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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↗

VS2DRTI: Simulating heat and reactive solute transport in variably saturated porous media

Variably saturated groundwater flow, heat transport, and solute transport are important processes in environmental phenomena, such as the natural evolution of water chemistry of aquifers and streams, the storage of radioactive waste in a geologic repository, the contamination of water resources from acid-rock drainage, and the geologic sequestration of carbon dioxide. Up to now, our ability to simulate these processes simultaneously with fully coupled reactive transport models has been limited to complex and often difficult-to-use models. To address the need for a simple and easy-to-use model, the VS2DRTI software package has been developed for simulating water flow, heat transport, and reactive solute transport through variably saturated porous media. The underlying numerical model, VS2DRT, was created by coupling the flow and transport capabilities of the VS2DT and VS2DH models with the equilibrium and kinetic reaction capabilities of PhreeqcRM. Flow capabilities include two-dimensional, constant-density, variably saturated flow; transport capabilities include both heat and multicomponent solute transport; and the reaction capabilities are a complete implementation of geochemical reactions of PHREEQC. The graphical user interface includes a preprocessor for building simulations and a postprocessor for visual display of simulation results. To demonstrate the simulation of multiple processes, the model is applied to a hypothetical example of injection of heated waste water to an aquifer with temperature-dependent cation exchange. VS2DRTI is freely available public domain software.

Groundwater↗

Potential Chemical Effects of Changes in the Source of Water Supply for the Albuquerque Bernalillo County Water Utility Authority

Chemical modeling was used by the U.S. Geological Survey, in cooperation with the Albuquerque Bernalillo County Water Utility Authority (henceforth, Authority), to gain insight into the potential chemical effects that could occur in the Authority's water distribution system as a result of changing the source of water used for municipal and industrial supply from ground water to surface water, or to some mixture of the two sources. From historical data, representative samples of ground-water and surface-water chemistry were selected for modeling under a range of environmental conditions anticipated to be present in the distribution system. Mineral phases calculated to have the potential to precipitate from ground water were compared with the compositions of precipitate samples collected from the current water distribution system and with mineral phases calculated to have the potential to precipitate from surface water and ground-water/surface-water mixtures. Several minerals that were calculated to have the potential to precipitate from ground water in the current distribution system were identified in precipitate samples from pipes, reservoirs, and water heaters. These minerals were the calcium carbonates aragonite and calcite, and the iron oxides/hydroxides goethite, hematite, and lepidocrocite. Several other minerals that were indicated by modeling to have the potential to precipitate were not found in precipitate samples. For most of these minerals, either the kinetics of formation were known to be unfavorable under conditions present in the distribution system or the minerals typically are not formed through direct precipitation from aqueous solutions. The minerals with potential to precipitate as simulated for surface-water samples and ground-water/surface-water mixtures were quite similar to the minerals with potential to precipitate from ground-water samples. Based on the modeling results along with kinetic considerations, minerals that appear most likely to either dissolve or newly precipitate when surface water or ground-water/surface-water mixtures are delivered through the Authority's current distribution system are carbonates (particularly aragonite and calcite). Other types of minerals having the potential to dissolve or newly precipitate under conditions present throughout most of the distribution system include a form of silica, an aluminum hyroxide (gibbsite or diaspore), or the Fe-containing mineral Fe3(OH)8. Dissolution of most of these minerals (except perhaps the Fe-containing minerals) is not likely to substantially affect trace-element concentrations or aesthetic characteristics of delivered water, except perhaps hardness. Precipitation of these minerals would probably be of concern only if the quantities of material involved were large enough to clog pipes or fixtures. The mineral Fe3(OH)8 was not found in the current distribution system. Some Fe-containing minerals that were identified in the distribution system were associated with relatively high contents of selected elements, including As, Cr, Cu, Mn, Pb, and Zn. However, these Fe-containing minerals were not identified as minerals likely to dissolve when the source of water was changed from ground water to surface water or a ground-water/surface-water mixture. Based on the modeled potential for calcite precipitation and additional calculations of corrosion indices ground water, surface water, and ground-water/surface-water mixtures are not likely to differ greatly in corrosion potential. In particular, surface water and ground-water/surface-water mixtures do not appear likely to dissolve large quantities of existing calcite and expose metal surfaces in the distribution system to substantially increased corrosion. Instead, modeling calculations indicate that somewhat larger masses of material would tend to precipitate from surface water or ground-water/surface-water mixtures compared to ground water alone.

Scientific Investigations Report↗

Relation of physical and chemical characteristics of streams to fish communities in the Red River of the North basin, Minnesota and North Dakota, 1993-95

