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USGS2003

Geochemistry of the furnace magnetite bed, Franklin, New Jersey, and the relationship between stratiform iron oxide ores and stratiform zinc oxide-silicate ores in the New Jersey highlands

The New Jersey Highlands terrace, which is an exposure of the Middle Proterozoic Grenville orogenic belt located in northeastern United States, contains stratiform zinc oxide-silicate deposits at Franklin and Sterling Hill and numerous massive magnetite deposits. The origins of the zinc and magnetite deposits have rarely been considered together, but a genetic link is suggested by the occurrence of the Furnace magnetite bed and small magnetite lenses immediately beneath the Franklin zinc deposit. The Furnace bed was metamorphosed and deformed along with its enclosing rocks during the Grenvillian orogeny, obscuring the original mineralogy and obliterating the original rock fabrics. The present mineralogy is manganiferous magnetite plus calcite. Trace hydrous silicates, some coexisting with fluorite, have fluorine contents that are among the highest ever observed in natural assemblages. Furnace bed calcite has ??13C values of -5 ?? 1 per mil relative to Peedee belemnite (PDB) and ??18O values of 11 to 20 per mil relative to Vienna-standard mean ocean water (VSMOW). The isotopic compositions do not vary as expected for an original siderite layer that decarbonated during metamorphism, but they are consistent with nearly isochemical metamorphism of an iron oxide + calcite protolith that is chemically and minerlogically similar to iron-rich sediments found near the Red Sea brine pools and isotopically similar to Superior-type banded iron formations. Other magniferous magnite + calcite bodies occur at approximately the same stratigraphic position as far 50 km from the zinc deposits. A model is presented in which the iron and zinc deposits formed along the western edge of a Middle Proterozoic marine basin. Zinc was transported by sulfate-stable brines and was precipitated under sulfate-stable conditions as zincian carbonates and Fe-Mn-Zn oxides and silicates. Whether the zincian assemblages settled from the water column or formed by replacement reactions in shallowly buried sediments is uncertain. The iron deposits formed at interfaces between anoxic and oxygenated waters. The Furnace magnetite bed resulted from seawater oxidation of hydrothermally transported iron near a brine conduit. Iron deposits also formed regionally on the basin floor at the interface betveen anoxic deep waters and oxygenated shallower waters. These deposits include not only manganiferous magnetite + calcite bodies similar to the Furnace magnetite bed but also silicate-facies deposits that formed by iron oxide accumulation where detrital sediment was abundant. A basin margin model can be extended to Grenvillian stratiform deposits in the northwest Adirondacks of New York and the Mont Laurier basin of Quebec. In these areas iron deposits (pyrite or magnetite) are found basinward of marble-hosted sphalerite deposits, such as those in the Balmat-Edwards district. Whether the iron and zinc precipitated as sulfide assemblages or carbonate-oxide-silicate assemblages depended on whether sufficient organic matter or other reductants were available in local sediments or bottom waters to stabilize H2S.

New Jersey↗

USGS1979

Subsurface stratigraphy and geochemistry of late Quaternary evaporites, Searles Lake, California, with a section on radiocarbon ages of stratigraphic units

Searles Lake is a dry salt pan, about 100 km 2 in area, that lies on the floor of Searles Valley, in the desert of southeast California. Several salt bodies of late Quaternary age lie beneath the surface, mostly composed of sodium and potassium carbonate, sulfate, chloride, and borate minerals. Mud layers separate the salt bodies, which contain interstitial brine that is the source of large quantities of industrial chemicals. The value of annual production from the deposit exceeds $30 million; total production to date exceeds $1 billion. The salts and muds were deposited during Pleistocene and Holocene times by a series of large lakes (200 m maximum depth, 1,000 km 2 maximum area) that fluctuated in size in response to climatic change. Salts were deposited during major dry (interpluvial) episodes, muds during wet (pluvial) episodes that correlate with glacial advances in other parts of North America and the world. Data based on cores from the deposit are used in this paper to establish the stratigraphy of the deposit, the chemical and mineral compositions of successive units, and the total quantities of components contained by them. These parameters are then used to determine the geochemical evolution of the sedimentary layers. The results provide a refined basis for reconstructing the limnology of Searles Lake and the regional climate during late Quaternary time. Six main stratigraphic units were distinguished and informally named earlier on the basis of their dominant composition: Unit Typical thickness 14C age, uncorrected (in meters) (years B.P.) Overburden Mud 7 0 to >3,500 Upper Salt 15 >3,500 to 10,500 Parting Mud 4 10,500 to 24,000 Lower Salt 12 24,000 to 32,500 Bottom Mud 30 32,500 to 130,000 Mixed Layer 200+ > 130,000 (The age of 130,000 years for the Mixed Layer is based on extrapolated sedimentation rates.) The Lower Salt is subdivided into seven salt units (S-l to S-7) and six mud units (M-2 to M-7), the Mixed Layer into six units (A to F). For each salt unit, the areal extent, volume, shape, mineralogy, and chemical composition of the solids and brines have been determined; for each mud unit (which originally extended over much of the basin), the shape and volume within a standard area, and the mineralogy, have been determined. The bulk compositions (brines plus salts) of the combined Lower Salt units S-l to S-5 and units S-6 and S-7, and the Upper Salt, were determined so that the total quantities and ratios of ions in the initial brines could be reconstructed. The 74 published HC dates on Searles Lake core samples from all but the oldest unit are supplemented by 14 new dates (determined by Minze Stuiver) on the Lower Salt. Most of the age control comes from dates based on disseminated organic carbon; two dates are on wood; dates on carbonate minerals are less reliable. Although the probable disequilibrium between the carbon in the lake and atmosphere (because of contamination, slow equilibrium rates, and other factors) causes disseminated carbon dates to be an estimated 500-2,500 years 'too old,' the ages of the major and minor units are relatively well established. The list above indicates rounded and uncorrected ages for the contacts of major units. The age of the only salt bed in the Lower Salt which indicates desiccation (S-5) is about 28,000 years. The average uncorrected sedimentation rate in the Parting Mud is 4

