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A comparison of methods for deriving solute flux rates using long-term data from streams in the mirror lake watershed

Calculation of chemical flux rates for streams requires integration of continuous measurements of discharge with discrete measurements of solute concentrations. We compared two commonly used methods for interpolating chemistry data (time-averaging and flow-weighting) to determine whether discrepancies between the two methods were large relative to other sources of error in estimating flux rates. Flux rates of dissolved Si and SO42- were calculated from 10 years of data (1981-1990) for the NW inlet and Outlet of Mirror Lake and for a 40-day period (March 22 to April 30, 1993) during which we augmented our routine (weekly) chemical monitoring with collection of daily samples. The time-averaging method yielded higher estimates of solute flux during high-flow periods if no chemistry samples were collected corresponding to peak discharge. Concentration-discharge relationships should be used to interpolate stream chemistry during changing flow conditions if chemical changes are large. Caution should be used in choosing the appropriate time-scale over which data are pooled to derive the concentration-discharge regressions because the model parameters (slope and intercept) were found to be sensitive to seasonal and inter-annual variation. Both methods approximated solute flux to within 2-10% for a range of solutes that were monitored during the intensive sampling period. Our results suggest that errors arising from interpolation of stream chemistry data are small compared with other sources of error in developing watershed mass balances.

Water, Air, & Soil Pollution↗

Hydric soils in a southeastern Oregon vernal pool

Vernal pools on the High Lava Plain of the northern Great Basin become ponded in most years, but their soils exhibit weak redoximorphic features indicative of hydric conditions. We studied the hydrology, temperature, redox potentials, soil chemistry, and soil morphology of a vernal pool to determine if the soils are hydric, and to evaluate hydric soil field indicators. We collected data for 3 yr from piezometers, Pt electrodes, and thermocouples. Soil and water samples were analyzed for pH, organic C, and extractable Fe and Mn. Soils were ponded from January through April or May, but subsurface saturation was never detected. Soil temperatures 50 cm below the surface rose above 5°C by March. Clayey Bt horizons perched water and limited saturation to the upper 10 cm. Redox potentials at a 5-cm depth were often between 200 and 300 mV, indicating anaerobic conditions, but producing soluble Fe 2+ concentrations <1 mg L −1 Extractable soil Fe contents indicated Fe depletion from pool surface horizons and accumulation at or near the upper Bt1 horizon. Depletions and concentrations did not satisfy the criteria of any current hydric soil indicators. We recommend development of new indicators based on acceptance of fewer, less distinct redox concentrations for recognition of a depleted A horizon, and on presence of a thin zone containing redox concentrations located in the upper part of the near-surface perching horizon.

Soil Science Society of America Journal↗

Aqueous geochemical data from the analysis of stream-water samples collected in June and August 2008&mdash;Taylor Mountains 1:250,000- and Dillingham D-4 1:63,360-scale quadrangles, Alaska

We report on the chemical analysis of water samples collected from the Taylor Mountains 1:250,000- and Dillingham D-4 1:63,360-scale quadrangles, Alaska. Reported parameters include pH, conductivity, water temperature, major cation and anion concentrations, and trace-element concentrations. We collected the samples as part of a multiyear U.S. Geological Survey project entitled "Geologic and Mineral Deposit Data for Alaskan Economic Development." Data presented here are from samples collected in June and August 2008. Minimal interpretation accompanies this data release. This is the fourth release of aqueous geochemical data from this project; data from samples collected in 2004, 2005, and 2006 were published previously. The data in this report augment but do not duplicate or supersede the previous data releases. Site selection was based on a regional sampling strategy that focused on first- and second-order drainages. Water sample sites were selected on the basis of landscape parameters that included physiography, wetland extent, lithological changes, and a cursory field review of mineralogy from pan concentrates. Stream water in the study area is dominated by bicarbonate (HCO 3 - ), although in a few samples more than 50 percent of the anionic charge can be attributed to sulfate (SO 4 2- ). The major-cation chemistry of these samples ranges from Ca 2+ -Mg 2+ dominated to a mix of Ca 2+ -Mg 2+ -Na + +K 2+ . In most cases, analysis of duplicate samples showed good agreement for the major cation and major anions with the exception of the duplicate samples at site 08TA565. At site 08TA565, Ca, Mg, Cl, and CaCO 3 exceeded 25 percent and the concentrations of trace elements As, Fe and Mn also exceeded 25 percent in this duplicate pair. Chloride concentration varied by more than 25 percent in 5 of the 11 duplicated samples. Trace-element concentrations in these samples generally were at or near the detection limit for the method used and, except for Co at site 08TA565, generally good agreement was determined between duplicate samples for elements with detectable concentrations. Major-ion concentrations were below detection limits in all field blanks, and the trace-element concentrations also were generally below detection limits; however, Co, Mn, Na, Zn, Cl, and Hg were detected in one or more field blank samples.

