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At least 1,639 records · Page 91Linked to original sources
USGS2020

Assessing mercury distribution using isotopic fractionation of mercury processes and sources adjacent and downstream of a legacy mine district in Tuscany, Italy

Mercury (Hg) concentrations and isotopic compositions in a range of sample types collected from the legacy Abbadia San Salvatore Mine (ASSM) area were used to evaluate the distribution of Hg in the region. The district generated more than 100,000 metric tons of Hg releasing extensive amounts of gaseous Hg emissions and producing large amounts of mine waste calcine from which Hg can be mobilized into the local and regional environments. Direct and indirect impact from cinnabar ore mining and processing resulted in elevated Hg concentrations in the calcine, soils, lake and stream sediments, and fish samples collected at and downstream of ASSM. The contribution of Hg from the different sources and processes resulted in a wide range of 202Hg and 199Hg isotopic compositions (-2.25 to 0.96‰, -0.12 to 0.72‰ respectively). Fish samples resulted in negative values for 202Hg (-0.53 to -1.21‰) and positive Hg (0.12 to 0.73‰). Primary cinnabar ore and present-day geothermal water and precipitate showed distinctly negative 202Hg (-0.96 to -2.25‰), whereas waste calcine were enriched in 202Hg (202Hg from about -1 to +1‰); soils and sediments show intermediate compositions, reflecting different extents of contributions from the various Hg sources and processes. These sources and processes of Hg include weathering cinnabar, gaseous Hg emissions from ore processing, and geothermal activity to a lesser extent. Hg speciation in concert with Hg isotope ratios can better ascertain source attribution and assist in identifying Hg pathways into the environment to distinguish the more bioavailable forms of Hg entering the ecosystem.

Tuscany↗
USGS2006

Larval exposure to environmentally relevant mixtures of alkylphenolethoxylates reduces reproductive competence in male fathead minnows

The ubiquitous presence of nonylphenolethoxylate/octylphenolethoxylate (NPE/OPE) compounds in aquatic environments adjacent to wastewater treatment plants (WWTP) warrants an assessment of the endocrine disrupting potential of these complex mixtures on aquatic vertebrates. In this study, fathead minnow larvae were exposed for 64 days to a mixture of NPE/OPE, which closely models the NPE/OPE composition of a major metropolitan WWTP effluent. Target exposure concentrations included a total NPE/OPE mixture load of 200% of the WWTP effluent concentration (148 μg/L), 100% of the WWTP effluent concentration (74 μg/L) and 50% of the WWTP effluent concentration (38 μg/L). The NPE/OPE mixture contained 0.2% 4- t -octylphenol, 2.8% 4-nonylphenol, 5.1% 4-nonylphenolmonoethoxylate, 9.3% 4-nonylphenoldiethoxylate, 0.9% 4- t -octylphenolmonoethoxylate, 3.1% 4- t -octylphenoldiethoxylate, 33.8% 4-nonylphenolmonoethoxycarboxylate, and 44.8% 4-nonylphenoldiethoxycarboxylate. An additional exposure of 5 μg/L 4-nonylphenol (nominal) was conducted. The exposure utilized a flow-through system supplied by ground water and designed to deliver consistent concentrations of applied chemicals. Following exposure, larvae were raised to maturity. Upon sexual maturation, exposed male fish were allowed to compete with control males in a competitive spawning assay. Nest holding ability of control and exposed fish was carefully monitored for 7 days. All male fish were then sacrificed and analyzed for plasma vitellogenin, developmental changes in gonadal tissues, alterations in the development of secondary sexual characters, morphometric changes, and changes to reproductive behavior. When exposed to the 200% NPE/OPE treatment most larvae died within the first 4 weeks of exposure. Both the 100% and 50% NPE/OPE exposures caused a significant decrease in reproductive behavior, as indicated by an inability of many of the previously exposed males to acquire and hold a nest site required for reproduction. In contrast, the 5 μg/L 4-nonylphenol exposure resulted in significantly enhanced reproductive behavior compared to that of control males and a majority of the nesting sites were held by previously exposed males. No significant change in the development of gonadal tissues was observed. The 100% NPE/OPE exposure resulted in a significant reduction in the gonadal somatic index and in the prominence of secondary sexual characteristics of exposed larvae. This study indicates that NPE/OPE mixtures have an effect on the reproductive competence of previously exposed male fathead minnows. In addition, 4-nonylphenol concentrations utilized in all exposures were below regulatory guidelines, suggesting that evaluation of 4-nonylphenol alone may not be sufficient for identifying potentially adverse effects of this suite of compounds usually found as mixtures in the aquatic environment.