Professional Paper↗

USGS1989

Geochemistry of the Floridan aquifer system in Florida and in parts of Georgia, South Carolina, and Alabama

The chemical quality of the ground water in the Floridan aquifer system is determined primarily by mineral-water interaction. However, some changes in water quality have been imposed by development, particularly near coastal pumping centers. A total of 601 chemical analyses, all from different wells, most completed in the upper part of the aquifer system, were used to describe the variations in water chemistry and to study the processes responsible for observed changes. The Floridan aquifer system is a vertically continuous sequence of Tertiary carbonate rocks that are of generally high permeability and are hydraulically connected in varying degrees. The rocks are principally limestone and dolomite, but they grade into limy sands and clays near the aquifer system's updip limits. Major minerals in the aquifer system are calcite, dolomite, and, locally, gypsum or quartz; minor minerals include apatite, glauconite, and clay minerals such as kaolinite and montmorillonite. Trace amounts of metallic oxides or sulfides are present in some areas. The aquifer system consists of the Upper and Lower Floridan aquifers, separated in most places by a less permeable confining unit that has highly variable hydraulic properties. Only the Upper Floridan aquifer is present throughout the study area. Freshwater enters the aquifer system in outcrop areas located primarily in central Georgia and north-central Florida. Discharge occurs chiefly to streams and springs and, to a lesser extent, directly into the sea. Most of the flow into and out of the system takes place where it is unconfined or where the upper confining unit is thin. Secondary permeability developed by dissolution of aquifer material is most prominent in these areas of dynamic flow. Dissolved-solids concentrations in water from the Upper Floridan aquifer generally range from less than 25 milligrams per liter near outcrops to more than 25,000 milligrams per liter along the coasts. The dominant cations in the ground water are Ca2+, Mg2+, and Na+; the dominant anions are HCO3-, Cl-, and SO42-, The concentration of Ca2+ is controlled primarily by calcite saturation. Concentrations of Mg2+, NA+, and Cl- are highest where mixing of freshwater and saltwater occurs. Concentrations of HCO3- reflect the control of calcite solubility. The concentration of SO42- is highest where gypsiferous rock units are present in the aquifer system. The major geochemical processes that occur in the Upper Floridan aquifer, based on water-quality maps and computations using a geochemical model, are (1) dissolution of aquifer minerals toward equilibrium, (2) mixing of ground water with recharge, leakage, or seawater, (3) sulfate reduction, and (4) cation exchange between water and aquifer minerals. Similar processes apparently control minor dissolved constituents, although quantification is difficult with the available data. Statistical tests of available nutrient data indicate that concentrations of N (nitrogen) species in unconfined recharge areas may be increasing over time; more detailed studies of all N species are needed to test this hypothesis, however. Data on trace metals, radionuclides, and man-made organic contaminants are limited. Available data indicate that most freshwater within the Upper Floridan is potable, but detection of pesticides in a few samples indicates that the system is susceptible to contamination from the land surface in some areas, particularly where its upper confining unit is thin or absent. Geochemical models were used to examine changes in major chemical elements along selected ground-water paths within the Upper Floridan aquifer. Water in the Upper Floridan aquifer can be categorized into four hydrochemical facies, whose exact distribution is determined by confined or unconfined conditions of the aquifer and by chloride concentrations. The reaction models are considered plausible based on available chemical, isotopic, and hydrologic information, and they

Alabama, Florida, Georgia, South Carolina↗

USGS2014

Mercury concentrations and distribution in soil, water, mine waste leachates, and air in and around mercury mines in the Big Bend region, Texas, USA

Samples of soil, water, mine waste leachates, soil gas, and air were collected from areas mined for mercury (Hg) and baseline sites in the Big Bend area, Texas, to evaluate potential Hg contamination in the region. Soil samples collected within 300 m of an inactive Hg mine contained elevated Hg concentrations (3.8–11 µg/g), which were considerably higher than Hg in soil collected from baseline sites (0.03–0.05 µg/g) distal (as much as 24 km) from mines. Only three soil samples collected within 300 m of the mine exceeded the probable effect concentration for Hg of 1.06 µg/g, above which harmful effects are likely to be observed in sediment-dwelling organisms. Concentrations of Hg in mine water runoff (7.9–14 ng/L) were generally higher than those found in springs and wells (0.05–3.1 ng/L), baseline streams (1.1–9.7 ng/L), and sources of drinking water (0.63–9.1 ng/L) collected in the Big Bend region. Concentrations of Hg in all water samples collected in this study were considerably below the 2,000 ng/L drinking water Hg guideline and the 770 ng/L guideline recommended by the U.S. Environmental Protection Agency (USEPA) to protect aquatic wildlife from chronic effects of Hg. Concentrations of Hg in water leachates obtained from leaching of mine wastes varied widely from <0.001 to 760 µg of Hg in leachate/g of sample leached, but only one leachate exceeded the USEPA Hg industrial soil screening level of 31 µg/g. Concentrations of Hg in soil gas collected at mined sites (690–82,000 ng/m 3 ) were highly elevated compared to soil gas collected from baseline sites (1.2–77 ng/m 3 ). However, air collected from mined areas at a height of 2 m above the ground surface contained concentrations of Hg (4.9–64 ng/m 3 ) that were considerably lower than Hg in soil gas from the mined areas. Although concentrations of Hg emitted from mine-contaminated soils and mine wastes were elevated, persistent wind in southwest Texas disperses Hg in the air within a few meters of the ground surface.