Alaska↗

Anderson Ranch wetlands hydrologic characterization in Taos County, New Mexico

The Anderson Ranch property (study area), located in Taos County, north-central New Mexico, was transferred from Chevron Mining, Inc. (CMI) to the Bureau of Land Management (BLM) as part of a Natural Resource Damage Assessment and Restoration (NRDAR) court-ordered settlement. The study area supports freshwater emergent wetlands and freshwater ponds. The settlement states that CMI will provide the land and a monetary settlement to support the restoration of the wetlands on the property. To best manage the study area, the BLM requires an understanding of potential effects of climate variability and groundwater withdrawals on the wetland function. This study, completed by the U.S. Geological Survey in cooperation with the BLM, provides an initial hydrologic characterization of the study area, which included literature review, collection of groundwater-level and aqueous-chemistry data, completion of a vegetation survey, and preliminary data analysis. The data compiled, collected, and analyzed as part of this study indicate that the wetlands within the study area are groundwater fed and that the water maintaining the wetlands is modern. Surface-water levels in the pond and groundwater levels in the surrounding wetland fluctuate seasonally. The hydraulic gradient in the study area is from northeast to southwest. Evapotranspiration is a main driver of water demand within the study area.

New Mexico↗

Bibliography of geology and hydrology, eastern New Mexico

The High Plains of the eastern New Mexico region are recognized as an abundant and varied source of natural resources. The bibliography of over 1,900 references concerned with geology, hydrology, chemistry, and geography has been compiled to assist physical science researchers in their study of this region. (Kosco-USGS)

Water-Resources Investigations Report↗

One-Dimensional Transport with Equilibrium Chemistry (OTEQ) - A reactive transport model for streams and rivers

OTEQ is a mathematical simulation model used to characterize the fate and transport of waterborne solutes in streams and rivers. The model is formed by coupling a solute transport model with a chemical equilibrium submodel. The solute transport model is based on OTIS, a model that considers the physical processes of advection, dispersion, lateral inflow, and transient storage. The equilibrium submodel is based on MINTEQ, a model that considers the speciation and complexation of aqueous species, acid-base reactions, precipitation/dissolution, and sorption. Within OTEQ, reactions in the water column may result in the formation of solid phases (precipitates and sorbed species) that are subject to downstream transport and settling processes. Solid phases on the streambed may also interact with the water column through dissolution and sorption/desorption reactions. Consideration of both mobile (waterborne) and immobile (streambed) solid phases requires a unique set of governing differential equations and solution techniques that are developed herein. The partial differential equations describing physical transport and the algebraic equations describing chemical equilibria are coupled using the sequential iteration approach. The model's ability to simulate pH, precipitation/dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between instream chemistry and hydrologic transport at the field scale. This report details the development and application of OTEQ. Sections of the report describe model theory, input/output specifications, model applications, and installation instructions. OTEQ may be obtained over the Internet at http://water.usgs.gov/software/OTEQ.

Techniques and Methods↗

Natural or fertilizer-derived uranium in irrigation drainage: A case study in southeastern Colorado, U.S.A.

