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USGS1992

Thermodynamics and kinetics of reactions involving vanadium in natural systems: Accumulation of vanadium in sedimentary rocks

A critical review of thermodynamic data for aqueous and solid V species is presented to evaluate dissolution, transport, and precipitation of V under natural conditions. Emphasis is given to results of experimental studies of V chemistry, especially those for which the experimental conditions are near those found in nature. Where possible, data are obtained for or corrected to the reference conditions of 298.15K, 1 atm (1.01325 bar) and zero ionic strength. Vanadium [IV] (V IV ) and vanadium[V] (V V ) are the most soluble forms of V in nature, and their complexes with fluoride, sulfate, and oxalate may act to increase V solubility under oxidizing conditions. Because redox behavior is of fundamental importance to understanding natural V chemistry, the kinetics of reduction of V IV to V III H 2 S were studied. Although H 2 S is predicted from thermodynamic data to be capable of reducing V IV to V III , this reaction has not been demonstrated experimentally. Experiments were carried out under conditions of temperature (45°C), pH (3.6–6.8), ionic strength (0.05–0.1 m), and V concentrations (9.8–240 μmolar) likely to be found in nature. Because the reaction is very slow, H 2 S concentrations in excess of natural conditions were used (8.1 × 10 −4 to 0.41 atm). The results show that V IV is reduced to V III under a variety of conditions. The rate increases with increasing pH, but is not appreciably affected by ionic strength (as represented by the concentration of KCl, which was used as the supporting electrolyte in all cases). Prior to initiation of the reaction, there is an induction period, the length of which increases with increasing KCl concentration or decreasing pH. Attempts to model the reaction mechanism by numerical methods have failed to produce a satisfying fit of the results, indicating partial reaction orders, a complex mechanism, or involvement of a variety of intermediate species. The results of the thermodynamic and kinetic studies were applied to understanding the genesis of V deposits such as those commonly found on the Colorado Plateau. Vanadium in these sandstone-hosted deposits is present mostly in the reduced oxidation state, V III . Because of the insolubility of V III oxyhydroxides, it is likely that a more oxidized form of V (either [IV] or [V]) was transported to the site of mineralization, and that the V was reduced in situ and subsequently precipitated. A probable reductant is hydrogen sulfide; the presence of pyrite cogenetic with the V minerals documents the presence of H 2 S during mineralization. The experiments described here show that H 2 S could have reduced V IV to V III , and thus led to the formation of these deposits.

Geochimica et Cosmochimica Acta↗

USGS1993

Sulfur isotope and porewater geochemistry of Florida escarpment seep sediments

Distributions of porewater constituents, SO 4 = , NH 4 + , Cl − , ∑CO 2 , and H 2 S, solid phase iron, and sulfur concentrations, and the sulfur isotopic composition of dissolved and solid phases were investigated in sediments from abyssal seeps at the base of the Florida escarpment. Despite the apparent similarity of seep sediment porewater chemistry to that of typical marine sediments undergoing early diagenesis, relationships between chemical distributions and isotopic measurements revealed that the distribution of pore fluid constituents was dominated by processes occurring within the platform rather than by in situ microbial processes. Ammonium and sulfate concentrations were linearly correlated with chloride concentrations, indicating that variations in porewater chemistry were controlled by the admixture of seawater and a sulfate depleted brine with a chlorinity of 27.5 ± 1.9%. and 2.2 ± 1.3 mM ammonium concentration. At sites dominated by seepage, dissolved sulfate isotopic composition remained near seawater values despite depletion in porewater concentrations. Porewater ∑CO 2 concentrations were found to be elevated relative to seawater, but not to the extent predicted from the observed sulfate depletion. Sediment solid phase sulfur was predominantly pyrite, at concentrations as high as 20% S by weight. In contrast to typical marine deposits, pyrite concentrations were not related to the quantity of sedimentary organic matter. Pyrite δ 34 S values ranged from −29%. to + 21%. (CDT). However, only positive δ 34 S values were observed at sites associated with high pyrite concentrations. Isotopically heavy pyrite was observed at sites with porewater sulfate of seawater-like isotopic composition. Isotopically light pyrite was associated with sites where porewater sulfate exhibited δ 34 S values greater than those in seawater, indicating the activity of in situ microbial sulfate reduction. Thus, dual sulfide sources are suggested to explain the range in sediment pyrite isotopic composition: a δ 34 S enriched (+10 to +20%.) source adverted from within the Florida platform, and a lighter 34 S depleted component generated in situ from microbial reduction of seawater sulfate. The degree of pyritization of seep sediments was as high as 0.9 and was controlled by pyrite concentrations, which varied over a wider range than did the non-pyrite solid phase iron concentrations. The highest non-sulfide solid phase iron concentrations were observed in sediments that are believed to be at the “front” of the advancing seep fluids (i.e., hemipelagic sediments newly exposed to the seep fluids), indicating that dissolution of hemipelagic background sediment may be the source of at least half of the iron to the highly pyritized seep sediments. Porewater sulfide concentrations were variable, reaching a maximum of 5.7 mM, and were not correlated with the degree of pyritization of the sediments, suggesting that iron was not particularly limiting to pyrite formation.