Texas↗

USGS2021

Interactive PHREEQ-N-AMDTreat water-quality modeling tools to evaluate performance and design of treatment systems for acid mine drainage

The PHREEQ-N-AMDTreat aqueous geochemical modeling tools described herein simulate changes in pH and solute concentrations resulting from passive and active treatment of acidic or alkaline mine drainage (AMD). The “user-friendly” interactive tools, which are publicly available software, utilize PHREEQC equilibrium aqueous and surface speciation models and kinetics models for O 2 ingassing and CO 2 outgassing, iron and manganese oxidation and precipitation, limestone dissolution, and organic carbon oxidation combined with reduction of nitrate, sulfate, and ferric iron. Reactions with synthetic caustic chemicals (CaO, Ca(OH) 2 , NaOH, Na 2 CO 3 ) or oxidizing agents (H 2 O 2 ) also may be simulated separately or combined with sequential kinetic steps. A user interface facilitates input of water chemistry data for one or two (mixed) influent AMD solutions and adjustment of kinetic variables. Graphical and tabular output indicates the changes in pH, metals and other solute concentrations, total dissolved solids, and specific conductance of treated effluent plus the cumulative quantity of precipitated solids as a function of retention time or the amount of caustic agent added. By adjusting kinetic variables or chemical dosing, the effects of independent or sequential treatment steps that have different retention time (volume/flow rate), aeration rate, quantities of reactive solids, and temperature can be simulated for the specified influent quality. The size (land area) of a treatment system can then be estimated using reaction time estimates (volume for a corresponding treatment step is the product of reaction time and flow rate; area is volume divided by depth). Given the estimated system size, the AMDTreat cost-analysis model may be used to compute approximate costs for installation (capital) and annual operations and maintenance. Thus, various passive and/or active treatment strategies can be identified that could potentially achieve the desired effluent quality, but require different land area, equipment, and costs for construction and operation.

Applied Geochemistry↗

USGS1986

Uranium series disequilibrium in a young surficial uranium deposit, northeastern Washington, U.S.A.

A recently discovered ore-grade accumulation of U in organic-rich sediments of late Quaternary age provides an opportunity for studying the early association of U, U-daughters, and organic matter in a natural setting. The U occurs in valley-fill sediments of peat, peaty clay, silt, and sand along the north fork of Flodelle Creek, Stevens County, Washington. Radiometric techniques (delayed neutron, high-resolution gamma-ray spectrometry, thin-source alpha spectrometry) were employed to determine the abundance and distribution of U-series nuclides, the extent of secular equilibrium within the U decay series, and the apparent U-series ages of U incorporation. Sixteen lithologically distinct intervals were sampled from a 292 cm core. Uranium contents range from 140 to 2790 ppm and are positively correlated with organic contents. Measured alpha activity ratios of 234 U/ 238 U (1.31–1.38) are very similar to those reported in coexisting waters, suggesting a rather constant isotopic composition of introduced U. Much lower Th contents of <10–40 ppm are controlled by the type and abundance of silicate detritus. The youth of the host sediments (<15 000 a) and the paucity of associated radioactivity suggested large excesses of U relative to radioactive daughters and such excesses were observed, particularly in the shallowest intervals. Apparent ages of U emplacement determined by the (alpha) activity ratio of 230 Th daughter to 234 U parent show a general increase with depth and fair agreement with estimated depositional ages. This observation suggests dominantly syndepositional or early post depositional emplacement of U followed by decay-generated buildup of 230 Th daughter with time. However, interval by interval comparisons of the relative abundances of other daughters, particularly 226 Ra and 210 Pb, indicate variability caused by processes other than closed-system growth and decay, probably because chemically diverse daughters that are decay-generated in situ have differing mobilities and because upwelling ground water continuously adds more U and minor amounts of daughters. If 230 Th is considered the least susceptible to these modifications, the data suggest some addition of 234 U in the deepest intervals and some loss of 226 Ra and/or gain of 222 Rn throughout the studied core.

Washington↗

USGS2017

Fidelity of the Sr/Ca proxy in recording ocean temperature in the western Atlantic coral Siderastrea siderea

Massive corals provide a useful archive of environmental variability, but careful testing of geochemical proxies in corals is necessary to validate the relationship between each proxy and environmental parameter throughout the full range of conditions experienced by the recording organisms. Here we use samples from a coral-growth study to test the hypothesis that Sr/Ca in the coral Siderastrea siderea accurately records sea-surface temperature (SST) in the subtropics (Florida, USA) along 350 km of reef tract. We test calcification rate, measured via buoyant weight, and linear extension (LE) rate, estimated with Alizarin Red-S staining, as predictors of variance in the Sr/Ca records of 39 individual S. siderea corals grown at four outer-reef locations next to in-situ temperature loggers during two, year-long periods. We found that corals with calcification rates < 1.7 mg cm −2 d −1 or < 1.7 mm yr −1 LE returned spuriously high Sr/Ca values, leading to a cold-bias in Sr/Ca-based SST estimates. The threshold-type response curves suggest that extension rate can be used as a quality-control indicator during sample and drill-path selection when using long cores for SST paleoreconstruction. For our corals that passed this quality control step, the Sr/Ca-SST proxy performed well in estimating mean annual temperature across three sites spanning 350 km of the Florida reef tract. However, there was some evidence that extreme temperature stress in 2010 (cold snap) and 2011 (SST above coral-bleaching threshold) may have caused the corals not to record the temperature extremes. Known stress events could be avoided during modern calibrations of paleoproxies.

Geochemistry, Geophysics, Geosystems↗

USGS2022

Characterization of arsenic species in microbial mats from an inactive gold mine

Filamentous cyanobacterial mats and Fe oxyhydroxide-rich bacterial mats collected near an inactive gold mine in California are enriched in arsenic (As) approximately 1000-fold relative to the waters in contact with them. The predominant organism in the cyanobacterial mat could not be identified using morphological characteristics, but the unique morphology of the sheath-forming β protobacterium Leptothrix ochracea was used to identify this species in Fe oxyhydroxide mat samples from several sites near the gold mine. Leptothrix sheaths commonly exceed 10 μm in length and have an average diameter of 1 μm . The Fe-oxyhydroxide mats are dominated by L. ochracea sheaths, but use of fluorescently tagged genetic stains reveals the presence of sheathless bacteria that presumably also promote the formation of Fe oxyhydroxide. X-ray absorption fine structure (XAFS) spectroscopy was used to identify As species in these microbial mats. Mat-associated As is predominantly As(V), even when As(III) is the primary dissolved species in contact with the mats. The species of As(V) associated with the cyanobacterial mat could not be conclusively identified; however, it is not associated with Fe oxyhydroxide or other minerals, based on comparison to XAFS spectra of As adsorbed to various substrates. In addition, the cyanobacterial mat XAFS spectrum is different from that of aqueous As(V), suggesting that As(V) in the mat lacks some or all of the coordinating water molecules present in aqueous solution. We hypothesize that As is associated with the exopolysaccharide (EPS) matrix secreted by the cyanobacteria. In Leptothrix -dominated Fe-oxyhydroxide bacterial mats, XAFS analysis clearly indicates that As(V) is associated with the Fe oxyhydroxide as an adsorbed and/or coprecipitated complex.