Drainage from heavily cultivated soils may be contaminated with U that is leached from the soil or added as a trace constituent of PO4-based commercial fertilizer. The effect of decades-long application of U-rich fertilizer on the U concentration of irrigation drainage was investigated in a small (14.2 km2) drainage basin in southeastern Colorado. The basin was chosen because previous reports indicated locally anomalous concentrations of dissolved NO3(6-36 mg l-1) and dissolved U (61 ??g l-1) at the mouth of the only stream. Results of this study indicated minimal impact of fertilizer-U compared to natural U leached from the local soils. Detailed sampling of the stream along a 6 mile (9.7 km) reach through heavily cultivated lands indicated marked decoupling of the buildup of dissolved NO3 and U. Dissolved U increased markedly in the upstream half of the reach and correlated positively with increases in Na, Mg, SO4, B and Li derived from leaching of surrounding shaley soils. In contrast, major increases in dissolved NO3 occurred farther downstream where stream water was heavily impacted by ground water return from extensively fertilized fields. Nitrogen isotopic measurements confirmed that dissolved NO3 originated from fertilizer and soil organic N (crop waste). Uranium isotopic measurements of variably uraniferous waters showed little evidence of contamination with fertilizer-derived U of isotopically distinct 234U/238U alpha activity ratio (A.R. = 1.0). Leaching experiments using local alkaline soil, irrigation water and U-rich fertilizer confirmed the ready leachability of soil-bound U and the comparative immobility of U added with liquid fertilizer. Relatively insoluble precipitates containing Ca-P-U were formed by mixing liquid fertilizer with water containing abundant dissolved Ca. In the local soils soluble Ca is provided by dissolution of abundant gypsum. Similar studies are needed elsewhere because the mobility of fertilizer-derived U is dependent on fertilizer type, porewater chemistry and soil properties (pH, moisture, mineralogy, texture).

Applied Geochemistry↗

Applications of mineral surface chemistry to environmental problems

Environmental surface chemistry involves processes that occur at the interface between the regolith, hydrosphere and atmosphere. The more limited scope of the present review addresses natural and anthropogenically-induced inorganic geochemical reactions between solutes in surface and ground waters and soil and aquifer substrates. Important surficial reactions include sorption, ion exchange, dissolution, precipitation and heterogeneous oxidation/reduction processes occurring at the solid/aqueous interface. Recent research advances in this field have addressed, both directly and indirectly, societal issues related to water quality, pollution, biogeochemical cycling, nutrient budgets and chemical weathering related to long term global climate change. This review will include recent advances in the fundamental and theoretical understanding of these surficial processes, breakthroughs in experimental and instrumental surface characterization, and development of methodologies for field applications.

Reviews of Geophysics↗

Aqueous geochemical data from the analysis of stream-water samples collected in June and July 2005 — Taylor Mountains 1:250,000 scale quadrangle, Alaska

We report on the chemical analysis of water samples collected from the Taylor Mountains 1:250,000-scale quadrangle. Parameters for which data are reported include pH, conductivity, water temperature, major cation and anion concentrations, trace-element concentrations, and dissolved organic-carbon concentrations. Samples were collected as part of a multiyear U.S. Geological Survey project "Geologic and Mineral Deposit Data for Alaskan Economic Development." Data presented here are from samples collected in June and July of 2005. The data are being released at this time with minimal interpretation. This is the second release of aqueous geochemical data from this project; 2004 aqueous geochemical data were published previously ( Wang and others, 2006 ). The data in this report augment but do not duplicate or supersede the previous data release. Site selection was based on a regional sampling strategy that focused on first- and second-order drainages. Water sample site selection was based on landscape parameters that included physiography, wetland extent, lithological changes, and a cursory field review of mineralogy from pan concentrates. Stream water in the Taylor Mountians quadrangle is dominated by bicarbonate (HCO 3- ), though in a few samples more than 50 percent of the anionic charge can be attributed to sulfate (SO 4 2- ). The major-cation chemistry ranges from Ca 2+ /Mg 2+ dominated to a mix of Ca 2+ /Mg 2+ /Na + +K + . In general, good agreement was found between the major cations and anions in the duplicate samples. Many trace elements in these samples were at or near the analytical method detection limit, but good agreement was found between duplicate samples for elements with detectable concentrations. With the exception of a total mercury concentration of 0.33 ng/L detected in a field blank, field blank major-ion and trace-elements concentrations were below detection.

