water. Quality-control samples (blanks or replicates, or samples for matrix spikes) were collected from approximately 26 percent of the wells, and the analyses of these samples were used to evaluate the quality of the data for the ground-water samples. Assessment of the quality-control results showed that the quality of the environmental data was good, with low bias and low variability, and as a result, less than 0.1 percent of the analytes detected in ground-water samples were censored. This study did not attempt to evaluate the quality of water delivered to consumers; after withdrawal from the ground, water typically is treated, disinfected, and (or) blended with other waters to maintain acceptable water quality. Regulatory thresholds apply to treated water that is delivered (or, supplied) to the consumer, not to raw ground water. However, to provide some context for the results, concentrations of constituents measured in the raw ground water were compared with regulatory and non-regulatory thresholds established by the U.S. Environmental Protection Agency (USEPA) and the California Department of Public Health (CDPH) and thresholds established for aesthetic concerns (secondary maximum contaminant levels, SMCL-CA) by CDPH. Most constituents that were detected in ground-water samples were reported at concentrations below their established health-based thresholds. VOCs, pesticides and pesticide degradates, and potential wastewater-indicator compounds were detected in about 33 percent or less of the 42 SCRV grid wells. Concentrations of all detected organic constituents were below established health-based thresholds. Perchlorate was detected in approximately 12 percent of the SCRV grid wells; all concentrations reported were below the NL-CA threshold. Additional constituents, including major ions, trace elements, and nutrients were collected at 26 wells (16 grid wells and 10 understanding wells) of the 53 wells sampled f

Data Series

Mercury concentrations vary within and among individual bird feathers: A critical evaluation and guidelines for feather use in mercury monitoring programs

Feathers are widely used to represent mercury contamination in birds. Yet, few recommendations exist that provide guidance for using bird feathers in mercury monitoring programs. We conducted a literature review and 5 experiments to show that mercury concentrations vary substantially within (vane >100% higher than calamus) and among (>1000%) individual feathers from the same bird. We developed a research tool and guidelines for using bird feathers for mercury studies based on three components: 1) variability of feather mercury concentrations within an individual bird (coefficient of variation [CV]), 2) desired accuracy of the measured mercury concentration, and 3) feather and bird mass. Our results suggest a general rule that if the goal is to limit analytical and processing costs by using whole feathers in only one sample boat, then to achieve an accuracy within 10% of a bird’s overall average feather mercury concentration a bird with a CV≤10% must be <190 g (size of large shorebird). To achieve an accuracy within 20%, a bird with a CV≤10% must be <920 g (size of large duck). When >1 sample boat is needed to fit the required number of feathers to achieve the desired accuracy, results suggest homogenizing feathers and analyzing an aliquot of ≥20 mg for mercury. This study indicates increasing the number of feathers typically used per bird to assess mercury concentrations.

Environmental Toxicology and Chemistry

A compilation of whole-rock and glass major-element geochemistry of Kilauea Volcano, Hawai'i, near-vent eruptive products: January 1983 through September 2001

This report presents major-element geochemical data from 652 glasses (~6,520 analyses) and 795 whole-rock aliquots from 1,002 fresh samples of olivine-tholeiitic lava collected throughout the near-continuous eruption of Kïlauea Volcano, Hawai'i, from January 1983 through September 2001. The data presented herein provide a unique temporal compilation of lava geochemistry that best reflects variations of pre-eruptive magma compositions during prolonged rift-zone eruption. This document serves as a repository for geochemical data referred to in U.S. Geological Survey Professional Paper 1676 (Heliker, Swanson, and Takahashi, eds., 2003) which includes multidisciplinary research papers pertaining to the first twenty years of Puu Oo-Kupaianaha eruption activity. Details of eruption characteristics and nomenclature are provided in the introductory chapter of that volume (Heliker and Mattox, 2003). Geochemical relations among all or portions of this data set are depicted and interpreted by Thornber (2003), Thornber and others (2003) and Thornber (2001). Trace element compositions and Nd, Sr and Pb isotopic analyses of representative samples of this select eruption suite will be provided in a separate and complimentary open file report. From 1983 to October 2001, approximately 2,500 eruption samples were collected and archived by the U.S. Geological Survey’s Hawaiian Volcano Observatory (HVO). Geochemical data for 1,002 of these samples are included here. Previous reports present bulk-lava major- element chemistry for eruption samples collected from 1983 to 1986 and from 1990 to 1994 (Neal and others, 1988 and Mangan and others, 1995, respectively). Major element glass chemistry and thermometry data for samples collected from 1983 to 1994 is reported by Helz and Hearn (1998) and whole-rock and glass chemistry for samples collected from September 1994 to October 2001 is provided by Thornber and others (2002). This report is a compilation of previously published data along with unpublished whole-rock data for the 1986–1990 eruptive interval (episode 48, see Heliker and Mattox, 2003). The geochemical data in this report is mostly limited to well-quenched samples collected at or near their respective vents. The samples include tephra and spatter, in addition to lava dipped from lava lakes, lava tubes, and surface lava flows. The details of sample collection techniques as described by Thornber and others (2002) are generally applicable for this entire sampling interval. Specifically excluded from this database are samples of distal surface flows, many of which were collected for topical studies of emplacement dynamics (for example, Cashman and others, 1999). Samples of sluggish or crystal-laden tube flows collected during eruptive pauses were also excluded, because they bear visual, petrographic and geochemical evidence for crystal accumulation during surface-flow stagnation. In addition, the pre-1992 whole-rock major element data reported here has been corrected to compensate for minor analytical discrepancies between pre- and post-1991 XRF analyses. These discrepancies resulted from a change in instrumentation at the USGS Denver analytical laboratories. This select suite of time-constrained geochemical data is suitable for constructing petrologic models of pre-eruptive magmatic processes associated with prolong rift zone eruption of Hawaiian shield volcanoes.