Fish community composition was determined at 33 reaches (average length 150 meters) at 22 sites in the Red River of the North Basin during 1994. Sites were selected to represent a range of stream sizes and ecoregions within the basin. Physical and chemical characteristics (classified in data sets of instream habitat, terrestrial habitat, hydrology, and water quality) were determined for various sites for periods ranging from two to 48 years. Instream habitat measurements were made from 1993 through 1995 for 31 reaches at 19 sites. Terrestrial habitat measures of land use/land cover, soils, and riparian zones were determined from a geographical information system coverage for 23 reaches at 14 sites. The geographical information system coverage used data from aerial photographs taken from 1990 and 1991, National Wetlands Inventory data, soils maps from the Natural Resource Conservation Service, and data from the U.S. Department of Agriculture soils data base. Water chemistry data were collected from 14 sites in the basin from 1993 through 1994. Hydrologic variability was determined from U.S. Geological Survey gaging records. Correlation analysis, cluster analysis, and principal components analysis were used to determine representative variables which accounted for the most variation in each data set. The representative variables and the fish community data were analyzed with canonical correspondence analysis to determine the relative effect of each source of environmental influence on fish community composition. Instream habitat, terrestrial habitat, and hydrologic variability were analyzed together. Water chemistry data were analyzed separately due to a lack of corresponding sites. Within the instream habitat data set, measures of habitat volume (channel width and depth) and habitat diversity were most significant in explaining the variability of the fish communities. The amount of nonagricultural land and riparian zone integrity from the terrestrial habitat data set were also useful in explaining fish community composition. Variability of mean monthly discharge and the frequency of high and low discharge events during the three years prior to fish sampling were the most influential of the hydrologic variables.The first two axes of the canonical correspondence analysis accounted for 43.3 percent of the variation in the fish community and 52.5 percent of the variation in the environmental-species relation. Water-quality indicators such as the percent of fine material in suspended sediment, minimum dissolved oxygen concentrations, minimum concentrations of dissolved organic carbon, and the range of concentrations of major ions and nutrients were the variables that were most important in the canonical correspondence analysis of water-quality data with fish. No single environmental variable or data set appeared to be more important than another in explaining variation in the fish community. The environmental factors affecting the fish communities of the Red River of the North are interrelated. For the most part, instream environmental conditions (instream habitat, hydrology, and water chemistry) appear to be more important in explaining variability in fish community composition than factors related to the agricultural nature of the basin.

Minnesota, North Dakota, South Dakota↗

Characterization of the hydrology, water chemistry, and aquatic communities of selected springs in the St. Johns River Water Management District, Florida, 2004

The hydrology, water chemistry, and aquatic communities of Silver Springs, De Leon Spring, Gemini Springs, and Green Spring in the St. Johns River Water Management District, Florida, were studied in 2004 to provide a better understanding of each spring and to compile data of potential use in future water-management decisions. Ground water that discharges from these and other north-central Florida springs originates from the Upper Floridan aquifer of the Floridan aquifer system, a karstic limestone aquifer that extends throughout most of the State's peninsula. This report summarizes data about flow, water chemistry, and aquatic communities, including benthic invertebrates, fishes, algae, and aquatic macrophytes collected by the U.S. Geological Survey, the St. Johns River Water Management District, and the Florida Department of Environmental Protection during 2004, as well as some previously collected data. Differences in water chemistry among these springs reflect local differences in water chemistry in the Upper Floridan aquifer. The three major springs sampled at the Silver Springs group (the Main Spring, Blue Grotto, and the Abyss) have similar proportions of cations and anions but vary in nitrate and dissolved oxygen concentrations. Water from Gemini Springs and Green Spring has higher proportions of sodium and chloride than the Silver Springs group. Water from De Leon Spring also has higher proportions of sodium and chloride than the Silver Springs group but lower proportions of calcium and bicarbonate. Nitrate concentrations have increased over the period of record at all of the springs except Green Spring. Compounds commonly found in wastewater were found in all the springs sampled. The most commonly detected compound was the insect repellant N,N'-diethyl-methyl-toluamide (DEET), which was found in all the springs sampled except De Leon Spring. The pesticide atrazine and its degradate 2-chloro-4-isopropylamino-6-amino-s-triazine (CIAT) were detected in water from the Silver Springs group and in both boils at Gemini Springs. No pesticides were detected in water samples from De Leon Spring and Green Spring. Evidence of denitrification was indicated by the presence of excess nitrogen gas in water samples from most of the springs. Aquatic communities varied among the springs. Large floating mats of cyanobacteria (blue-green algae), identified as Lyngbya wollei, were observed in De Leon Spring during all sampling events in 2004. At Gemini Springs, the dominant periphyton was Rhizoclonium sp. Of the three springs sampled for benthic invertebrates, De Leon Spring had the highest overall species richness and most disturbance intolerant species (Florida Index = 4). Green Spring had the lowest species richness of the springs sampled. Based on qualitative comparisons, overall macroinvertebrate species richness seemed to be negatively related to magnesium, potassium, sodium, and specific conductance. Invertebrate abundance was greatest when dissolved oxygen and nitrate were high but phosphorus and potassium concentrations were low. Dipteran abundance seemed to be positively associated with specific conductance and total organic carbon but negatively associated with nitrate-N. Amphipods were the numerically dominant group collected in most (six of nine) collections. Shifts in amphipod abundance of the two species collected (Gammarus sp. and Hyalella azteca) varied by season among the three springs, but there were no trends evident in the variation. Fish populations were relatively species-rich at the Silver Springs group, De Leon Spring, and Gemini Springs, but not at Green Spring. Nonindigenous fish species were observed at all springs except Green Spring.