Alaska↗

Tracer-based characterization of hyporheic exchange and benthic biolayers in streams

Shallow benthic biolayers at the top of the streambed are believed to be places of enhanced biogeochemical turnover within the hyporheic zone. They can be investigated by reactive stream tracer tests with tracer recordings in the streambed and in the stream channel. Common in-stream measurements of such reactive tracers cannot localize where the processing primarily takes place, whereas isolated vertical depth profiles of solutes within the hyporheic zone are usually not representative of the entire stream. We present results of a tracer test where we injected the conservative tracer bromide together with the reactive tracer resazurin into a third-order stream and combined the recording of in-stream breakthrough curves with multidepth sampling of the hyporheic zone at several locations. The transformation of resazurin was used as an indicator of metabolism, and high-reactivity zones were identified from depth profiles. The results from our subsurface analysis indicate that the potential for tracer transformation (i.e., the reaction rate constant) varied with depth in the hyporheic zone. This highlights the importance of the benthic biolayer, which we found to be on average 2 cm thick in this study, ranging from one third to one half of the full depth of the hyporheic zone. The reach-scale approach integrated the effects of processes along the reach length, isolating hyporheic processes relevant for whole-stream chemistry and estimating effective reaction rates.

Water Resources Research↗

Influence of test method variables on sensitivity of Neocloeon triangulifer to a reference toxicant in short-term, effluent style evaluations

Recent literature has demonstrated the sensitivity of mayflies to environmental contaminants. However, to date, there are no methods approved by the US Environmental Protection Agency for using sensitive insects like mayflies in whole-effluent toxicity or receiving water toxicity tests. The parthenogenetic mayfly Neocloeon triangulifer has been shown to be amenable to continuous culture in the laboratory, and methods have been described for its use in both acute and chronic toxicity studies. The goal of the present study was to investigate aspects of N. triangulifer testing and culturing methods that might require adjustment so that they are applicable for testing effluents and receiving waters in a short-term exposure. To this end, the influence of organism age, test duration, and test temperature on sensitivity to NaCl as a reference toxicant were tested (concentrations ranging from 182 to 2489 mg/L). Further studies were conducted to assess the utility of commercially available diets and the influence of nutrient amendment of water on organism growth and sensitivity. Seven-day NaCl tests started with less than 24-h-old larvae were similar in sensitivity to 14-day and full life chronic tests, and were much more sensitive than those started with 7-day-old organisms. Reducing test temperature from 25 °C to 22 °C had a minor influence on culture timing, and little impact on sensitivity to NaCl. In other experiments, reconstituted test water supplemented with nutrients to potentially improve in-test food quality had minimal effect on growth at 7 days and did not significantly alter acute sensitivity to NaCl relative to unamended reconstituted water. A suitable commercially available, ready-to-feed diet substitute for cultured diatoms was not found. Testing N. triangulifer in effluents or receiving waters with the methods recommended will complement similar methods for Ceriodaphnia dubia .

Environmental Toxicology and Chemistry↗

Development and evaluation of a gas chromatographic method for the determination of triazine herbicides in natural water samples

A multi-residue method is described for the determination o triazine herbicides in natural water samples. The technique uses solvent extraction followed by gas chromatographic separation and detection employing nitrogen-selective devices. Seven compounds can be determined simultaneously at a nominal detection limit of 0.1 μg/L in a 1-litre sample. Three different natural water samples were used for error analysis via evaluation of recovery efficiencies and estimation of overall method precision. As an alternative to liquid-liquid partition (solvent extraction) for removal of compounds of interest from water, solid-phase extraction (SPE) techniques employing chromatographic grade silicas with chemically modified surfaces have been examined. SPE is found to provide rapid and efficient concentration with quantitative recovery of some triazine herbicides from natural water samples. Concentration factors of 500 to 1000 times are obtained readily by the SPE technique.