Geochimica et Cosmochimica Acta↗

USGS1991

Geochemistry of dissolved inorganic carbon in a Coastal Plain aquifer. 2. Modeling carbon sources, sinks, and δ13C evolution

Stable isotope data for dissolved inorganic carbon (DIC), carbonate shell material and cements, and microbial CO 2 were combined with organic and inorganic chemical data from aquifer and confining-bed pore waters to construct geochemical reaction models along a flowpath in the Black Creek aquifer of South Carolina. Carbon-isotope fractionation between DIC and precipitating cements was treated as a Rayleigh distillation process. Organic matter oxidation was coupled to microbial fermentation and sulfate reduction. All reaction models reproduced the observed chemical and isotopic compositions of final waters. However, model 1, in which all sources of carbon and electron-acceptors were assumed to be internal to the aquifer, was invalidated owing to the large ratio of fermentation CO 2 to respiration CO 2 predicted by the model (5–49) compared with measured ratios (two or less). In model 2, this ratio was reduced by assuming that confining beds adjacent to the aquifer act as sources of dissolved organic carbon and sulfate. This assumption was based on measured high concentrations of dissolved organic acids and sulfate in confining-bed pore waters (60–100 μM and 100–380 μM, respectively) relative to aquifer pore waters (from less than 30 μM and 2–80 μM, respectively). Sodium was chosen as the companion ion to organic-acid and sulfate transport from confining beds because it is the predominant cation in confining-bed pore waters. As a result, excessive amounts of Na-for-Ca ion exchange and calcite precipitation (three to four times more cement than observed in the aquifer) were required by model 2 to achieve mass and isotope balance of final water. For this reason, model 2 was invalidated. Agreement between model-predicted and measured amounts of carbonate cement and ratios of fermentation CO 2 to respiration CO 2 were obtained in a reaction model that assumed confining beds act as sources of DIC, as well as organic acids and sulfate. This assumption was supported by measured high concentrations of DIC in confining beds (2.6–2.7 mM). Results from this study show that geochemical models of confined aquifer systems must incorporate the effects of adjacent confining beds to reproduce observed groundwater chemistry accurately.

South Carolina↗

USGS1996

Quality and petrographic characteristics of Paleocene coals from the Hanna basin, Wyoming

Coal beds from the Ferris and Hanna Formations, in the Hanna basin, south-central Wyoming, exhibit distinct differences in ash yield, sulfur content, and petrographic and palynologic constituents. These differences are interpreted to be controlled by tectonic changes of the Hanna basin and adjoining uplifts during evolutionary development, which, in turn, controlled mire chemistry and sedimentation. These conditions created two very different settings under which the peats developed during deposition of the Ferris and the Hanna Formations. In addition, there appears to be a geographic (latitudinal) and/or climatic control on the coal characteristics manifested by major differences of Paleocene coals in the Hanna basin compared to those in the Raton basin in Colorado and New Mexico and the Powder River basin in Wyoming.Coal beds from the Ferris and Hanna Formations, in the Hanna basin, south-central Wyoming, exhibit distinct differences in ash yield, sulfur content, and petrographic and palynologic constituents. These differences are interpreted to be controlled by tectonic changes of the Hanna basin and adjoining uplifts during evolutionary development, which, in turn, controlled mire chemistry and sedimentation. These conditions created two very different settings under which the peats developed during deposition of the Ferris and the Hanna Formations. In addition, there appears to be a geographic (latitudinal) and/or climatic control on the coal characteristics manifested by major differences of Paleocene coals in the Hanna basin compared to those in the Raton basin in Colorado and New Mexico and the Powder River basin in Wyoming.