Open-File Report↗

Use of benthic invertebrate community structure and the sediment quality triad to evaluate metal-contaminated sediment in the upper Clark Fork River, Montana

The upper Clark Fork River, above Flathead River, is contaminated with large amounts of As, Cd, Cu, Pb, Mn, and Zn ores from past mining activities. The contaminated area extends from the Butte and Anaconda area to at least 230 km downstream to Milltown Reservoir. Both the upper Clark Fork River and Milltown Reservoir have been designated as U.S. Environmental Protection Agency Superfund sites because of metal-contaminated bottom sediments. We evaluated the impacts of past mining activities on the Clark Fork River ecosystem using benthic invertebrate community assessment, residue chemistry, and toxicity testing. Oligochaeta and Chironomidae generally accounted for over 90% of the benthic invertebrate community in the soft sediment depositional areas. Taxa of Oligochaeta and Chironomidae were predominantly pollution tolerant. Higher numbers of Chironomidae genera were present at stations with higher concentrations of metals in sediment identified as toxic by the amphipod Hyalella azteca in 28-d exposures. Frequency of mouthpart deformities in genera of Chironomidae was low and did not correspond to concentrations of metals in sediment. Total abundance of organisms/m 2 did not correspond to concentrations of metals in the sediment samples. Chemical analyses, laboratory toxicity tests, and benthic community evaluations all provide evidence of metal-induced degradation to aquatic communities in both the reservoir and the river. Using a weight-of-evidence approach-the Sediment Quality Triad - provided good concurrence among measures of benthic community structure, sediment chemistry, and laboratory toxicity.

Montana↗

West Florida Shelf: A natural laboratory for the study of ocean acidificiation

Declining oceanic pH and carbonate-ion concentrations are well-known consequences of increased atmospheric and surface-ocean partial pressure of carbon dioxide (pCO2). The possible subject of shifts in seawater carbonate chemistry on biocalcification and survival rates of marine organisms provides questions amenable to both experimental and field study (Kleypas and Langdon, 2006). To date, limited quantitative data exist with which to formalize and test hypotheses regarding such impacts, particularly in continental-shelf settings. The continental shelves of Florida provide an ideal natural laboratory in which to test latitudinal (and temperature and depth) shifts in habitat ranges of calcifying organisms. Both the east and west Florida shelves extend from warm temperate to subtropical latitudes; additionally, the west Florida shelf has very little siliciclastic influx to mask the carbonate production. This study utilizes the natural laboratory of the west and southwest Florida shelf (fig 1.1) to examine the transition from foramol (predominately foraminifera and molluscan) carbonate sediments, characteristic of the west-central Florida shelf, to chlorozoan (algal and coral) sediments characteristic of the southwest Florida shelf. The west Florida shelf is a mixed siliciclastic carbonate ramp that to the south transitions to the carbonate-dominated southwest Florida shelf (Enos, 1977; Brooks and others, 2003). The west Florida shelf is a distally steepened carbonate ramp that is ~250 kilometers (km) wide (Read, 1985). It is covered by a veneer of unconsolidated sediment consisting of mainly biogenic carbonate and quartz in the near shore, with subordinate amounts of phosphate. The sediment-distribution pattern is largely a function of proximity to source, with physical processes playing a minor role in distribution. The carbonate sand-and-gravel fraction is produced by organisms within the depositional basin of the west Florida shelf (Brooks and others, 2003). The southwest Florida shelf is a rimmed carbonate margin where organisms produce virtually all of the substrate; it also exhibits a greater sediment thickness as compared to the west Florida shelf (Enos, 1977). Temperature, which is usually associated with latitude, plays a major role in locations of foramol versus chlorozoan assemblages, but other factors beyond latitude influence temperature on the west and southwest Florida shelves. The potential of cooler, deep-water upwelling and transport over the bottom waters of the shelf may have a significant role in the species assemblage at the sediment/water interface and ultimately on location of foramol versus chlorozoan production. Deep water transported onto and over the shelf may also have environmental ramifications beyond temperature by bringing in water of different chemistry.

Open-File Report↗

Response of aquatic macrophytes to human land use perturbations in the watersheds of Wisconsin lakes, U.S.A.

Aquatic macrophyte communities were assessed in 53 lakes in Wisconsin, U.S.A. along environmental and land use development gradients to determine effects human land use perturbations have on aquatic macrophytes at the watershed and riparian development scales. Species richness and relative frequency were surveyed in lakes from two ecoregions: the Northern Lakes and Forests Ecoregion and the Southeastern Wisconsin Till Plain Ecoregion. Lakes were selected along a gradient of watershed development ranging from undeveloped (i.e., forested), to agricultural to urban development. Land uses occurring in the watershed and in perimeters of different width (0–100, 0–200, 0–500, and 0–1000 m from shore, in the watershed) were used to assess effects on macrophyte communities. Snorkel and SCUBA were used to survey aquatic macrophyte species in 18 quadrats of 0.25 m 2 along 14 transects placed perpendicular to shore in each lake. Effects of watershed development (e.g., agriculture and/or urban) were tested at whole-lake (entire littoral zone) and near-shore (within 7 m of shore) scales using canonical correspondence analysis (CCA) and linear regression. Overall, species richness was negatively related to watershed development, while frequencies of individual species and groups differed in level of response to different land use perturbations. Effects of land use in the perimeters on macrophytes, with a few exceptions, did not provide higher correlations compared to land use at the watershed scale. In lakes with higher total watershed development levels, introduced species, particularly Myriophyllum spicatum , increased in abundance and native species, especially potamids, isoetids, and floating-leaved plants, declined in abundance. Correlations within the northern and southeastern ecoregions separately were not significant. Multivariate analyses suggested species composition is driven by environmental responses as well as human development pressures. Both water chemistry and land use variables loaded positively with the first CCA axis indicating that these factors are correlated. Land use pressures in Wisconsin are greater in the southeastern portion of the state where lakes have higher concentrations of water chemistry variables including alkalinity, conductivity, pH, calcium, magnesium, and nitrogen. This creates a complex gradient that influences species composition of macrophyte communities from lake to lake.