International Journal of Environmental Analytical ↗

Urbanization influences on aquatic communities in northeastern Illinois streams

Biotic indices and sediment trace element concentrations for 43 streams in northeastern Illinois (Chicago area) from the 1980s and 1990s were examined along an agricultural to urban land cover gradient to explore the relations among biotic integrity, sediment chemistry, and urbanization. The Illinois fish Alternative Index of Biotic Integrity (AIBI) ranged from poor to excellent in agricultural/rural streams, but streams with more than 10 percent watershed urban land (about 500 people/mi2) had fair or poor index scores. A macroinvertebrate index (MBI) showed similar trends. A qualitative habitat index (PIBI) did not correlate to either urban indicator. The AIBI and MBI correlated with urban associated sediment trace element concentrations. Elevated copper concentrations in sediment occurred in streams with greater than 40 percent watershed urban land. The number of intolerant fish species and modified index of biotic integrity scores increased in some rural, urbanizing, and urban streams from the 1980s to 1990s, with the largest increases occurring in rural streams with loamy/sandy surficial deposits. However, smaller increases also occurred in urban streams with clayey surficial deposits and over 50 percent watershed urban land. These data illustrate the potentially complex spatial and temporal relations among biotic integrity, sediment chemistry, watershed urban land, population density, and regional and local geologic setting.

Illinois↗

Transcriptomic effects-based monitoring for endocrine active chemicals: Assessing relative contribution of treated wastewater to downstream pollution

The present study investigated whether a combination of targeted analytical chemistry information with unsupervised, data-rich biological methodology (i.e., transcriptomics) could be utilized to evaluate relative contributions of wastewater treatment plant (WWTP) effluents to biological effects. The effects of WWTP effluents on fish exposed to ambient, receiving waters were studied at three locations with distinct WWTP and watershed characteristics. At each location, 4 d exposures of male fathead minnows to the WWTP effluent and upstream and downstream ambient waters were conducted. Transcriptomic analyses were performed on livers using 15 000 feature microarrays, followed by a canonical pathway and gene set enrichment analyses. Enrichment of gene sets indicative of teleost brain–pituitary–gonadal–hepatic (BPGH) axis function indicated that WWTPs serve as an important source of endocrine active chemicals (EACs) that affect the BPGH axis (e.g., cholesterol and steroid metabolism were altered). The results indicated that transcriptomics may even pinpoint pertinent adverse outcomes (i.e., liver vacuolization) and groups of chemicals that preselected chemical analytes may miss. Transcriptomic Effects-Based monitoring was capable of distinguishing sites, and it reflected chemical pollution gradients, thus holding promise for assessment of relative contributions of point sources to pollution and the efficacy of pollution remediation.

Environmental Science & Technology↗

Microbial transformations of arsenic in the environment: From soda lakes to aquifers

Arsenic is a highly toxic element that supports a surprising range of biogeochemical transformations. The biochemical basis of these microbial interactions is described, with an emphasis on energy-yielding redox biotransformations that cycle between the As5+ and As3+ oxidation states. The subsequent impact of As3+-oxidising and As 5+-reducing prokaryotes on the chemistry of selected environments is also described, focusing on soda lakes with naturally high concentrations of the metalloid and on Southeast Asian aquifer sediments, where the microbial reduction of sorbed As5+ and subsequent mobilisation of As 3+ into water abstracted for drinking and irrigation threaten the lives of millions.