Conference Paper↗

USGS1987

Survival of spotted salamander eggs in temporary woodland ponds of coastal Maryland

Temporary ponds on the Atlantic Coastal Plain in maryland were characterized according to water chemistry, rain input, phytoplankton, zooplankton and use by the spotted salamander Ambystoma maculatum during March-October 1983-1984. Neither the number of egg masses per unit of pond surface (abundance) nor the survival of spotted salamander embryos was significantly correlated (P>0.05) with pond pH. Rainfall during May-July significantly increased the hydrogen ion concentration of 5 of 11 ponds evaluated for the impact of rainfall during the previous 48h and the previous week. Survival of egg masses transferred among eight ponds with pH3.66-4.45 and one pond with pH5.18 was significantly reduced (P<or=0.05) only at pH 3.66. Embryonic survival was negatively correlated (P<or=0.05) with the concentration of aluminium in the pond water. The abundance of egg masses was positively correlated (P<or=0.05) with water temperature and magnesium concentration, and total chlorophyll during the larval period. Yearly variability of pond characteristics (e.g. water chemistry, pond longevity) and amphibian reproduction make it difficult to determine the effects of acidic deposition on the spotted salamander. At the present time, pond longevity, water temperature and possibly, oxygen content, seem more important to spotted salamander reproduction than chemical changes caused by annual acidic deposition.

Environmental Pollution↗

USGS1988

Accumulation and bioconcentration of polycyclic aromatic hydrocarbons in a nearshore estuarine environment near a Pensacola (Florida) creosote contamination site

Long-term accumulation of creosote wastes at a wood-preserving facility near Pensacola, Florida, has produced high levels of organic contamination of groundwaters near Pensacola Bay. Impacts of this contamination on the nearshore environment of the bay were examined by analysis of water, sediment and tissues of two mollusc species. One of the species (Thais haemastoma) was native to the study area. Individuals of the other test species (Crassostrea virginica) were placed in cages at the test sites for a 6-week period. Contamination at the nearshore estuarine sites was assessed by comparison to a control site in an uncontaminated area of the bay, as well as a small stream which forms a direct surface-water link between the creosote storage ponds and the bay. The study focused on polycyclic aromatic hydrocarbons (PAH), the primary components of creosote. Very little PAH in water or in the surface layer of estuarine sediments was detected, despite heavy pollution of the stream sediments. This is attributed to various degradation processes which attack the PAH compounds once they discharge into the estuary, and to the likelihood of intermittent and localised release of contaminants to the estuary. Examination of sediment cores and mollusc tissues, which provide a record integrated over time and space, revealed some accumulation of a few PAH, notably fluoranthene, pyrene, benzo(a)anthracene, chrysene and phenanthrene. In the sediments, the highest concentrations of these compounds appeared below the surface, within a depth range of 8-13 cm. Bioaccumulation of fluoranthene, pyrene and phenanthrene in both mollusc species was up to ten times greater at test sites than at the control site. This contrasts with naphthalene, the bioaccumulation of which was no greater at test sites than at the control site. These differences in bioaccumulation factors relate to structural chemistry of the compounds which control their solubility, bioavailability, susceptibility to degradation and capacity for depuration by the organism.Long-term accumulation of creosote wastes at a wood-preserving facility near Pensacola, Florida, has produced high levels of organic contamination of groundwaters near Pensacola Bay. Impacts of this contamination on the nearshore environment of the bay were examined by analysis of water, sediment and tissues of two mollusc species. Very little PAH in water or in the surface layer of estuarine sediments was detected, despite heavy pollution of the stream sediments. This is attributed to various degradation processes which attack the PAH compounds once they discharge into the estuary, and to the likelihood of intermittent and localized release of contaminants to the estuary. There was some accumulation of a few PAH, notably fluoranthene, pyrene, benzo(a)anthracene, chrysene and phenanthrene. In the sediments, the highest concentrations of these compounds appeared below the surface, within a depth range of 8-13 cm. Bioaccumulation of fluoranthene, pyrene and phenanthrene in both mollusc species was up to ten times greater at test sites than at the control site. Differences in bioaccumulation factors relate to structural chemistry of the compounds which control their solubility, bioavailability, susceptibility to degradation and capacity for depuration by the organism.