Wisconsin↗

The presence and distribution of polycyclic aromatic hydrocarbons and inorganic elements in water and lakebed materials and the potential for bioconcentration in biota at established sampling sites on Lake Powell, Utah and Arizona

The National Park Service is responsible for monitoring the effects of visitor use on the quality of water, lakebed material (bottom sediments), and biota, in Lake Powell, Utah and Arizona. A sampling program was begun in 2010 to assess the presence, distribution, and concentrations of organic and inorganic compounds in the water column and bottom sediment. In response to an Environmental Impact Statement regarding personal watercraft and as a continuation from previous studies by the U.S. Geological Survey and the National Park Service, Glen Canyon National Recreation Area, water samples were collected and analyzed for polycyclic aromatic hydrocarbons (PAHs) using semipermeable membrane devices and inorganic elements using a fixed-bottle sampler deployed at established monitoring sites during 2010 and 2011. Lakebed material samples were also analyzed for polycyclic aromatic hydrocarbons and inorganic elements, some of which could be harmful to aquatic biota if present at concentrations above established aquatic life criteria. Of the 44 PAH compounds analyzed, 26 individual compounds were detected above the censoring limit in the water column by semipermeable membrane devices. The highest number of compounds detected were at Lone Rock Beach, Wahweap Marina, Rainbow Bridge National Monument, and Antelope Marina which are all located in the southern part of Lake Powell where visitation and boat use is high. Because PAHs can remain near their source, the potential for bioconcentration is highest near these sites. The PAH compound found in the highest concentration was phenol (5,902 nanograms per liter), which is included in the U.S. Environmental Protection Agency’s priority pollutants list. The dissolved inorganic chemistry of water samples measured at the sampling sites in Lake Powell defined three different patterns of elements: (1) concentrations were similar between sites in the upper part of the lake near Farley Canyon downstream to Halls Crossing Marina, a distance of about 36 lake miles, (2) concentrations varied depending on the element between Halls Crossing Marina downstream to the mouth of the Escalante River, a distance of about 33 lake miles, and (3) concentrations were similar between sites from below the mouth of the Escalante River to Glen Canyon Dam, a distance of about 68 lake miles. Analysis of lakebed bottom sediment material samples detected PAH compounds at all sampling sites except at Halls Crossing Marina, Stanton Creek, and Forgotten Canyon. Twenty-four of 44 PAHs analyzed in lakebed material were detected above the reporting limit. Perylene was the most prevalent compound detected above the reporting limit in lakebed material and was detected at three sampling sites. Concentrations of perylene ranged from an estimate of 24.0 to 47.9 micrograms per kilogram (μg/kg). Fluoranthene had the highest concentration of any PAH and was detected at the Wahweap Marina with a concentration of 565 μg/kg. The highest sum of concentrations for all compounds found in lakebed material samples at one site was at the Wahweap Marina, which had concentrations five times higher than the next highest site. The three major tributaries to Lake Powell—the Colorado, Escalante, and San Juan Rivers—all showed elevated concentrations of inorganic elements in their delta sediments for most elements relative to the majority of the sediment samples taken from the lake itself. However, there were four lake sites that had concentrations for most inorganic elements that equaled or exceeded those of the tributaries. Two of these sites were at the northeast part of the lake, nearest to the Colorado River as it enters Lake Powell (Farley Canyon and Blue Notch Canyon), one was at the Escalante River below 50-Mile Canyon, and other was at Antelope Marina.

Arizona;Utah↗

Test well DO-CE 88 at Cambridge, Dorchester County, Maryland

Test well DO-CE 88 at Cambridge, Maryland, penetrated 3,299 feet of unconsolidated Quaternary, Tertiary and Cretaceous sediments and bottomed in quartz-monzonite gneiss. The well was drilled to provide data for a study of the aquifer system of the northern Atlantic Coastal Plain. Twenty-one core samples were collected. Six sand zones were tested for aquifer properties and sampled for ground-water chemistry. Point-water heads were measured at seven depths. Environmental heads (which ranged from -18.33 to +44.16 feet relative to sea level) indicate an upward component of flow. A temperature log showed a maximum temperature of 41.9 degrees Celsius and a mean temperature gradient of 0.00838 degrees Celsius per foot. The water analyses delineated the freshwater-saltwater transition zone between 2,650 and 3,100 feet. The ground water changes progressively downward from a sodium bicarbonate to a sodium chloride character. Clays in the analyzed core samples belong to the montmorillonite and kaolinite groups, and mean cation exchange capacity ranged from 8.3 to 38.9 milliequivalents per 100 grams. Vertical and horizontal hydraulic conductivities measured in cores ranged from 1.5 x 10-s to 1.3 feet per day and from 7.3 x 10-6 to 1.3 feet per day, respectively, but the most permeable sands were not cored. Porosity was 1.5 percent in the quartz monzonite bedrock and ranged from 22.4 to 41 percent in the overlying sediments. Transmissivities from aquifer tests ranged from 25 to 850 feet squared per day, horizontal hydraulic conductivities ranged from 2.5 to 85 feet squared per day, and intrinsic permeabilities ranged from 0.8 to 23 micrometers squared. Fossils identified in core samples include palynomorphs, dinoflagellates, and foraminifers.