Aquatic Toxicology↗
USGS2015

Biodynamics of copper oxide nanoparticles and copper ions in an oligochaete: Part I: relative importance of water and sediment as exposure routes

Copper oxide (CuO) nanoparticles (NPs) are widely used, and likely released into the aquatic environment. Both aqueous (i.e., dissolved Cu) and particulate Cu can be taken up by organisms. However, how exposure routes influence the bioavailability and subsequent toxicity of Cu remains largely unknown. Here, we assess the importance of exposure routes (water and sediment) and Cu forms (aqueous and nanoparticulate) on Cu bioavailability and toxicity to the freshwater oligochaete, Lumbriculus variegatus , a head-down deposit-feeder. We characterize the bioaccumulation dynamics of Cu in L. variegatus across a range of exposure concentrations, covering both realistic and worst-case levels of Cu contamination in the environment. Both aqueous Cu (Cu-Aq; administered as Cu(NO 3 ) 2 ) and nanoparticulate Cu (CuO NPs), whether dispersed in artificial moderately hard freshwater or mixed into sediment, were weakly accumulated by L. variegatus . Once incorporated into tissues, Cu elimination was negligible, i.e., elimination rate constants were in general not different from zero for either exposure route or either Cu form. Toxicity was only observed after waterborne exposure to Cu-Aq at very high concentration (305 µgL -1 ), where all worms died. There was no relationship between exposure route, Cu form or Cu exposure concentration on either worm survival or growth. Slow feeding rates and low Cu assimilation efficiency (approximately 30%) characterized the uptake of Cu from the sediment for both Cu forms. In nature, L. variegatus is potentially exposed to Cu via both water and sediment. However, sediment progressively becomes the predominant exposure route for Cu in L. variegatus as Cu partitioning to sediment increases.

Aquatic Toxicology↗
USGS2019

Control of invasive sea lampreys using the piscicides TFM and niclosamide: Toxicology, successes & future prospects

The invasion of the Laurentian Great Lakes of North America by sea lampreys ( Petromyzon marinus ) in the early 20th century contributed to the depletion of commercial, recreational and culturally important fish populations, devastating the economies of communities that relied on the fishery. Sea lamprey populations were subsequently controlled using an aggressive integrated pest-management program which employed barriers and traps to prevent sea lamprey from migrating to their spawning grounds and the use of the piscicides (lampricides) 3-trifluoromethyl-4-nitrophenol (TFM) and niclosamide to eliminate larval sea lampreys from their nursery streams. Although sea lampreys have not been eradicated from the Great Lakes, populations have been suppressed to less than 10% of their peak numbers in the mid-1900s. The ongoing use of lampricides provides the foundation for sea lamprey control in the Great Lakes, one of the most successful invasive species control programs in the world. Yet, significant gaps remain in our understanding of how lampricides are taken-up and handled by sea lampreys, how lampricides exert their toxic effects, and how they adversely affect non-target invertebrate and vertebrates species. In this review we examine what has been learned about the uptake, handling and elimination, and the mode of TFM and niclosamide toxicity in lampreys and in non-target animals, particularly in the last 10 years. It is now clear that the mode of TFM toxicity is the same in non-target fishes and lampreys, in which TFM interferes with oxidative phosphorylation by the mitochondria leading to decreased ATP production. Vulnerability to TFM is related to abiotic factors such as water pH and alkalinity, which we propose changes the relative amounts of the bioavailable un-ionized form of TFM in the gill microenvironment. Niclosamide, which is also a molluscicide used to control snails in areas prone to schistosomiasis infections of humans, also likely works by uncoupling oxidative phosphorylation, but less is known about other aspects of its toxicology. The effects of TFM include reductions in energy stores, particularly glycogen and high energy phosphagens. However, non-target fishes readily recover from sub-lethal TFM exposure as demonstrated by the rapid restoration of energy stores and clearance of TFM. Although both TFM and niclosamide are non-persistent in the environment and critical for sea lamprey control, increasing public and institutional concerns about pesticides in the environment makes it imperative to explore other means of sea lamprey control. Accordingly, we also address possible “next-generation” strategies of sea lamprey control including genetic tools such as RNA interference and CRISPR-Cas9 to impair critical physiological processes (e.g. reproduction, digestion, metamorphosis) in lamprey, and the use of green chemistry to develop more environmentally benign chemical methods of sea lamprey control.