Florida↗

USGS1991

Radon-222 and its parent radionuclides in groundwater from two study areas in New Jersey and Maryland, U.S.A.

A study of groundwater chemistry and radionuclide mobility in New Jersey and Maryland was conducted to investigate natural processes that control the mobility of radionuclides in the water-rock system. Groundwater was sampled from two geological units in New Jersey and from six in Maryland. The water sampled was from aquifiers in fractured metamorphic rocks of varying composition and metamorphic grade. In both areas, groundwater chemistry was affected most by aquifier mineralogy and lithology; concentrations of total dissolved U, 226Ra and 222Rn were similarly affected. In evey sample for which measurements were made, dissolved Utotal and 226Ra were present in much lower concentrations than 222Rn when expressed in terms of their radioactivity. On the other hand, the total amount of 222Rn that could be produced in these rocks, given their U contents, is much higher than the concentrations observed in groundwater. Thus, the emanating efficiencies of the aquifer rocks studied must be near 10% or less. Such low emanating efficiencies require that a fraction of the 226Ra in the rock be located close to the water-rock interface so that 222Rn, when produced, can be rapidly and efficiently transferred to the aqueous phase. This condition is established when a similar fraction of the U is in a readily leachable position. No known U or Ra solids were supersaturated in any of the samples. Thus, adsorption processes probably play a role in limiting mobilities of Utotal and 226Ra. Concentrations of Utotal and 226Ra found in the water samples are comparable to those found in experimental studies of adsorption onto mineral surfaces. ?? 1991.

Maryland, New Jersey↗

USGS2007

A simulation-based approach for estimating premining water quality: Red Mountain Creek, Colorado

Regulatory agencies are often charged with the task of setting site-specific numeric water quality standards for impaired streams. This task is particularly difficult for streams draining highly mineralized watersheds with past mining activity. Baseline water quality data obtained prior to mining are often non-existent and application of generic water quality standards developed for unmineralized watersheds is suspect given the geology of most watersheds affected by mining. Various approaches have been used to estimate premining conditions, but none of the existing approaches rigorously consider the physical and geochemical processes that ultimately determine instream water quality. An approach based on simulation modeling is therefore proposed herein. The approach utilizes synoptic data that provide spatially-detailed profiles of concentration, streamflow, and constituent load along the study reach. This field data set is used to calibrate a reactive stream transport model that considers the suite of physical and geochemical processes that affect constituent concentrations during instream transport. A key input to the model is the quality and quantity of waters entering the study reach. This input is based on chemical analyses available from synoptic sampling and observed increases in streamflow along the study reach. Given the calibrated model, additional simulations are conducted to estimate premining conditions. In these simulations, the chemistry of mining-affected sources is replaced with the chemistry of waters that are thought to be unaffected by mining (proximal, premining analogues). The resultant simulations provide estimates of premining water quality that reflect both the reduced loads that were present prior to mining and the processes that affect these loads as they are transported downstream. This simulation-based approach is demonstrated using data from Red Mountain Creek, Colorado, a small stream draining a heavily-mined watershed. Model application to the premining problem for Red Mountain Creek is based on limited field reconnaissance and chemical analyses; additional field work and analyses may be needed to develop definitive, quantitative estimates of premining water quality.

Colorado↗

USGS2008

Growing up green on serpentine soils: Biogeochemistry of serpentine vegetation in the Central Coast Range of California