California↗

USGS2008

Dissolved metals and associated constituents in abandoned coal-mine discharges, Pennsylvania, USA. Part 1: Constituent quantities and correlations

Complete hydrochemical data are rarely reported for coal-mine discharges (CMD). This report summarizes major and trace-element concentrations and loadings for CMD at 140 abandoned mines in the Anthracite and Bituminous Coalfields of Pennsylvania. Clean-sampling and low-level analytical methods were used in 1999 to collect data that could be useful to determine potential environmental effects, remediation strategies, and quantities of valuable constituents. A subset of 10 sites was resampled in 2003 to analyze both the CMD and associated ochreous precipitates; the hydrochemical data were similar in 2003 and 1999. In 1999, the flow at the 140 CMD sites ranged from 0.028 to 2210 L s-1, with a median of 18.4 L s-1. The pH ranged from 2.7 to 7.3; concentrations (range in mg/L) of dissolved (0.45-??m pore-size filter) SO4 (34-2000), Fe (0.046-512), Mn (0.019-74), and Al (0.007-108) varied widely. Predominant metalloid elements were Si (2.7-31.3 mg L-1), B (<1-260 ??g L-1), Ge (<0.01-0.57 ??g L-1), and As (<0.03-64 ??g L-1). The most abundant trace metals, in order of median concentrations (range in ??g/L), were Zn (0.6-10,000), Ni (2.6-3200), Co (0.27-3100), Ti (0.65-28), Cu (0.4-190), Cr (<0.5-72), Pb (<0.05-11) and Cd (<0.01-16). Gold was detected at concentrations greater than 0.0005 ??g L-1 in 97% of the samples, with a maximum of 0.0175 ??g L-1. No samples had detectable concentrations of Hg, Os or Pt, and less than half of the samples had detectable Pd, Ag, Ru, Ta, Nb, Re or Sn. Predominant rare-earth elements, in order of median concentrations (range in ??g/L), were Y (0.11-530), Ce (0.01-370), Sc (1.0-36), Nd (0.006-260), La (0.005-140), Gd (0.005-110), Dy (0.002-99) and Sm (<0.005-79). Although dissolved Fe was not correlated with pH, concentrations of Al, Mn, most trace metals, and rare earths were negatively correlated with pH, consistent with solubility or sorption controls. In contrast, As was positively correlated with pH. None of the 140 CMD samples met all US Environmental Protection Agency (USEPA) continuous-concentration criteria for protection of freshwater aquatic organisms; the samples exceeded criteria for Al, Fe, Co, Ni, and/or Zn. Ten percent of the samples exceeded USEPA primary drinking-water standards for As, and 33% exceeded standards for Be. Only one sample met drinking-water standards for inorganic constituents in a public water supply. Except for S, the nonmetal elements (S > C > P = N = Se) were not elevated in the CMD samples compared to average river water or seawater. Compared to seawater, the CMD samples also were poor in halogens (Cl > Br > I > F), alkalies (Na > K > Li > Rb > Cs), most alkaline earths (Ca > Mg > Sr), and most metalloids but were enriched by two to four orders of magnitude with Fe, Al, Mn, Co, Be, Sc, Y and the lanthanide rare-earth elements, and one order of magnitude with Ni and Zn. The ochre samples collected at a subset of 10 sites in 2003 were dominantly goethite with minor ferrihydrite or lepidocrocite. None of the samples for this subset contained schwertmannite or was Al rich, but most contained minor aluminosilicate detritus. Compared to concentrations in global average shale, the ochres were rich in Fe, Ag, As and Au, but were poor in most other metals and rare earths. The ochres were not enriched compared to commercial ore deposits mined for Au or other valuable metals. Although similar to commercial Fe ores in composition, the ochres are dispersed and present in relatively small quantities at most sites. Nevertheless, the ochres could be valuable for use as pigment.

Applied Geochemistry↗

USGS2006

Mercury in coal and the impact of coal quality on mercury emissions from combustion systems

The proportion of Hg in coal feedstock that is emitted by stack gases of utility power stations is a complex function of coal chemistry and properties, combustion conditions, and the positioning and type of air pollution control devices employed. Mercury in bituminous coal is found primarily within Fe-sulfides, whereas lower rank coal tends to have a greater proportion of organic-bound Hg. Preparation of bituminous coal to reduce S generally reduces input Hg relative to in-ground concentrations, but the amount of this reduction varies according to the fraction of Hg in sulfides and the efficiency of sulfide removal. The mode of occurrence of Hg in coal does not directly affect the speciation of Hg in the combustion flue gas. However, other constituents in the coal, notably Cl and S, and the combustion characteristics of the coal, influence the species of Hg that are formed in the flue gas and enter air pollution control devices. The formation of gaseous oxidized Hg or particulate-bound Hg occurs post-combustion; these forms of Hg can be in part captured in the air pollution control devices that exist on coal-fired boilers, without modification. For a given coal type, the capture efficiency of Hg by pollution control systems varies according to type of device and the conditions of its deployment. For bituminous coal, on average, more than 60% of Hg in flue gas is captured by fabric filter (FF) and flue-gas desulfurization (FGD) systems. Key variables affecting performance for Hg control include Cl and S content of the coal, the positioning (hot side vs. cold side) of the system, and the amount of unburned C in coal ash. Knowledge of coal quality parameters and their effect on the performance of air pollution control devices allows optimization of Hg capture co-benefit.