Great Lakes↗
USGS2020

Relative toxicity and sublethal effects of NaCl and energy-related saline wastewaters on prairie amphibians

Increasing salinity in freshwater environments is a growing problem due both to the negative influences of salts on ecosystems and their accumulation and persistence in environments. Two major sources of increased salinity from sodium chloride salts (NaCl) are saline wastewaters co-produced during energy production (herein, wastewaters) and road salts. Effects of road salts have received more attention, but legacy contamination from wastewaters is widespread in some regions and spills still occur. Amphibians are sensitive to contaminants, including NaCl, because of their porous skin and osmoregulatory adaptations to freshwater. However, similarities and differences between effects of wastewaters and road salts have not been investigated. Therefore, we investigated the relative influence of wastewaters and NaCl at equivalent concentrations of chloride on three larval amphibian species that occur in areas with increased salinity. We determined acute toxicity and growth effects on Boreal Chorus Frogs ( Pseudacris maculata ), Northern Leopard Frogs ( Rana pipiens ), and Barred Tiger Salamanders ( Ambystoma mavortium ). We posited that wastewaters would have additive effects on amphibians compared to NaCl because wastewaters often have additional toxic heavy metals and other contaminants. For NaCl, toxicity was higher for frogs than the salamander. Toxicity of wastewaters was also similar between chorus and leopard frogs. Only chorus frog survival was lower when exposed to wastewater compared to NaCl. Mass and length of leopard and chorus frog larvae decreased with increasing salinity after only 96 hours of exposure but did not for tiger salamanders. Size of leopard frogs was lower when exposed to NaCl compared to wastewater. However, growth effects were similar between wastewater and NaCl for chorus frogs. Taken together, our results suggest that previous studies on effects of road salt could inform future studies and management of wastewater-contaminated ecosystems, and vice versa. Nevertheless, effects of road salts and wastewaters may be context-, species-, and trait-specific and require further investigations. The negative influence of salts on imperiled amphibians underscores the need to restore landscapes with increased salinity and reduce future salinization of freshwater ecosystems.

Aquatic Toxicology↗
USGS2017

Can personality predict individual differences in brook trout spatial learning ability?

While differences in individual personality are common in animal populations, understanding the ecological significance of variation has not yet been resolved. Evidence suggests that personality may influence learning and memory; a finding that could improve our understanding of the evolutionary processes that produce and maintain intraspecific behavioural heterogeneity. Here, we tested whether boldness, the most studied personality trait in fish, could predict learning ability in brook trout. After quantifying boldness, fish were trained to find a hidden food patch in a maze environment. Stable landmark cues were provided to indicate the location of food and, at the conclusion of training, cues were rearranged to test for learning. There was a negative relationship between boldness and learning as shy fish were increasingly more successful at navigating the maze and locating food during training trials compared to bold fish. In the altered testing environment, only shy fish continued using cues to search for food. Overall, the learning rate of bold fish was found to be lower than that of shy fish for several metrics suggesting that personality could have widespread effects on behaviour. Because learning can increase plasticity to environmental change, these results have significant implications for fish conservation.