Serpentine soils derived from the weathering of ultramafic rocks and their metamorphic derivatives (serpentinites) are chemically prohibitive for vegetative growth. Evaluating how serpentine vegetation is able to persist under these chemical conditions is difficult to ascertain due to the numerous factors (climate, relief, time, water availability, etc.) controlling and affecting plant growth. Here, the uptake, incorporation, and distribution of a wide variety of elements into the biomass of serpentine vegetation has been investigated relative to vegetation growing on an adjacent chert-derived soil. Soil pH, electrical conductivity, organic C, total N, soil extractable elements, total soil elemental compositions and plant digestions in conjunction with spider diagrams are utilized to determine the chemical relationships of these soil and plant systems. Plant available Mg and Ca in serpentine soils exceed values assessed in chert soils. Magnesium is nearly 3 times more abundant than Ca in the serpentine soils; however, the serpentine soils are not Ca deficient with Ca concentrations as high as 2235 mg kg-1. Calcium to Mg ratios (Ca:Mg) in both serpentine and chert vegetation are greater than one in both below and above ground tissues. Soil and plant chemistry analyses support that Ca is not a limiting factor for plant growth and that serpentine vegetation is actively moderating Mg uptake as well as tolerating elevated concentrations of bioavailable Mg. Additionally, results demonstrate that serpentine vegetation suppresses the uptake of Fe, Cr, Ni, Mn and Co into its biomass. The suppressed uptake of these metals mainly occurs in the plants' roots as evident by the comparatively lower metal concentrations present in above ground tissues (twigs, leaves and shoots). This research supports earlier studies that have suggested that ion uptake discrimination and ion suppression in the roots are major mechanisms for serpentine vegetation to tolerate the chemistry of serpentine soils. ?? 2008 Elsevier Ltd.

Applied Geochemistry↗

USGS2009

Mineralogy of soils from two continental-scale transects across the United States and Canada and its relation to soil geochemistry and climate

Quantitative mineralogy correlates with major-, minor- and trace-element chemistry for 387 samples of A-horizon and deeper soils collected from east-west and north-south transects across the USA and Canada, where the deeper soils were collected beneath the A-horizon samples. Concentrations of the major elements correlate with specific mineral phases. Minor- and trace-element concentrations correlate with the same phases as the major elements with which they share similar geochemical behavior. Concentrations of quartz and feldspar correlate with precipitation trends east of the Rocky Mountains, and are independent of the underlying rock type and age, indicating that the weathering of soils in this region may have reached a steady-state mineralogy. Other trends in mineralogy relate to physiographic province. The combination of quantitative mineralogy and chemical analysis yields a much richer portrait of soils than can be gained from chemistry alone, because the origins of chemical trends and the chemical availability of specific elements are related to mineralogy.

Applied Geochemistry↗

USGS2011

Using stable isotopes to understand hydrochemical processes in and around a Prairie Pothole wetland in the Northern Great Plains, USA

Millions of internally drained wetland systems in the Prairie Potholes region of the northern Great Plains (USA and Canada) provide indispensable habitat for waterfowl and a host of other ecosystem services. The hydrochemistry of these systems is complex and a crucial control on wetland function, flora and fauna. Wetland waters can have high concentrations of SO 2- 4 due to the oxidation of large amounts of pyrite in glacial till that is in part derived from the Pierre shale. Water chemistry including δ 18 O H2O , δ 2 H H2O , and δ 34 S SO4 values, was determined for groundwater, soil pore water, and wetland surface water in and around a discharge wetland in North Dakota. The isotopic data for the first time trace the interaction of processes that affect wetland chemistry, including open water evaporation, plant transpiration, and microbial SO 4 reduction.