Elements↗

Acidic Depositions: Effects on Wildlife and Habitats

The phenomenon of 'acid rain' is not new; it was recognized in the mid-1800s in industrialized Europe. In the 1960s a synthesis of information about acidification began in Europe, along with predictions of ecological effects. In the U.S. studies of acidification began in the 1920s. By the late 1970s research efforts in the U.S. and Canada were better coordinated and in 1980 a 10-year research program was undertaken through the National Acid Precipitation Assessment Plan (NAPAP) to determine the causes and consequences of acidic depositions. Much of the bedrock in the northeastern U.S. and Canada contains total alkalinity of <200 ?eq 1-1, thus, it lacks acid-neutralizing capacity. In the U.S. about 5% of the land area and in Canada about 43 % of the land area is sensitive to acidic depositions. Further, these areas receive >20 kg/ha/yr of wet sulphate depositions and are vulnerable to acidifying processes. Acidic depositions contribute directly to acidifying processes of soil and soil water. Soils must have sufficient acid-neutralizing capacity or acidity of soil will increase. Natural soil-forming processes that lead to acidification can be accelerated by acidic depositions. Long-term effects of acidification are predicted, which will reduce soil productivity mainly through reduced availability of nutrients and mobilization of toxic metals. Severe effects may lead to major alteration of soil chemistry, soil biota, and even loss of vegetation. Several species of earthworms and several other taxa of soil-inhabiting invertebrates, which are important food of many vertebrate wildlife species, are affected by low pH in soil. Loss of canopy in declining sugar maples results in loss of insects fed on by certain neotropical migrant bird species. No definitive studies categorically link atmospheric acidic depositions with direct or indirect effects on wild mammals. Researchers have concentrated on vegetative and aquatic effects. Circumstantial evidence suggests that effects are probable for certain species of aquatic-dependent mammals (water shrew, mink, and otter) and that these species are at risk from the loss of foods or contamination of these foods by metals, especially methylmercury. Continued acidification of terrestrial habitats, to the extent that earthworm populations are broadly reduced, might expose some fossorial mammalian species to risk because of decline in their major prey species. Acidic deposition affects primarily aquatic habitats of avian species by disrupting food webs (ecological effects) and increasing amounts of available heavy metals (mercury, aluminum, cadmium) in prey of avian species (toxicological effects). The ecological effects of acidifying wetlands are to reduce acid-intolerant prey (invertebrates) and to change prey quality from high-calcium bearing prey to low-calcium bearing prey. The toxicological effects are to increase contamination by heavy metals, especially methylated mercury, in foods of breeding waterbirds. The combination of these 2 types of effects results in potentially lower survival of adults and reduced production, growth, or survival of young of many bird species. Effects of acidification on herpteofauna and their habitats are mainly reproductive failure of susceptible species and reduced or metal-contaminated foods for both amphibians and reptiles.

Wildlife Society Technical Review↗

Petrophysical analysis of geophysical logs of the National Drilling Company-U.S. Geological Survey ground-water research project for Abu Dhabi Emirate, United Arab Emirates

A program of borehole-geophysical logging was implemented to supply geologic and geohydrologic information for a regional ground-water investigation of Abu Dhabi Emirate. Analysis of geophysical logs was essential to provide information on geohydrologic properties because drill cuttings were not always adequate to define lithologic boundaries. The standard suite of logs obtained at most project test holes consisted of caliper, spontaneous potential, gamma ray, dual induction, microresistivity, compensated neutron, compensated density, and compensated sonic. Ophiolitic detritus from the nearby Oman Mountains has unusual petrophysical properties that complicated the interpretation of geophysical logs. The density of coarse ophiolitic detritus is typically greater than 3.0 grams per cubic centimeter, porosity values are large, often exceeding 45 percent, and the clay fraction included unusual clays, such as lizardite. Neither the spontaneous-potential log nor the natural gamma-ray log were useable clay indicators. Because intrinsic permeability is a function of clay content, additional research in determining clay content was critical. A research program of geophysical logging was conducted to determine the petrophysical properties of the shallow subsurface formations. The logging included spectral-gamma and thermal-decay-time logs. These logs, along with the standard geophysical logs, were correlated to mineralogy and whole-rock chemistry as determined from sidewall cores. Thus, interpretation of lithology and fluids was accomplished. Permeability and specific yield were calculated from geophysical-log data and correlated to results from an aquifer test. On the basis of results from the research logging, a method of lithologic and water-resistivity interpretation was developed for the test holes at which the standard suite of logs were obtained. In addition, a computer program was developed to assist in the analysis of log data. Geohydrologic properties were estimated, including volume of clay matrix, volume of matrix other than clay, density of matrix other than clay, density of matrix, intrinsic permeability, specific yield, and specific storage. Geophysical logs were used to (1) determine lithology, (2) correlate lithologic and permeable zones, (3) calibrate seismic reprocessing, (4) calibrate transient-electromagnetic surveys, and (5) calibrate uphole-survey interpretations. Logs were used at the drill site to (1) determine permeability zones, (2) determine dissolved-solids content, which is a function of water resistivity, and (3) design wells accordingly. Data and properties derived from logs were used to determine transmissivity and specific yield of aquifer materials.