Hawai'i

Interlaboratory comparison of three sediment bioaccumulation tests

Standard bioaccumulation tests are commonly conducted using Macoma nasuta (clam), and Alitta virens (polychaete) for marine tests, and Lumbriculus variegatus (an oligochaete) for freshwater tests. Because the interlaboratory variability associated with these tests is unknown, four experienced laboratories conducted standard 28-day bioaccumulation tests with the above species using sediments contaminated with polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs). Chemical analysis of tissue samples was performed by a single laboratory. The intralaboratory variance among replicates was relatively low for PCB tissue concentrations, with coefficients of variation (CVs) ranging from 9% to 28% for all laboratories and species, with the exception of one laboratory reporting higher variability for L . variegatus (CV = 51%). Intralaboratory variance for PCB tissue concentrations was higher than interlaboratory variance for A. virens and L . variegatus , and the magnitude of difference (MOD) for laboratory means ranged from 1.4 to 2.0 across species. Intralaboratory variability was also low for lipid content, and lipid normalization of PCB and PAH body residues generally had little impact on variability. In addition to variability across bioassay laboratories, analytical variability was evaluated by different laboratories measuring the concentration of PCBs and total lipids in a subsample of tissue homogenate of sediment-exposed test organisms. Variability associated with tissue analysis was higher than bioassay laboratory variability only in tests with L . variegatus . Statistical differences between samples may be observed due to the low intralaboratory variability; however, the biological significance of these differences may be limited because the MOD is low. Considering the MOD when comparing bioaccumulation across treatments accounts for uncertainty related to inherent variability of the test in the interpretation of statistically significant results.

Massachusetts

Water quality, sediment characteristics, aquatic habitat, geomorphology, and mussel population status of the Clinch River, Virginia and Tennessee, 2009-2011

Chemical, physical, and biological data were collected during 2009-2011 as part of a study of the Clinch River in Virginia and Tennessee. The data from this study, data-collection methods, and laboratory analytical methods used in the study are documented in this report. The study was conducted to describe the conditions of the Clinch River and to determine if there are measurable differences in chemical, physical, or biological characteristics in a segment of the river where freshwater mussel populations are in decline, have low density, richness, little to no recruitment, and lack endangered species (low-quality reach) compared to a segment of the river where mussel assemblages have relatively high density, richness, evidence of recruitment, and support endangered species (high-quality reach). Five continuous water-quality monitors were installed and operated on the mainstem of the Clinch River and two tributaries. Discrete water-quality sample sets were collected during base-flow and stormflow conditions two sites on the Clinch River and on the Guest River, a tributary to the Clinch River predominantly in the Appalachian Plateaus Physiographic Province. Base-flow water-quality samples were collected in July and August 2011 at 15 sites along the mainstem of the Clinch River. Other analyses included longitudinal sampling along the mainstem of the Clinch River at 10 sites to evaluate bed-sediment chemistry, habitat condition, and mollusk community status. In situ freshwater mussel growth and mortality experiments were conducted with hatchery propogated Villosa iris (rainbow mussels). Tissue from the V. iris as well as tissue from 16 Actinonaias pectorosa mussels were analyzed for trace metals, and V. iris mussel tissue was analyzed for organic compounds. Data collected during this investigation were analyzed by various U.S. Geological Survey or U.S. Fish and Wildlife Service laboratories.

Tennessee, Virginia