Applied Geochemistry↗

USGS2015

Characteristics and environmental aspects of slag: a review

Slag is a waste product from the pyrometallurgical processing of various ores. Based on over 150 published studies, this paper provides an overview of mineralogical and geochemical characteristics of different types of slag and their environmental consequences, particularly from the release of potentially toxic elements to water. This chapter reviews the characteristics of both ferrous (steel and blast furnace Fe) and non-ferrous (Ag, Cu, Ni, Pb, Sn, Zn) slag. Interest in slag has been increasing steadily as large volumes, on the order of hundreds of millions of tonnes, are produced annually worldwide. Research on slag generally focuses on potential environmental issues related to the weathering of slag dumps or on its utility as a construction material or reprocessing for secondary metal recovery. The chemistry and mineralogy of slag depend on the metallurgical processes that create the material and will influence its fate as waste or as a reusable product. The composition of ferrous slag is dominated by Ca and Si. Steel slag may contain significant Fe, whereas Mg and Al may be significant in Fe slag. Calcium-rich olivine-group silicates, melilite-group silicates that contain Al or Mg, Ca-rich glass, and oxides are the most commonly reported major phases in ferrous slag. Calcite and trace amounts of a variety of sulfides, intermetallic compounds, and pure metals are typically also present. The composition of non-ferrous slag, most commonly from base-metal production, is dominated by Fe and Si with significant but lesser amounts of Al and Ca. Silicates in the olivine, pyroxene, and melilite groups, as well as glass, spinels, and SiO 2 (i.e., quartz and other polymorphs) are commonly found in non-ferrous slag. Sulfides and intermetallic compounds are less abundant than the silicates and oxides. The concentrations of some elements exceed generic USEPA soil screening levels for human contact based on multiple exposure pathways; these elements include Al, Cr, Cu, Fe, Mn, Pb, and Zn based on bulk chemical composition. Each slag type usually contains a specific suite of elements that may be of environmental concern. In general, non-ferrous slag may have a higher potential to negatively impact the environment compared to ferrous slag, and is thus a less attractive material for reuse, based on trace element chemistry, principally for base metals. However, the amount of elements released into the environment is not always consistent with bulk chemical composition. Many types of leaching tests have been used to help predict slag’s long-term environmental behavior. Overall, ferrous slags produce an alkaline leachate due to the dissolution of Ca oxides and silicates derived from compounds originally added as fluxing agents, such as lime. Ferrous slag leachate is commonly less metal-rich than leachate from non-ferrous slag generated during base metal extraction; the latter leachate may even be acidic due to the oxidation of sulfides. Because of its characteristics, ferrous slag is commonly used for construction and environmental applications, whereas both non-ferrous and ferrous slag may be reprocessed for secondary metal recovery. Both types of slag have been a source of some environmental contamination. Research into the environmental aspects of slag will continue to be an important topic whether the goal is its reuse, recycling, or remediation.

Applied Geochemistry↗

USGS2015

Arsenic and antimony geochemistry of mine wastes, associated waters and sediments at the Giant Mine, Yellowknife, Northwest Territories, Canada

Elevated levels of arsenic (As) and antimony (Sb) in water and sediments are legacy residues found downstream from gold-mining activities at the Giant Mine in Yellowknife, Northwest Territories (NWT), Canada. To track the transport and fate of As and Sb, samples of mine-waste from the mill, and surface water, sediment, pore-water, and vegetation downstream of the mine were collected. Mine waste, pore-water, and sediment samples were analyzed for bulk chemistry, and aqueous and solid-state speciation. Sediment and vegetation chemistry were evaluated using scanning electron microscope imaging, synchrotron-based element mapping and electron microprobe analysis. The distributions of As and Sb in sediments were similar, yet their distributions in the corresponding pore-waters were mostly dissimilar, and the mobility of As was greater than that of Sb. Competition for sorption sites is the most likely cause of elevated Sb concentrations in relatively oxidized pore-water and surface water. The aqueous and solid-state speciation of As and Sb also differed. In pore-water, As(V) dominated in oxidizing environments and As(III) in reducing environments. In contrast, the Sb(V) species dominated in all but one pore-water sample, even under reducing conditions. Antimony(III) appears to preferentially precipitate or adsorb onto sulfides as evidenced by the prevalence of an Sb(III)-S secondary solid-phase and the lack of Sb(III)(aq) in the deeper zones. The As(V)–O solid phase became depleted with depth below the sediment–water interface, and the Sb(V)–O phase persisted under relatively reducing conditions. In the surficial zone at a site populated by Equisetum fluviatile (common horsetail), As and Sb were associated with organic material and appeared mobile in the root zone. In the zone below active plant growth, As and Sb were associated primarily with inorganic phases suggesting a release and reprecipitation of these elements upon plant death. The co-existence of reduced and oxidized As and Sb species, instability of some phases under changing redox conditions, and plant uptake and release pose challenges for remediation efforts at the mine.