Behavioural Processes↗
USGS2015

Statistical guidelines for assessing marine avian hotspots and coldspots: A case study on wind energy development in the U.S. Atlantic Ocean

Estimating patterns of habitat use is challenging for marine avian species because seabirds tend to aggregate in large groups and it can be difficult to locate both individuals and groups in vast marine environments. We developed an approach to estimate the statistical power of discrete survey events to identify species-specific hotspots and coldspots of long-term seabird abundance in marine environments. We illustrate our approach using historical seabird data from survey transects in the U.S. Atlantic Ocean Outer Continental Shelf (OCS), an area that has been divided into “lease blocks” for proposed offshore wind energy development. For our power analysis, we examined whether discrete lease blocks within the region could be defined as hotspots (3 × mean abundance in the OCS) or coldspots (1/3 ×) for individual species within a given season. For each of 74 species/season combinations, we determined which of eight candidate statistical distributions (ranging in their degree of skewedness) best fit the count data. We then used the selected distribution and estimates of regional prevalence to calculate and map statistical power to detect hotspots and coldspots, and estimate the p -value from Monte Carlo significance tests that specific lease blocks are in fact hotspots or coldspots relative to regional average abundance. The power to detect species-specific hotspots was higher than that of coldspots for most species because species-specific prevalence was relatively low (mean: 0.111; SD: 0.110). The number of surveys required for adequate power (> 0.6) was large for most species (tens to hundreds) using this hotspot definition. Regulators may need to accept higher proportional effect sizes, combine species into groups, and/or broaden the spatial scale by combining lease blocks in order to determine optimal placement of wind farms. Our power analysis approach provides a general framework for both retrospective analyses and future avian survey design and is applicable to a broad range of research and conservation problems.

U.S. Atlantic Ocean Outer Continental Shelf↗
USGS2004

A visual basic program to generate sediment grain-size statistics and to extrapolate particle distributions

Measures that describe and summarize sediment grain-size distributions are important to geologists because of the large amount of information contained in textural data sets. Statistical methods are usually employed to simplify the necessary comparisons among samples and quantify the observed differences. The two statistical methods most commonly used by sedimentologists to describe particle distributions are mathematical moments (Krumbein and Pettijohn, 1938) and inclusive graphics (Folk, 1974). The choice of which of these statistical measures to use is typically governed by the amount of data available (Royse, 1970). If the entire distribution is known, the method of moments may be used; if the next to last accumulated percent is greater than 95, inclusive graphics statistics can be generated. Unfortunately, earlier programs designed to describe sediment grain-size distributions statistically do not run in a Windows environment, do not allow extrapolation of the distribution's tails, or do not generate both moment and graphic statistics (Kane and Hubert, 1963; Collias et al., 1963; Schlee and Webster, 1967; Poppe et al., 2000) 1 . Owing to analytical limitations, electro-resistance multichannel particle-size analyzers, such as Coulter Counters, commonly truncate the tails of the fine-fraction part of grain-size distributions. These devices do not detect fine clay in the 0.6–0.1 μm range (part of the 11-phi and all of the 12-phi and 13-phi fractions). Although size analyses performed down to 0.6 μm microns are adequate for most freshwater and near shore marine sediments, samples from many deeper water marine environments (e.g. rise and abyssal plain) may contain significant material in the fine clay fraction, and these analyses benefit from extrapolation. The program (GSSTAT) described herein generates statistics to characterize sediment grain-size distributions and can extrapolate the fine-grained end of the particle distribution. It is written in Microsoft Visual Basic 6.0 and provides a window to facilitate program execution. The input for the sediment fractions is weight percentages in whole-phi notation (Krumbein, 1934; Inman, 1952), and the program permits the user to select output in either method of moments or inclusive graphics statistics (Fig. 1). Users select options primarily with mouse-click events, or through interactive dialogue boxes.