Applied Geochemistry↗

USGS2014

Contaminants from Cretaceous black shale: I. Natural weathering processes controlling contaminant cycling in Mancos Shale, southwestern United States, with emphasis on salinity and selenium

Soils derived from black shale can accumulate high concentrations of elements of environmental concern, especially in regions with semiarid to arid climates. One such region is the Colorado River basin in the southwestern United States where contaminants pose a threat to agriculture, municipal water supplies, endangered aquatic species, and water-quality commitments to Mexico. Exposures of Cretaceous Mancos Shale (MS) in the upper basin are a major contributor of salinity and selenium in the Colorado River. Here, we examine the roles of geology, climate, and alluviation on contaminant cycling (emphasis on salinity and Se) during weathering of MS in a Colorado River tributary watershed. Stage I (incipient weathering) began perhaps as long ago as 20 ka when lowering of groundwater resulted in oxidation of pyrite and organic matter. This process formed gypsum and soluble organic matter that persist in the unsaturated, weathered shale today. Enrichment of Se observed in laterally persistent ferric oxide layers likely is due to selenite adsorption onto the oxides that formed during fluctuating redox conditions at the water table. Stage II weathering (pedogenesis) is marked by a significant decrease in bulk density and increase in porosity as shale disaggregates to soil. Rainfall dissolves calcite and thenardite (Na 2 SO 4 ) at the surface, infiltrates to about 1 m, and precipitates gypsum during evaporation. Gypsum formation (estimated 390 kg m −2 ) enriches soil moisture in Na and residual SO 4 . Transpiration of this moisture to the surface or exposure of subsurface soil (slumping) produces more thenardite. Most Se remains in the soil as selenite adsorbed to ferric oxides, however, some oxidizes to selenate and, during wetter conditions is transported with soil moisture to depths below 3 m. Coupled with little rainfall, relatively insoluble gypsum, and the translocation of soluble Se downward, MS landscapes will be a significant nonpoint source of salinity and Se to the Colorado River well into the future. Other trace elements weathering from MS that are often of environmental concern include U and Mo, which mimic Se in their behavior; As, Co, Cr, Cu, Ni, and Pb, which show little redistribution; and Cd, Sb, V, and Zn, which accumulate in Stage I shale, but are lost to varying degrees from upper soil intervals. None of these trace elements have been reported previously as contaminants in the study area.

Colorado↗

USGS2007

Composition of pore water in lake sediments, research site "B", Osage County, Oklahoma: Implications for lake water quality and benthic organisms

Shallow ground water at US Geological Survey research site B in northeastern Oklahoma is contaminated with NaCl-rich brine from past and present oil production operations. Contaminated ground water provides a potential source of salts, metals, and hydrocarbons to sediment and water of adjacent Skiatook Lake. A former brine storage pit 10 m in diameter that is now submerged just offshore from site B provides an additional source of contamination. Cores of the upper 16–40 cm of lake sediment were taken at the submerged brine pit, near an offshore saline seep, and at a location containing relatively uncontaminated lake sediment. Pore waters from each 2-cm interval were separated by centrifugation and analyzed for dissolved anions, cations, and trace elements. High concentrations of dissolved Cl − in pore waters (200–5000 mg/L) provide the most direct evidence of contamination, and contrast sharply with an average value of only about 37 mg/L in Skiatook Lake. Chloride/Br − mass ratios of 220–240 in contaminated pore waters are comparable to values in contaminated well waters collected onshore. Dissolved concentrations of Se, Pb, Cu and Ni in Cl − -rich pore waters exceed current US Environmental Protection Agency criteria for probable toxicity to aquatic life. At the submerged brine storage pit, the increase of Cl − concentration with depth is consistent with diffusion-dominant transport from deeper contaminated sediments. Near the offshore saline seep, pore water Cl − concentrations are consistently high and vary irregularly with depth, indicating probable Cl − transport by layer-directed advective flow. Estimated annual contributions of Cl − to the lake from the brine storage pit (∼20 kg) and the offshore seep (∼9 kg) can be applied to any number of similar sources. Generous estimates of the number of such sources at site B indicate minimal impact on water quality in the local inlet of Skiatook Lake. Similar methodologies can be applied at other sites of NaCl contamination surrounding Skiatook Lake and elsewhere.

Oklahoma↗

USGS1998

Hydrology and geochemistry of a slag-affected aquifer and chemical characteristics of slag-affected ground water, northwestern Indiana and northeastern Illinois

Slag is a by-product of steel manufacturing and a ubiquitous fill material in northwestern Indiana. Ground water associated with slag deposits generally is characterized by high pH and elevated concentrations of many inorganic water-quality constituents. The U.S. Geological Survey, in cooperation with the Indiana Department of Environmental Management, conducted a study in northwestern Indiana from June 1995 to September 1996 to improve understanding of the effects of slag deposits on the water quality of a glacial-outwash aquifer. The Bairstow Landfill, a slag-fill deposit overlying the Calumet aquifer near Hammond, Indiana, was studied to represent conditions in slag-deposit settings that are common in northwestern Indiana. Ground water from 10 observation wells, located in four nests at the site, and surface water from the adjacent Lake George were analyzed for values of field-measured parameters and concentrations of major ions, nutrients, trace elements, and bulk properties. Solid-phase samples of slag and aquifer sediment collected during drilling were examined with X-ray diffraction and geochemical digestion and analysis. Concentrations of calcium, potassium, sodium, and sulfate were highest in wells screened partly or fully in slag. Potassium concentrations in ground water ranged from 2.9 to 120 milligrams per liter (mg/L), were highest in water from slag deposits, and decreased with depth. The highest concentrations for aluminum, barium, molybdenum, nickel, and selenium were in water from the slag. Silica concentrations were highest in wells screened directly beneath the slag-aquifer interface, and magnesium concentrations were highest in intermediate and deep aquifer wells. Silica concentrations in shallow and intermediate aquifer wells ranged from 27 to 41 mg/L and were about 10 times greater than those in water from slag deposits. The highest concentrations for chromium, lead, and zinc were in ground water from immediately below the slag-aquifer interface. The solid-phase analyses indicated that calcite, dolomite, and quartz generally were present throughout the slag-aquifer system; barian celestite, cristobalite, manganese-bearing calcite, and minrecordite were present in fewer samples. Trace elements that are liberated from the slag may be incorporated as impurities during precipitation of major minerals, sorbed onto clays and other grainsize fractions not analyzed as part of this study, or present in low-abundance minerals that were not detected by the X-ray analysis. Mass-balance and speciation programs were used to identify geochemical processes that may be occurring as water infiltrates through the slag, flows into the aquifer, and discharges into Lake George. The geochemical models indicate that precipitation of calcite may be occurring where slag-affected water enters the aquifer. Models also indicate that dolomite precipitation and clay-mineral dissolution may be occurring at the slag-aquifer interface; however, dolomite precipitation is generally believed to require geologically long time periods. Silica may be dissolving where slag-affected ground water enters the aquifer and may be precipitating where slag-affected ground water discharges to the lakebed of Lake George. In addition to the site-specific study, a statistical analysis of regional water quality was done to compare ground water in wells affected and unaffected by slag. When com-pared to wells in background locations in the Calumet aquifer, wells screened in slag across northwestern Indiana and northeastern Illinois generally had relatively higher pH and specific-conductance values and relatively higher concentrations of alkalinity, dissolved solids, suspended solids, total organic carbon, calcium, potassium, sodium, chloride, aluminum, barium, and possibly magnesium, sulfate, chromium, cobalt, copper, cyanide, manganese, mercury, nickel, and vanadium. When compared to wells in slag and wells in background locations, ground water from immediately beneath or immediately downgradient from slag had relatively high concentrations of arsenic and silica. Water-quality characteristics in ground water at the Bairstow Landfill were similar to water-quality characteristics in slag-contact and slag-affected wells throughout northwestern Indiana.