Northwest Territories↗

USGS2016

Use of mineral/solution equilibrium calculations to assess the potential for carnotite precipitation from groundwater in the Texas Panhandle, USA

This study investigated the potential for the uranium mineral carnotite (K 2 (UO 2 ) 2 (VO 4 ) 2 ·3H 2 O) to precipitate from evaporating groundwater in the Texas Panhandle region of the United States. The evolution of groundwater chemistry during evaporation was modeled with the USGS geochemical code PHREEQC using water-quality data from 100 groundwater wells downloaded from the USGS National Water Information System (NWIS) database. While most modeled groundwater compositions precipitated calcite upon evaporation, not all groundwater became saturated with respect to carnotite with the system open to CO 2 . Thus, the formation of calcite is not a necessary condition for carnotite to form. Rather, the determining factor in achieving carnotite saturation was the evolution of groundwater chemistry during evaporation following calcite precipitation. Modeling in this study showed that if the initial major-ion groundwater composition was dominated by calcium-magnesium-sulfate (>70 precent Ca + Mg and >50 percent SO 4 + Cl) or calcium-magnesium-bicarbonate (>70 percent Ca + Mg and <70 percent HCO 3 + CO 3 ) and following the precipitation of calcite, the concentration of calcium was greater than the carbonate alkalinity (2 m Ca +2 > m HCO 3 − + 2 m CO 3 −2 ) carnotite saturation was achieved. If, however, the initial major-ion groundwater composition is sodium-bicarbonate (varying amounts of Na, 40–100 percent Na), calcium-sodium-sulfate, or calcium-magnesium-bicarbonate composition (>70 percent HCO 3 + CO 3 ) and following the precipitation of calcite, the concentration of calcium was less than the carbonate alkalinity (2 m Ca +2 < m HCO 3 - + 2 m CO 3 −2 ) carnotite saturation was not achieved. In systems open to CO 2, carnotite saturation occurred in most samples in evaporation amounts ranging from 95 percent to 99 percent with the partial pressure of CO 2 ranging from 10 −3.5 to 10 −2.5 atm. Carnotite saturation occurred in a few samples in evaporation amounts ranging from 98 percent to 99 percent with the partial pressure of CO 2 equal to 10 −2.0 atm. Carnotite saturation did not occur in any groundwater with the system closed to CO 2 .

Texas↗

USGS2020

Batch extraction method to estimate total dissolved solids (TDS) release from coal refuse and overburden

A rapid batch extraction method was evaluated to estimate potential for total dissolved solids (TDS) release by 65 samples of rock from coal and gas-bearing strata of the Appalachian Basin in eastern USA. Three different extractant solutions were considered: deionized water (DI), DI equilibrated with 10% CO 2 atmosphere (DI + CO 2 ), or 30% H 2 O 2 under 10% CO 2 (H 2 O 2 +CO 2 ). In all extractions, 10 g of pulverized rock (<0.5-mm) were mixed with 20 mL of extractant solution and shaken for 4 h at 50 rpm and 20–22 °C. The 65 rock samples were classified as coal (n=3), overburden (n = 17), coal refuse that had weathered in the field (n = 14), unleached coal refuse that had oxidized during indoor storage (n = 20), gas-bearing shale (n = 10), and pyrite (n = 1). Extracts were analyzed for specific conductance (SC), TDS, pH, and major and trace elements, and subsequently speciated to determine ionic contributions to SC. The pH of extractant blanks decreased in the order DI (6.0), DI + CO 2 (5.1), and H 2 O 2 +CO 2 (2.6). The DI extractant was effective for mobilizing soluble SO 4 and Cl salts. The DI + CO 2 extractant increased weathering of carbonates and resulted in equivalent or greater TDS than the DI leach of the same material. The H 2 O 2 +CO 2 extractant increased weathering of sulfides (and carbonates) and resulted in the greatest TDS production and lowest pH values. Of the 65 samples, 19 had leachate chemistry data from previous column experiments and 35 were paired to 10 field sites with leachate chemistry data. When accounting for the water-to-rock ratio, TDS from DI and DI + CO 2 extractions were correlated to TDS from column experiments while TDS from H 2 O 2 +CO 2 extractions was not. In contrast to column experiments, field SC was better correlated to SC measured from H 2 O 2 +CO 2 extractions than DI extractions. The field SC and SC from H 2 O 2 +CO 2 extractions were statistically indistinguishable for 7 of 9 paired data sets while SC from DI extractions underestimated field SC in 5 of 9 cases. Upscaling comparisons suggest that (1) weathering reactions in the field are more aggressive than DI water or synthetic rainwater extractants used in batch or column tests, and (2) a batch extraction method utilizing 30% H 2 O 2 (which is mildly acidic without CO 2 enrichment) could be effective for identifying rocks that will release high amounts of TDS.