Maryland↗

Questa baseline and pre-mining ground-water quality investigation. 25. Summary of results and baseline and pre-mining ground-water geochemistry, Red River Valley, Taos County, New Mexico, 2001-2005

Active and inactive mine sites are challenging to remediate because of their complexity and scale. Regulations meant to achieve environmental restoration at mine sites are equally challenging to apply for the same reasons. The goal of environmental restoration should be to restore contaminated mine sites, as closely as possible, to pre-mining conditions. Metalliferous mine sites in the Western United States are commonly located in hydrothermally altered and mineralized terrain in which pre-mining concentrations of metals were already anomalously high. Typically, those pre-mining concentrations were not measured, but sometimes they can be reconstructed using scientific inference. Molycorp?s Questa molybdenum mine in the Red River Valley, northern New Mexico, is located near the margin of the Questa caldera in a highly mineralized region. The State of New Mexico requires that ground-water quality standards be met on closure unless it can be shown that potential contaminant concentrations were higher than the standards before mining. No ground water at the mine site had been chemically analyzed before mining. The aim of this investigation, in cooperation with the New Mexico Environment Department (NMED), is to infer the pre-mining ground-water quality by an examination of the geologic, hydrologic, and geochemical controls on ground-water quality in a nearby, or proximal, analog site in the Straight Creek drainage basin. Twenty-seven reports contain details of investigations on the geological, hydrological, and geochemical characteristics of the Red River Valley that are summarized in this report. These studies include mapping of surface mineralogy by Airborne Visible-Infrared Imaging Spectrometry (AVIRIS); compilations of historical surface- and ground- water quality data; synoptic/tracer studies with mass loading and temporal water-quality trends of the Red River; reaction-transport modeling of the Red River; environmental geology of the Red River Valley; lake-sediment chemistry; geomorphology and its effect on ground-water flow; geophysical studies on depth to ground-water table and depth to bedrock; bedrock fractures and their potential influence on ground-water flow; leaching studies of scars and waste-rock piles; mineralogy and mineral chemistry and their effect on ground-water quality; debris-flow hazards; hydrology and water balance for the Red River Valley; ground-water geochemistry of selected wells undisturbed by mining in the Red River Valley; and quality assurance and quality control of water analyses. Studies aimed specifically at the Straight Creek natural-analog site include electrical surveys; high-resolution seismic survey; age-dating with tritium/helium; water budget; ground-water hydrology and geochemistry; and comparison of mineralogy and lithology to that of the mine site. The highly mineralized and hydrothermally altered volcanic rocks of the Red River Valley contain several percent pyrite in the quartz-sericite-pyrite (QSP) alteration zone, which weather naturally to acid-sulfate surface and ground waters that discharge to the Red River. Weathering of waste-rock piles containing pyrite also contributes acid water that eventually discharges into the Red River. These acid discharges are neutralized by circumneutral-pH, carbonate-buffered surface and ground waters of the Red River. The buffering capacity of the Red River, however, decreases from the town of Red River to the U.S. Geological Survey (USGS) gaging station near Questa. During short, but intense, storm events, the buffering capacity is exceeded and the river becomes acid from the rapid flushing of acidic materials from natural scar areas. The lithology, mineralogy, elevation, and hydrology of the Straight Creek proximal analog site were found to closely approximate those of the mine site with the exception of the mine site?s Sulphur Gulch catchment. Sulphur Gulch contains three subcatchments?upper Sulphur Gulch, Blind Gulch, and Spring Gulc

New Mexico↗

Temporal trends in water-quality constituent concentrations and annual loads of chemical constituents in Michigan watersheds, 1998–2013

In 1998, the Michigan Department of Environmental Quality and the U.S. Geological Survey began the Water Chemistry Monitoring Program for select streams in the State of Michigan. Objectives of this program were to provide assistance with (1) statewide water-quality assessments, (2) the National Pollutant Discharge Elimination System permitting process, and (3) water-resource management decisions. As part of this program, water-quality data collected from 1998 to 2013 were analyzed to identify potential trends for select constituents that were sampled. Sixteen water-quality constituents were analyzed at 32 stations throughout Michigan. Trend analysis on the various water-quality data was done using either the uncensored Seasonal Kendall test or through Tobit regression. In total, 79 trends were detected in the constituents analyzed for 32 river stations sampled for the study period—53 downward trends and 26 upward trends were detected. The most prevalent trend detected throughout the State was for ammonia, with 11 downward trends and 1 upward trend estimated. In addition to trends, constituent loads were estimated for 31 stations from 2002 to 2013 for stations that were sampled 12 times per year. Loads were computed using the Autobeale load computation program, which used the Beale ratio estimator approach to estimate an annual load. Constituent loads were the largest in large watershed streams with the highest annual flows such as the Saginaw and Grand Rivers. Likewise, constituent loads were the smallest in smaller tributaries that were sampled as part of this program such as the Boardman and Thunder Bay Rivers.