Computers & Geosciences↗
USGS2005

Origin of secondary sulfate minerals on active andesitic stratovolcanoes

Sulfate minerals in altered rocks on the upper flanks and summits of active andesitic stratovolcanoes result from multiple processes. The origin of these sulfates at five active volcanoes, Citlalte??petl (Mexico), and Mount Adams, Hood, Rainier, and Shasta (Cascade Range, USA), was investigated using field observations, petrography, mineralogy, chemical modeling, and stable-isotope data. The four general groups of sulfate minerals identified are: (1) alunite group, (2) jarosite group, (3) readily soluble Fe- and Al-hydroxysulfates, and (4) simple alkaline-earth sulfates such as anhydrite, gypsum, and barite. Generalized assemblages of spatially associated secondary minerals were recognized: (1) alunite+silica??pyrite??kaolinite?? gypsum??sulfur, (2) jarosite+alunite+silica; (3) jarosite+smectite+silica??pyrite, (4) Fe- and Al-hydroxysulfates+silica, and (5) simple sulfates+silica??Al-hydroxysulfates??alunite. Isotopic data verify that all sulfate and sulfide minerals and their associated alteration assemblages result largely from the introduction of sulfur-bearing magmatic gases into meteoric water in the upper levels of the volcanoes. The sulfur and oxygen isotopic data for all minerals indicate the general mixing of aqueous sulfate derived from deep (largely disproportionation of SO2 in magmatic vapor) and shallow (oxidation of pyrite or H2S) sources. The hydrogen and oxygen isotopic data of alunite indicate the mixing of magmatic and meteoric fluids. Some alunite-group minerals, along with kaolinite, formed from sulfuric acid created by the disproportionation of SO2 in a condensing magmatic vapor. Such alunite, observed only in those volcanoes whose interiors are exposed by erosion or edifice collapse, may have ??34S values that reflect equilibrium (350??50 ??C) between aqueous sulfate and H2S. Alunite with ??34S values indicating disequilibrium between parent aqueous sulfate and H2S may form from aqueous sulfate created in higher level low-temperature environments in which SO2 is scrubbed out by groundwater or where H2S is oxidized. Jarosite-group minerals associated with smectite in only slightly altered volcanic rock are formed largely from aqueous sulfate derived from supergene oxidation of hydrothermal pyrite above the water table. Soluble Al- and Fehydroxysulfates form in low-pH surface environments, especially around fumaroles, and from the oxidation of hydrothermal pyrite. Anhydrite/gypsum, often associated with native sulfur and occasionally with small amounts of barite, also commonly form around fumaroles. Some occurrences of anhydrite/gypsum may be secondary, derived from the dissolution and reprecipitation of soluble sulfate. Edifice collapse may also reveal deep veins of anhydrite/gypsum??barite that formed from the mixing of saline fluids with magmatic sulfate and dilute meteoric water. Alteration along structures associated with both hydrothermal and supergene sulfates, as well as the position of paleo-water tables, may be important factors in edifice collapse and resulting debris flows at some volcanoes. ?? 2004 Elsevier B.V. All rights reserved.

Chemical Geology↗
USGS2008

Integrated Fe- and S-isotope study of seafloor hydrothermal vents at East Pacific Rise 9-10°N

In this study, we report on coupled Fe- and S-isotope systematics of hydrothermal fluids and sulfide deposits from the East Pacific Rise at 9–10°N to better constrain processes affecting Fe-isotope fractionation in hydrothermal environments. We aim to address three fundamental questions: (1) Is there significant Fe-isotope fractionation during sulfide precipitation? (2) Is there significant variability of Fe-isotope composition of the hydrothermal fluids reflecting sulfide precipitation in subsurface environments? (3) Are there any systematics between Fe- and S-isotopes in sulfide minerals? The results show that chalcopyrite, precipitating in the interior wall of a hydrothermal chimney displays a limited range of δ 56 Fe values and δ 34 S values, between − 0.11 to − 0.33‰ and 2.2 to 2.6‰ respectively. The δ 56 Fe values are, on average, slightly higher by 0.14‰ relative to coeval vent fluid composition while δ 34 S values suggest significant S-isotope fractionation (− 0.6 ± 0.2‰) during chalcopyrite precipitation. In contrast, systematically lower δ 56 Fe and δ 34 S values relative to hydrothermal fluids, by up to 0.91‰ and 2.0‰ respectively, are observed in pyrite and marcasite precipitating in the interior of active chimneys. These results suggest isotope disequilibrium in both Fe- and S-isotopes due to S-isotopic exchange between hydrothermal H 2 S and seawater SO 4 2− followed by rapid formation of pyrite from FeS precursors, thus preserving the effects of a strong kinetic Fe-isotope fractionation during FeS precipitation. In contrast, δ 56 Fe and δ 34 S values of pyrite from inactive massive sulfides, which show evidence of extensive late-stage reworking, are essentially similar to the hydrothermal fluids. Multiple stages of remineralization of ancient chimney deposits at the seafloor appear to produce minimal Fe-isotope fractionation. Similar affects are indicated during subsurface sulfide precipitation as demonstrated by the lack of systematic differences between δ 56 Fe values in both high-temperature, Fe-rich black smokers and lower-temperature, Fe-depleted vents.