Illinois, Indiana↗

USGS1998

Flow of river water into a Karstic limestone aquifer. 1. Tracing the young fraction in groundwater mixtures in the Upper Floridan Aquifer near Valdosta, Georgia

The quality of water in the Upper Floridan aquifer near Valdosta, Georgia is affected locally by discharge of Withlacoochee River water through sinkholes in the river bed. Data on transient tracers and other dissolved substances, including Cl − , 3 H, tritiogenic helium-3 ( 3 He), chlorofluorocarbons (CFC-11, CFC-12, CFC-113), organic C (DOC), O 2 (DO), H 2 S, CH 4 , δ 18 O, δD, and 14 C were investigated as tracers of Withlacoochee River water in the Upper Floridan aquifer. The concentrations of all tracers were affected by dilution and mixing. Dissolved Cl − , δ 18 O, δD, CFC-12, and the quantity ( 3 H+ 3 He) are stable in water from the Upper Floridan aquifer, whereas DOC, DO, H 2 S, CH 4 , 14 C, CFC-11, and CFC-113 are affected by microbial degradation and other geochemical processes occurring within the aquifer. Groundwater mixing fractions were determined by using dissolved Cl − and δ 18 O data, recognizing 3 end-member water types in the groundwater mixtures: (1) Withlacoochee River water (δ 18 O=−2.5±0.3‰, Cl − =12.2±2 mg/l), (2) regional infiltration water (δ 18 O=−4.2±0.1‰, Cl − =2.3±0.1 mg/l), and (3) regional paleowater resident in the Upper Floridan aquifer (δ 18 O=−3.4±0.1‰, Cl − =2.6±0.1 mg/l) (uncertainties are ±1σ). Error simulation procedures were used to define uncertainties in mixing fractions. Fractions of river water in groundwater range from 0 to 72% and average 10%. The influence of river-water discharge on the quality of water in the Upper Floridan aquifer was traced from the sinkhole area on the Withlacoochee River 25 km SE in the direction of regional groundwater flow. Infiltration of water is most significant to the N and NW of Valdosta, but becomes negligible to the S and SE in the direction of general thickening of post-Eocene confining beds overlying the Upper Floridan aquifer.

Georgia↗

USGS2021

Hydrogeologic framework, geochemistry, groundwater-flow system, and aquifer hydraulic properties used in the development of a conceptual model of the Ogallala, Edwards-Trinity (High Plains), and Dockum aquifers in and near Gaines, Terry, and Yoakum Counties, Texas