Michigan↗

Test well DO-CE 88 at Cambridge, Dorchester County, Maryland

Test well DO-CE 88 at Cambridge, Maryland, penetrated 3,299 feet of unconsolidated Quaternary, Tertiary and Cretaceous sediments and bottomed in quartz-monzonite gneiss. The well was drilled to provide data for a study of the aquifer system of the northern Atlantic Coastal Plain. Twenty-one core samples were collected. Six sand zones were tested for aquifer properties and sampled for ground-water chemistry. Point-water heads were measured at seven depths. Environmental heads (which ranged from - 18.33 to + 44.16 feet relative to sea level)indicate an upward component of flow. A temperature log showed a maximum temperature of 41.9 degrees Celsius and a mean temperature gradient of 0.00838 degrees Celsius per foot. The water analyses delineated the freshwater-saltwater transition zone between 2,650 and 3,100 feet. The ground water changes progressively downward from a sodium bicarbonate to a sodium chloride character. Clays in the analyzed core samples belong to the montmorillonite and kaolinite groups, and mean cation exchange capacity ranged from 8.3 to 38.9 milliequivalents per 100 grams. Vertical and horizontal hydraulic conductivities measured in cores ranged from 1.5 x 10 6 to 1.3 feet per day and from 7.3 x 10 -6 to 1.3 feet per day, respectively, but the most permeable sands were not cored. Porosity was 1.5 percent in the quartz monzonite bedrock and ranged from 22.4 to 41 percent in the overlying sediments. Transmissivities from aquifer tests ranged from 25 to 850 feet squared per day; horizontal hydraulic conductivities ranged from.2.5 to 85 feet squared per day, and intrinsic permeabilities ranged from 0.8 to 23 micrometers squared. Fossils identified in core samples include palynomorphs, dinoflagellates, and foraminifers.

Water Supply Paper↗

Effects of multi-scale environmental characteristics on agricultural stream biota in eastern Wisconsin

The U.S. Geological Survey examined 25 agricultural streams in eastern Wisconsin to determine relations between fish, invertebrate, and algal metrics and multiple spatial scales of land cover, geologic setting, hydrologic, aquatic habitat, and water chemistry data. Spearman correlation and redundancy analyses were used to examine relations among biotic metrics and environmental characteristics. Riparian vegetation, geologic, and hydrologic conditions affected the response of biotic metrics to watershed agricultural land cover but the relations were aquatic assemblage dependent. It was difficult to separate the interrelated effects of geologic setting, watershed and buffer land cover, and base flow. Watershed and buffer land cover, geologic setting, reach riparian vegetation width, and stream size affected the fish IBI, invertebrate diversity, diatom IBI, and number of algal taxa; however, the invertebrate FBI, percentage of EPT, and the diatom pollution index were more influenced by nutrient concentrations and flow variability. Fish IBI scores seemed most sensitive to land cover in the entire stream network buffer, more so than watershed-scale land cover and segment or reach riparian vegetation width. All but one stream with more than approximately 10 percent buffer agriculture had fish IBI scores of fair or poor. In general, the invertebrate and algal metrics used in this study were not as sensitive to land cover effects as fish metrics. Some of the reach-scale characteristics, such as width/depth ratios, velocity, and bank stability, could be related to watershed influences of both land cover and geologic setting. The Wisconsin habitat index was related to watershed geologic setting, watershed and buffer land cover, riparian vegetation width, and base flow, and appeared to be a good indicator of stream quality. Results from this study emphasize the value of using more than one or two biotic metrics to assess water quality and the importance of environmental characteristics at multiple scales.

Wisconsin↗

Evaluation of ground-water and boron sources by use of boron stable-isotope ratios, tritium, and selected water-chemistry constituents near Beverly Shores, northwestern Indiana, 2004