Chemical Geology↗
USGS2019

Aluminum mobility in mildly acidic mine drainage: Interactions between hydrobasaluminite, silica and trace metals from the nano to the meso-scale

Aluminum precipitates control the hydrochemistry and mineralogy of a broad variety of environments on Earth (e.g., acid mine drainage, AMD, coastal wetlands, boreal and alpine streams, tropical acid sulfate soils, laterites and bauxites, …). However, the geochemical and mineralogical processes controlling Al (and other associated metals and metalloids) transport and removal in those environments are not fully understood. The geochemical system of Paradise Portal (Colorado, USA) comprises sulfate-rich mildly acidic waters, the hydrochemistry of which is directly controlled by the massive precipitation of hydrobasaluminite Al 4 (SO 4 )(OH) 10 ·12-36H 2 O. Three connected but discernible aluminum precipitation stages were identified and described: 1) nanoparticle formation and size decrease along the creek, 2) hydrobasaluminite neoformation on the riverbed, and 3) precipitate accretion and accumulation on the riverbed leading to Al and Fe banded formations. The co-occurrence of Al and Si in the system was observed, recording significant amounts of Si accompanying the three different components of the system (i.e., nanoparticles and fresh and aged Al-precipitates). Also, abrupt and minor changes in the sedimentary record were described and proposed to be the response of the system to seasonal and interannual changes in AMD chemistry. Concerning the mobility of other metals and metalloids, P, Th, V, W, Ti and B showed a tendency to be preferentially incorporated into hydrobasaluminite, while others like Be, As, Se or Ba tend to remain dissolved in the water.

Chemical Geology↗
USGS2022

The role of organic matter diversity on the Re-Os systematics of organic-rich sedimentary units: Insights into the controls of isochron age determinations from the lacustrine Green River Formation

The range of 187 Re/ 188 Os values measured from samples of five organic-rich lacustrine mudstones units in the Eocene Green River Formation in the easternmost Uinta Basin covaries with organic matter diversity driven by changing water column conditions. A set of samples from the Douglas Creek Member has the highest pristane/phytane ratio and lowest β-carotane/ n -C 30 ratio compared to overlying units, indicating deposition in an oxic-anoxic environment with low salinity that would have allowed for the accumulation of a diverse assemblage of aquatic organisms. These samples define the broadest 187 Re/ 188 Os range of 1504. In contrast, samples from the R6 and Mahogany zones possess lower pristane/phytane ratios and higher β-carotane/ n -C 30 ratios indicating deposition in a more restricted lacustrine environment with elevated salinities and alkalinities that would have limited aquatic organic matter diversity. The R6 and Mahogany zones have the narrowest range of 187 Re/ 188 Os values measured in this study of 254.9 and 154.6, respectively. As noted by previous workers, these results suggest that organic matter diversity plays a primary role in determining the range of 187 Re/ 188 Os ratios in a sample set, and in turn the uncertainty of Re-Os age determinations from organic-rich sedimentary rocks. The Re-Os data from the R3 zone and R6 zone yield ages of 49.7 ± 3.4 Ma and 42.0 ± 18 Ma, respectively, which are statistically indistinguishable based on 2σ uncertainty from three previously reported Re-Os age determinations and those provided by 40 Ar/ 39 Ar geochronology of interbedded volcanic ash beds. Although the age uncertainty is high, these findings further highlight the importance of Re-Os geochronology in lacustrine basins, particularly those with thick mudstone successions that lack volcanic ash layers, reliable biostratigraphy , or magnetostratigraphic control. In these cases, even ages with large uncertainties can be useful to constrain burial history and thermal history models. Together, the initial 187 Os/ 188 Os ratios of five sets of samples analyzed from the Uinta Basin define the largest Os isotope stratigraphic record from any lacustrine basin compiled to date and record a shift from a value of 1.40 to 1.48 between the R3 and R4 zones in the lower part of the Parachute Creek Member. This small shift may signify a change in the chemical weathering products that entered the lake preserved 20 to 50 m above the contact between the Douglas Creek and the lower Parachute Creek members during a period when the basin transitioned from a shallow lake with mostly open hydrology to an alkaline lake with more frequent basin restrictions.