Applied Geochemistry↗

USGS2010

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↗

USGS2017

Investigating the influence of nitrate nitrogen on post-smolt Atlantic salmon Salmo salar reproductive physiology in water recirculation aquaculture systems

A major issue affecting land-based, closed containment Atlantic salmon Salmo salar growout production in water recirculation aquaculture systems (RAS) is precocious male maturation, which can negatively impact factors such as feed conversion, fillet yield, and product quality. Along with other water quality parameters, elevated nitrate nitrogen (NO 3 -N) has been shown to influence the reproductive development and endogenous sex steroid production in a number of aquatic animal species, including Atlantic salmon. We sought to determine whether elevated NO 3 -N in RAS can influence early maturation in post-smolt Atlantic salmon in an 8-month trial in replicated freshwater RAS. Post-smolt Atlantic salmon (102 ± 1 g) were stocked into six RAS, with three RAS randomly selected for dosing with high NO 3 -N (99 ± 1 mg/L) and three RAS set for low NO 3 -N (10 ± 0 mg/L). At 2-, 4-, 6-, and 8-months post-stocking, 5 fish were randomly sampled from each RAS, gonadosomatic index(GSI) data were collected, and plasma was sampled for 11-ketotestosterone (11-KT) quantification. At 4- and 8-months post-stocking, samples of culture tank and spring water (used as “makeup” or replacement water) were collected and tested for a suite of 42 hormonally active compounds using liquid chromatography/mass spectrometry , as well as for estrogenicity using the bioluminescent yeast estrogen screen (BLYES) reporter system. Finally, at 8-months post-stocking 8–9 salmon were sampled from each RAS for blood gas and chemistry analyses, and multiple organ tissues were sampled for histopathology evaluation. Overall, sexually mature males were highly prevalent in both NO 3 -N treatment groups by study’s end, and there did not appear to be an effect of NO 3 -N on male maturation prevalence based on grilse identification, GSI, and 11-KT results, indicating that other culture parameters likely instigated early maturation. No important differences were noted between treatment groups for whole blood gas and chemistry parameters, and no significant tissue changes were noted on histopathology. No hormones, hormone conjugates, or mycotoxins were detected in any water samples; phytoestrogens were generally detected at low levels but were unrelated to NO 3 -N treatment. Finally, low-level estrogenicity was detected in RAS water, but a NO 3 -N treatment effect could not be determined. The major findings of this study are i) the NO 3 -N treatments did not appear to be related to the observed male maturation, and ii) the majority of hormonally active compounds were not detectable in RAS water.

Aquacultural Engineering↗

USGS2016

Atmospheric inputs of organic matter to a forested watershed: Variations from storm to storm over the seasons

The objectives of this study were to determine the quantity and chemical composition of precipitation inputs of dissolved organic carbon (DOC) to a forested watershed; and to characterize the associated temporal variability. We sampled most precipitation that occurred from May 2012 through August 2013 at the Susquehanna Shale Hills Critical Zone Observatory (Pennsylvania, USA). Sub-event precipitation samples (159) were collected sequentially during 90 events; covering various types of synoptic meteorological conditions in all climatic seasons. Precipitation DOC concentrations and rates of wet atmospheric DOC deposition were highly variable from storm to storm, ranging from 0.3 to 5.6 mg C L −1 and from 0.5 to 32.8 mg C m −2 h −1 , respectively. Seasonally, storms in spring and summer had higher concentrations of DOC and more optically active organic matter than in winter. Higher DOC concentrations resulted from weather types that favor air advection, where cold frontal systems, on average, delivered more than warm/stationary fronts and northeasters. A mixed modeling statistical approach revealed that factors related to storm properties, emission sources, and to the chemical composition of the atmosphere could explain more than 60% of the storm to storm variability in DOC concentrations. This study provided observations on changes in dissolved organic matter that can be useful in modeling of atmospheric oxidative chemistry, exploring relationships between organics and other elements of precipitation chemistry, and in considering temporal changes in ecosystem nutrient balances and microbial activity.

Atmospheric Environment↗