Concentrations of boron greater than the U.S. Environmental Protection Agency (USEPA) 900 μg/L removal action level (RAL) standard were detected in water sampled by the USEPA in 2004 from three domestic wells near Beverly Shores, Indiana. The RAL regulates only human-affected concentrations of a constituent. A lack of well logs and screened depth information precluded identification of whether water from sampled wells, and their boron sources, were from human-affected or natural sources in the surficial aquifer, or associated with a previously defined natural, confined aquifer source of boron from the subtill or basal sand aquifers. A geochemically-based classification of the source of boron in ground water could potentially determine the similarity of boron to known sources or mixtures between known sources, or classify whether the relative age of the ground water predated the potential sources of contamination. The U.S. Geological Survey (USGS), in cooperation with the USEPA, investigated the use of a geochemical method that applied boron stable isotopes, and concentrations of boron, tritium, and other constituents to distinguish between natural and human-affected sources of boron in ground water and thereby determine if the RAL was applicable to the situation. Boron stable-isotope ratios and concentrations of boron in 17 ground-water samples and tritium concentrations in 9 ground-water samples collected in 2004 were used to identify geochemical differences between potential sources of boron in ground water near Beverly Shores, Indiana. Boron and δ 11 B analyses for this investigation were made on unacidified samples to assure consistency of the result with unacidified analyses of δ 11 B values from other investigations. Potential sources of boron included surficial-aquifer water affected by coal-combustion products (CCP) or domestic-wastewater, upward discharge of ground water from confined aquifers, and unaffected water from the surficial aquifer that was distant from human-affected boron sources. Boron concentrations in potential ground-water sources of boron were largest (15,700 to 24,400 μg/L) in samples of CCP-affected surficial aquifer water from four wells at a CCP landfill and smallest (27 to 63 μg/L) in three wells in the surficial aquifer that were distant from human-affected boron sources. Boron concentrations in water from the basal sand aquifer ranged from 656 μg/L to 1,800 μg/L. Boron concentrations in water from three domestic-wastewater-affected surficial aquifer wells ranged from 84 to 387 μg/L. Among the representative ground-water samples, boron concentrations from all four samples of CCP-affected surficial aquifer water and four of five samples of water from the basal sand aquifer had concentrations greater than the RAL. A comparison of boron concentrations in acid-preserved and unacidified samples indicated that boron concentrations reported for this investigation may be from about 11 to 16 percent less than would be reported in a standard analysis of an acidified sample. The stable isotope boron-11 was most enriched in comparison to boron-10 in ground water from a confined aquifer, the basal sand aquifer (δ 11 B, 24.6 to 34.0 per mil, five samples); it was most depleted in CCP-affected water from the surficial aquifer (δ 11 B, 0.1 to 6.6 per mil, four samples). Domestic-wastewater-affected water from the surficial aquifer (δ 11 B, 8.7 to 11.7 per mil, four samples) was enriched in boron-11, in comparison to individual samples of a borax detergent additive and a detergent with perborate bleach; it was intermediate in composition between basal sand aquifer water and CCP-affected water from the surficial aquifer. The similarity between a ground-water sample from the surficial aquifer and a hypothetical mixture of unaffected surficial aquifer and basal sand aquifer waters indicates the potential for long-term upward discharge of ground water into the surficial aquifer from one or more confined aquifers. Estimated δ 11 B values for acidified samples were depleted by 1.9 to 2.8 per mil in comparison to unacidified samples from the four wells sampled; those differences were small in comparison to the differences between δ 11 B values of representative sources of boron in ground water. Tritium concentrations ranged from 7.0 to 10.3 tritium units in six samples from the surficial aquifer and were less than 0.8 tritium units in three samples from the basal sand aquifer. Water from wells in the surficial aquifer represents predominantly modern, post-1972 recharge and sources of boron and other constituents. Water from the basal sand aquifer is associated with pre-1952 recharge from sources not affected by local boron inputs. Ground water from six wells (five domestic wells and one public-supply well) where the ground-water source was unknown had boron concentrations, boron isotope ratios, and tritium concentrations similar to water from the basal sand aquifer. Boron concentrations greater than the RAL were found in water from four of these six wells. The boron isotope and tritium data from these four wells indicate a natural source of boron in ground water; therefore, the RAL does not apply to boron concentrations in water from these wells. Water samples from two domestic wells where the ground-water source was unknown had boron concentrations less than the RAL and boron isotope ratios and tritium concentrations that were similar to domestic-wastewater-affected water from the surficial aquifer. The boron isotope ratio for a sample from one domestic well was similar to that of CCP-affected water from the surficial aquifer and detergent compositions; the boron concentration of that sample was less than the RAL. The classifications of differences among representative sources of boron in ground water and water samples from wells where the ground-water source was unknown generally agreed with distinctions based on strontium-87/strontium-86 ratios and concentrations of strontium, chloride, nitrate, and ammonia. This application of boron concentrations, boron isotope ratios, and tritium concentrations to classify differences in relation to potential sources of boron in ground water was able to distinguish between boron from natural sources and from human-affected sources that are subject to regulation.

Indiana↗

Chemical characteristics of urban stormwater sediments and implications for environmental management, Maricopa County, Arizona

Investigations of the chemical characteristics of urban stormwater sediments in the rapidly growing Phoenix metropolitan area of Maricopa County, Arizona, showed that the inorganic component of these sediments generally reflects geologic background values. Some concentrations of metals were above background values, especially cadmium, copper, lead, and zinc, indicating an anthropogenic contribution of these elements to the sediment chemistry. Concentrations, however, were not at levels that would require soil remediation according to guidelines of the U.S. Environmental Protection Agency. Arsenic concentrations generally were above recommended values for remediation at a few sites, but these concentrations seem to reflect geologic rather than anthropogenic factors. Several organochlorine compounds no longer in use were ubiquitous in the Phoenix area, although concentrations generally were low. Chlordane, DDT and its decay products DDE and DDD, dieldrin, toxaphene, and PCBs were found at almost all sites sampled, although some of the pesticides in which these compounds are found have been banned for almost 30 years. A few sites showed exceptionally high concentrations of organochlorine compounds. On the basis of published guidelines, urban stormwater sediments do not appear to constitute a major regional environmental problem with respect to the chemical characteristics investigated here. At individual sites, high concentrations of organic compounds - chlordane, dieldrin, PCBs, and toxaphene - may require some attention. The possible environmental hazard presented by low-level organochlorine contamination is not addressed in this paper; however, high levels of toxicity in urban sediments are difficult to explain. Sediment toxicity varied significantly with time, which indicates that these tests should be evaluated carefully before they are used for management decisions.Investigations of the chemical characteristics of urban stormwater sediments in the rapidly growing Phoenix metropolitan area of Maricopa County, Arizona, showed that the inorganic component of these sediments generally reflects geologic background values. Some concentrations of metals were above background values, especially cadmium, copper, lead, and zinc, indicating an anthropogenic contribution of these elements to the sediment chemistry. Concentrations, however, were not at levels that would require soil remediation according to guidelines of the U.S. Environmental Protection Agency. Arsenic concentrations generally were above recommended values for remediation at a few sites, but these concentrations seem to reflect geologic rather than anthropogenic factors. Several organochlorine compounds no longer in use were ubiquitous in the Phoenix area, although concentrations generally were low. Chlordane, DDT and its decay products DDE and DDD, dieldrin, toxaphene, and PCBs were found at almost all sites sampled, although some of the pesticides in which these compounds are found have been banned for almost 30 years. A few sites showed exceptionally high concentrations of organochlorine compounds. On the basis of published guidelines, urban stormwater sediments do not appear to constitute a major regional environmental problem with respect to the chemical characteristics investigated here. At individual sites, high concentrations of organic compounds - chlordane, dieldrin, PCBs, and toxaphene - may require some attention. The possible environmental hazard presented by low-level organochlorine contamination is not addressed in this paper; however, high levels of toxicity in urban sediments are difficult to explain. Sediment toxicity varied significantly with time, which indicates that these tests should be evaluated carefully before they are used for management decisions.