In 2014, the U.S. Geological Survey, in cooperation with Llano Estacado Underground Water Conservation District, Sandy Land Underground Water Conservation District, and South Plains Underground Water Conservation District (hereinafter referred to collectively as the “UWCDs”), began a multiphase study in and near Gaines, Terry, and Yoakum Counties, Texas, to develop a regional conceptual model of the hydrogeologic framework, geochemistry, groundwater-flow system, and hydraulic properties, primarily for the High Plains and Edwards-Trinity aquifer system and to a lesser degree for the Dockum aquifer. The High Plains aquifer system (hereinafter referred to as the “Ogallala aquifer”), contained within the Ogallala Formation in Texas, is the shallowest aquifer in the study area and is the primary source of water for agriculture and municipal supply in the areas managed by the UWCDs. Groundwater withdrawals from deeper aquifers (primarily the Edwards-Trinity [High Plains] aquifer system that is hereinafter referred to as the “Edwards-Trinity [High Plains] aquifer”) augmented by lesser amounts from the Dockum aquifer provide additional water sources in the study area. The Edwards-Trinity (High Plains) aquifer is contained within the Trinity and Fredericksburg Groups. The Dockum aquifer, a relatively minor source of water in the study area, is contained in the Dockum Group, which was evaluated as a single unit. The potential for continual declines of the groundwater in the Ogallala aquifer in the study area and the potential changes in water quality resulting from dewatering and increased vertical groundwater movement between adjacent water-bearing units have raised concerns about the amount and quality of available groundwater. The developed conceptual model helped in the understanding of the quantity and quality of the groundwater within the Ogallala, the Edwards-Trinity (High Plains), and to a lesser extent, the Dockum aquifers within the study area. The hydrogeologic framework was used to assess the vertical and lateral extents of hydrogeologic units, bed orientations, unit thicknesses, and location and orientation of paleochannels. In general, the Trinity and Fredericksburg Groups and Ogallala Formation exhibit a slight regional dip (dip angle of about 0.14 degrees) to the southeast with dip directions becoming more to the south with each successively overlying unit (105, 110, and 125 degrees for the bases of the Trinity and Fredericksburg Groups and Ogallala Formation, respectively). In general, the Trinity and Fredericksburg Groups thin to the south and are not present in the southern part of Gaines County, whereas the Ogallala Formation becomes thinner from west to east. The combined thickness of the Trinity and Fredericksburg Groups and Ogallala Formation is generally greatest in the north-central part of the study area and thinnest in the southeastern part of the study area. Paleochannel orientation varied over geologic time as formations were deposited and eroded. Water-quality samples were collected from 51 wells throughout the study area to better understand general water quality and to provide insight into groundwater-flow paths and recharge areas. Groundwater samples were spatially grouped on the basis of similarities found in the physicochemical properties, major ions, trace elements, nutrients, organic compounds, and selected stable isotopes and age tracers. Three groundwater groups were identified in the study area. The first groundwater group (Group 1), represented mostly by groundwater from the Ogallala and Edwards-Trinity (High Plains) aquifers in the northern half of the study area, is considered to be recent recharge, affected by land-use activities, as explained by the younger age, higher concentrations of nitrate plus nitrite, and more frequent detections of organic compounds. Groundwater wells in the second groundwater group (Group 2) are typically in the southwestern and northwestern parts of the study area, and the groundwater in this group is considered to be groundwater recharged during the Pleistocene period, as explained by the relatively old age of the groundwater, high strontium stable isotope ratios, and hydrogen and oxygen stable isotope ratios. The last groundwater group (Group 3) is likely a mixture of groundwater from the first or second groups (or both) with a third, highly mineralized groundwater as explained by having the highest dissolved-solids concentrations in the study area and having some similarities to geochemical characteristics of samples from the first and second groups. A groundwater-flow system analysis was done to understand the flow of groundwater throughout the aquifer system. Groundwater-level altitudes for the Ogallala, Edwards-Trinity (High Plains), and Dockum aquifers are generally higher in the northwestern part of the study area and lower in the southeastern part of the study area. Groundwater generally flows in a northwest to southeast direction across the study area in each of the aquifers. The groundwater-flow paths closely resemble the mapped paleochannels, indicating that within the study area, the groundwater flows preferentially along the paleochannels, especially within the Ogallala aquifer where dewatering of the aquifer results in a greater effect of the base structure on the flow of groundwater. The Ogallala aquifer is unsaturated in localized areas in the study area; unsaturated areas are generally near the southern extent of the Edwards-Trinity (High Plains) aquifer, with the largest unsaturated area west of Seminole, Tex. The saturated thickness of the Ogallala aquifer is thickest (more than 125 feet) southeast of Seminole and west of Brownfield, Tex., near the border between Terry and Yoakum Counties. The saturated thickness of the combined Ogallala and Edwards-Trinity (High Plains) aquifers ranges from less than 10 feet along the far southern edge of the study area to more than 350 feet north and east of Brownfield, Tex., and along the border between Terry and Yoakum Counties. The aquifer hydraulic properties, including hydraulic conductivity and specific yield, were estimated to better understand the ability of groundwater to move through the aquifer system and quantify the volume of available water in storage. The hydraulic-conductivity values varied greatly within the study area (ranging from about 0.03 to about 350 feet per day), and often large variations were found in the same area. Terry County contained the highest and lowest hydraulic conductivity values for the Ogallala aquifer, whereas Yoakum County contained the highest and lowest hydraulic conductivity values for the Edwards-Trinity (High Plains) aquifer. The highest hydraulic-conductivity values for the Dockum aquifer were in Gaines County, whereas the lowest hydraulic-conductivity values were in Terry County. The estimated specific yield values within the study area range from 0.01 to 0.36. Higher specific yield values generally occurred in the western part of the study area except in the Ogallala aquifer where higher specific yield values were in the east. The Ogallala aquifer had the lowest specific yield range and the least specific yield variability among the three aquifers, whereas the Dockum aquifer had the highest specific yield range and the greatest specific yield variability. Using the estimated saturated thickness and estimated specific yield grids, the water volumes of the Ogallala and Edwards-Trinity (High Plains) aquifers and the combined Ogallala and Edwards-Trinity (High Plains) aquifers were estimated. The available water in the Edwards-Trinity (High Plains) aquifer (16.6 million acre-feet) is almost double the available water in the Ogallala aquifer (8.8 million acre-feet). Although the Edwards-Trinity (High Plains) aquifer contains more available groundwater, pumping is more difficult because of the relatively low hydraulic conductivity and specific yield values compared to the Ogallala aquifer. Overall, the available water within the combined Ogallala and Edwards-Trinity (High Plains) aquifers is about 6.6, 10.2, and 8.6 million acre-feet for Gaines, Terry, and Yoakum Counties, respectively.

Texas↗

USGS2013

Long-distance transport of Hg, Sb, and As from a mined area, conversion of Hg to methyl-Hg, and uptake of Hg by fish on the Tiber River basin, west-central Italy

Stream sediment, stream water, and fish were collected from a broad region to evaluate downstream transport and dispersion of mercury (Hg) from inactive mines in the Monte Amiata Hg District (MAMD), Tuscany, Italy. Stream sediment samples ranged in Hg concentration from 20 to 1,900 ng/g, and only 5 of the 17 collected samples exceeded the probable effect concentration for Hg of 1,060 ng/g, above which harmful effects are likely to be observed in sediment-dwelling organisms. Concentrations of methyl-Hg in Tiber River sediment varied from 0.12 to 0.52 ng/g, and although there is no established guideline for sediment methyl-Hg, these concentrations exceeded methyl-Hg in a regional baseline site (<0.02 ng/g). Concentrations of Hg in stream water varied from 1.2 to 320 ng/L, all of which were below the 1,000 ng/L Italian drinking water Hg guideline and the 770 ng/L U.S. Environmental Protection Agency (USEPA) guideline recommended to protect against chronic effects to aquatic wildlife. Methyl-Hg concentrations in stream water varied from <0.02 to 0.53 ng/L and were generally elevated compared to the baseline site (<0.02 ng/L). All stream water samples contained concentrations of As (<1.0–6.2 μg/L) and Sb (<0.20–0.37 μg/L) below international drinking water guidelines to protect human health (10 μg/L for As and 20 μg/L for Sb) and for protection against chronic effects to aquatic wildlife (150 μg/L for As and 5.6 μg/L for Sb). Concentrations of Hg in freshwater fish muscle ranged from 0.052–0.56 μg/g (wet weight), mean of 0.17 μg/g, but only 17 % (9 of 54) exceeded the 0.30 μg/g (wet weight) USEPA fish muscle guideline recommended to protect human health. Concentrations of Hg in freshwater fish in this region generally decreased with increasing distance from the MAMD, where fish with the highest Hg concentrations were collected more proximal to the MAMD, whereas all fish collected most distal from Hg mines contained Hg below the 0.30 μg/g fish muscle guideline. Data in this study indicate some conversion of inorganic Hg to methyl-Hg and uptake of Hg in fish on the Paglia River, but less methylation of Hg and Hg uptake by freshwater fish in the larger Tiber River.