Water Supply Paper↗

Mineralogy and environmental geochemistry of historical iron slag, Hopewell Furnace National Historic Site, Pennsylvania, USA

The Hopewell Furnace National Historic Site in southeastern Pennsylvania, which features an Fe smelter that was operational in the 18th and 19th centuries, is dominated by three slag piles. Pile 1 slag, from the Hopewell Furnace, and pile 2 slag, likely from the nearby Cornwall Furnace, were both produced in cold-blast charcoal-fired smelters. In contrast, pile 3 slag was produced in an anthracite furnace. Ore samples from the nearby Jones and Hopewell mines that fed the smelter are mainly magnetite-rich with some sulfides (pyrite, chalcopyrite, sphalerite) and accessory silicates (quartz, garnet, feldspar, and clay minerals). Slag piles 1 and 2 are similar mineralogically containing predominantly skeletal and dendritic aluminian diopside and augite, skeletal forsteritic olivine, glass, rounded blebs of metallic Fe, and exotic quartz. Olivine is a major phase in all samples from pile 2, whereas it occurs in only a few samples from pile 1. Samples of the <2 mm-size fraction of surface composite slag material or crushed slag from at depth in piles 1 and 2 are mineralogically similar to the large surface slag fragments from those piles with the addition of phases such as feldspars, Fe oxides, and clay minerals that are either secondary weathering products or entrained from the underlying bedrock. Pile 3 slag contains mostly skeletal forsteritic olivine and Ti-bearing aluminian diopside, dendritic or fine-grained subhedral melilite, glass, euhedral spinel, metallic Fe, alabandite–oldhamite solid solution, as well as a sparse Ti carbonitride phase. The bulk chemistry of the slag is dominated by Al 2 O 3 (8.5–16.2 wt.%), CaO (8.2–26.2 wt.%), MgO (4.2–24.7 wt.%), and SiO 2 (36.4–59.8 wt.%), constituting between 81% and 97% of the mass of the samples. Piles 1 and 2 are chemically similar; pile 1 slag overall contains the highest Fe 2 O 3 , K 2 O and MnO, and the lowest MgO concentrations. Pile 3 slag is high in Al 2 O 3 , CaO and S, and low in Fe 2 O 3 , K 2 O and SiO 2 compared to the other piles. In general, piles 1 and 2 are chemically similar to each other, whereas pile 3 is distinct – a conclusion that reflects their mineralogy. The similarities and differences among piles in terms of mineralogy and major element chemistry result from the different smelting conditions under which the slag formed and include the fuel source, the composition of the ore and flux, the type of blast (cold versus hot), which affects the furnace temperature, and other beneficiation methods. The three distinct slag piles at Hopewell are enriched in numerous trace elements, such as As (up to 12 mg/kg), Cd (up to 0.4 mg/kg), Co (up to 31.8 mg/kg), Cu (up to 647 mg/kg), Mn (up to 0.69 wt.%), Pb (up to 172 mg/kg) and Zn (up to 393 mg/kg), together with Fe (13.9 wt.%), when compared to the average for the continental crust, with the <2 mm-size fraction commonly containing the highest concentrations. Enrichments in various elements (e.g., Cd, Co, Cu, Pb, Zn) were also found in the ore samples. Despite these enrichments, comparison of bulk chemistry trace-element concentrations to the environmental guidelines suggests most elements are likely not problematic with the exception of As, Co, Fe and Mn. Leachate tests that simulate weathering indicate Fe (up to 973 μg/L) and Mn (up to 133 μg/L) are readily released in potentially harmful concentrations compared to secondary drinking water and some aquatic ecosystem toxicity criteria. Aluminum and Cu, although not high in the solid compared to environmental guidelines, also exceed relevant criteria in leachate extracts with maximum concentrations of 2700 μg/L and 17.7 μg/L, respectively. In contrast, As and Co, which are significant in the solids, are not leached in concentrations that exceed guidelines (i.e., 3 μg/L or less for both elements). The weathering rates of the Fe metal and Fe oxides, which host Cu and some Fe, are likely higher than the silicate glass, which hosts the majority of Al, Mn and some Fe, and the crystalline silicates and spinels affecting which elements and how much are released into the environment and surrounding aquatic ecosystem. The mineral assemblages and their chemical composition, the bulk sample chemistry, and leachability of trace elements are all important components in understanding the potential environmental impacts of the slag piles.

Pennsylvania↗

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