Environmental Management↗

Comparison of two estrogen chemically activated luciferase expression cell bioassays to liquid chromatography–mass spectrometry for quantifying estrone in water samples

Chemically activated luciferase expression (CALUX) cell bioassays are popular tools for assessing endocrine activity of chemicals such as certain environmental contaminants. Although activity equivalents can be obtained from CALUX analysis, directly comparing these equivalents to those obtained from analytical chemistry methods can be problematic because of the complexity of endocrine active pathways. We explored the suitability of two estrogen CALUX bioassays (the Organisation for Economic Co-operation and Development–approved VM7Luc4E2 cell bioassay and the VM7LucERβc9 cell bioassay) for quantitation of estrogen. Quadrupole-time of flight ultraperformance liquid chromatography–mass spectrometry (LC/MS) was selected as a comparative method. Regression analysis of measured estrone (E1) calibration samples showed all three methods to be highly predictive of nominal concentrations ( p ≤ 7.5 × 10 –51 ). Extracts of water sampled from laboratory dilutor tanks containing E1 at 0, 20, and 200 ng/L alone and in combination with atrazine were selected to test the quantitative capabilities of the CALUX assays. Process controls (0 and 100 ng E1/L) and a separate E1 standard (10 ng/ml, used to prepare the E1 process control) were also tested. Levels of E1 determined by LC/MS analysis and bioanalytical equivalents (ng E1/L) determined by CALUX analyses were comparable except in certain instances where the samples required dilution prior to CALUX analyses (e.g., the E1 process control and E1 standard). In those instances, measurements by CALUX were slightly but significantly decreased relative to LC/MS. Atrazine had no effect on the ability of either LC/MS or the CALUX bioassays to quantify E1. The present study illustrates the CALUX bioassays as successful in quantifying an estrogen in simple water samples and further characterizes their utility for screening. Environ Toxicol Chem 2023;42:333–339. Published 2022. This article is a U.S. Government work and is in the public domain in the USA.

Environmental Toxicology and Chemistry↗

Trends in summer chemistry linked to productivity in lakes recovering from acid deposition in the Adirondack region of New York

The US Environmental Protection Agency established the Adirondack Effects Assessment Program (AEAP) to evaluate and monitor the status of biological communities in lakes in the Adirondack region of New York that have been adversely affected by acid deposition. This program includes chemical analysis of 30 lakes, sampled two to three times each summer. Results of trends analysis for lake chemistry and chlorophyll a (chlor a) are presented for 1994 to 2003, and a general comparison is made with recent results of the Adirondack Long-Term Monitoring (ALTM) Program, which included chemical analysis of all but two of these lakes (plus an additional 24 lakes) monthly, year-round for 1992-2004. Increases in pH were found in 25 of the 30 AEAP lakes (P < 0.05) and increases in acid-neutralizing capacity (ANC) were found in 12 of the 30 lakes (P < 0.05). Concentrations of both SO 42- and Mg 2+ decreased in 11 lakes (P < 0.05), whereas concentrations of NO 3- decreased in 20 lakes (P < 0.05). Concentrations of NH 4+ decreased in 10 lakes at a significance level of P < 0.05 and in three other lakes based on P < 0.1. Concentrations of inorganic and organic monomeric aluminum generally were below the reporting limit of 1.5 ??mol L-1, but decreases were detected in four and five lakes, respectively (P < 0.1). Concentrations of chlor a increased in seven lakes at a significance level of P < 0.05 and two lakes at a significance level of P < 0.1. A significant inverse correlation was also found between chlor a and NO 3- concentrations in nine lakes at a significance level of P < 0.05 and two lakes at a significance level of P < 0.1. Results of AEAP analysis of lake chemistry were similar to those of the ALTM Program, although decreases in SO 42- concentrations were more evident in the year-round ALTM record. Overall, the results suggest (a) a degree of chemical recovery from acidification during the summer, (b) an increase in phytoplankton productivity, and (c) a decreasing trend in NO 3- concentrations resulting from the increased productivity. ?? 2007 Springer Science+Business Media, Inc.

Ecosystems↗