Tiber River Basin↗

USGS2014

Reflections on a vision for integrated research and monitoring after 15 years

In May of 1998, Owen Bricker and his co-author Michael Ruggiero introduced a conceptual design for integrating the Nation’s environmental research and monitoring programs. The Framework for Integrated Monitoring and Related Research was an organizing strategy for relating data collected by various programs, at multiple spatial and temporal scales, and by multiple science disciplines to solve complex ecological issues that individual research or monitoring programs were not designed to address. The concept nested existing intensive monitoring and research stations within national and regional surveys, remotely sensed data, and inventories to produce a collaborative program for multi-scale, multi-network integrated environmental monitoring and research. Analyses of gaps in data needed for specific issues would drive decisions on network improvements or enhancements. Data contributions to the Framework from existing networks would help indicate critical research and monitoring programs to protect during budget reductions. Significant progress has been made since 1998 on refining the Framework strategy. Methods and models for projecting scientific information across spatial and temporal scales have been improved, and a few regional pilots of multi-scale data-integration concepts have been attempted. The links between science and decision-making are also slowly improving and being incorporated into science practice. Experiments with the Framework strategy since 1998 have revealed the foundational elements essential to its successful implementation, such as defining core measurements, establishing standards of data collection and management, integrating research and long-term monitoring, and describing baseline ecological conditions. They have also shown us the remaining challenges to establishing the Framework concept: protecting and enhancing critical long-term monitoring, filling gaps in measurement methods, improving science for decision support, and integrating the disparate integrated science efforts now underway. In the 15 years since the Bricker and Ruggiero (Ecol Appl 8(2):326–329, 1998) paper challenged us with a new paradigm for bringing sound and comprehensive science to environmental decisions, the scientific community can take pride in the progress that has been made, while also taking stock of the challenges ahead for completing the Framework vision.

Aquatic Geochemistry↗

USGS2014

Assessing the solubility controls on vanadium in groundwater, northeastern San Joaquin Valley, CA

The solubility controls on vanadium (V) in groundwater were studied due to concerns over possible harmful health effects of ingesting V in drinking water. Vanadium concentrations in the northeastern San Joaquin Valley ranged from <3 μg/L to 70 μg/L with a median of 21 μg/L. Concentrations of V were highest in samples collected from oxic groundwater (49% > 25 μg/L) and lowest in samples collected from anoxic groundwater (70% < 0.8 μg/L). In oxic groundwater, speciation modeling (SM) using PHREEQC predicted that V exists primarily as the oxyanion H 2 VO 4 − . Adsorption/desorption reactions with mineral surfaces and associated oxide coatings were indicated as the primary solubility control of V 5+ oxyanions in groundwater. Environmental data showed that V concentrations in oxic groundwater generally increased with increasing groundwater pH. However, data from adsorption isotherm experiments indicated that small variations in pH (7.4–8.2) were not likely as an important a factor as the inherent adsorption capacity of oxide assemblages coating the surface of mineral grains. In suboxic groundwater, accurate SM modeling was difficult since Eh measurements of source water were not measured in this study. Vanadium concentrations in suboxic groundwater decreased with increasing pH indicating that V may exist as an oxycationic species [e.g. V(OH) 3 + ]. Vanadium may complex with dissolved inorganic and organic ligands under suboxic conditions, which could alter the adsorption behavior of V in groundwater. Speciation modeling did not predict the existence of V-inorganic ligand complexes and organic ligands were not collected as part of this study. More work is needed to determine processes governing V solubility under suboxic groundwater conditions. Under anoxic groundwater conditions, SM predicts that aqueous V exists as the uncharged V(OH) 3 molecule. However, exceedingly low V concentrations show that V is sparingly soluble in anoxic conditions. Results indicated that V may be precipitating as V 3+ - or mixed V 3+ /Fe 3+ -oxides in anoxic groundwater, which is consistent with results of a previous study. The fact that V appears insoluble in anoxic (Fe reducing) redox conditions indicates that the behavior of V is different than arsenic (As) in aquifer systems where the reductive dissolution of Fe-oxides with As adsorbed to the surface is a well-documented mechanism for increasing As concentrations in groundwater. This hypothesis is supported by the relation of V to As concentrations in oxic versus anoxic redox conditions. Sequential extraction procedures (SEP) applied to aquifer material showed that the greatest amount of V was recovered by the nitric acid (HNO 3 ) extract (37–71%), followed by the oxalate-ascorbic acid extract (19–60%) and the oxalate extract (3–14%). These results indicate that V was not associated with the solid phase as an easily exchangeable fraction. Although the total amount of V recovered was greatest for the HNO 3 extract that targets V adsorbed to sorption sites of crystalline Al, Fe and Mn oxides, the greatest V saturation of sorption sites appeared to occur on the amorphous and poorly crystalline oxide solid phases targeted by the oxalate and oxalate-ascorbic acid extracts respectively. Adsorption isotherm experiments showed no correlation between V sorption and any of the fractions identified by the SEP. This lack of correlation indicates the application of an SEP alone is not adequate to estimate the sorption characteristics of V in an aquifer system.

California↗