Colorado, Utah, Wyoming↗
USGS2016

The effects of co-contaminants and native wetland sediments on the activity and dominant transformation mechanisms of a 1,1,2,2-tetrachloroethane (TeCA)-degrading enrichment culture

Bioremediation strategies, including bioaugmentation with chlorinated ethene-degrading enrichment cultures, have been successfully applied in the cleanup of subsurface environments contaminated with tetrachloroethene (PCE) and/or trichloroethene (TCE). However, these compounds are frequently found in the environment as components of mixtures that may also contain chlorinated ethanes and methanes. Under these conditions, the implementation of bioremediation may be complicated by inhibition effects, particularly when multiple dehalorespirers are present. We investigated the ability of the 1,1,2,2-tetrachloroethane (TeCA)-dechlorinating culture WBC-2 to biotransform TeCA alone, or a mixture of TeCA plus PCE and carbon tetrachloride (CT), in microcosms. The microcosms contained electron donors provided to biostimulate the added culture and sediment collected from a wetland where numerous “hotspots” of contamination with chlorinated solvent mixtures exist. The dominant TeCA biodegradation mechanism mediated by the WBC-2 culture in the microcosms was different in the presence of these wetland sediments than in the sediment-free enrichment culture or in previous WBC-2 bioaugmented microcosms and column tests conducted with wetland sediment collected at nearby sites. The co-contaminants and their daughter products also inhibited TeCA biodegradation by WBC-2. These results highlight the need to conduct biodegradability assays at new sites, particularly when multiple contaminants and dehalorespiring populations are present.

Chemosphere↗
USGS2012

Determination of nonylphenol isomers in landfill leachate and municipal wastewater using steam distillation extraction coupled with comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry

4-Nonylphenols (4-NPs) are known endocrine disruptors and by-products of the microbial degradation of nonylphenol polyethoxylate surfactants. One of the challenges to understanding the toxic effects of nonylphenols is the large number of isomers that may exist in environmental samples. In order to attribute toxic effects to specific compounds, a method is needed for the separation and quantitation of individual nonylphenol isomers. The pre-concentration methods of solvent sublimation, solid-phase extraction or liquid–liquid extraction prior to chromatographic analysis can be problematic because of co-extraction of thousands of compounds typically found in complex matrices such as municipal wastewater or landfill leachate. In the present study, steam distillation extraction (SDE) was found to be an effective pre-concentration method for extraction of 4-NPs from leachate and wastewater, and comprehensive two-dimensional gas chromatography (GC × GC) coupled with fast mass spectral data acquisition by time-of-flight mass spectrometry (ToFMS) enhanced the resolution and identification of 4-NP isomers. Concentrations of eight 4-NP isomers were determined in leachate from landfill cells of different age and wastewater influent and effluent samples. 4-NP isomers were about 3 times more abundant in leachate from the younger cell than the older one, whereas concentrations in wastewater effluent were either below detection limits or <1% of influent concentrations. 4-NP isomer distribution patterns were found to have been altered following release to the environment. This is believed to reflect isomer-specific degradation and accumulation of 4-NPs in the aquatic environment.

Journal of Chromatography A↗
USGS2009

The geochemistry of environmentally important trace elements in UK coals, with special reference to the Parkgate coal in the Yorkshire–Nottinghamshire Coalfield, UK

The Parkgate coal of Langsettian age in the Yorkshire–Nottinghamshire coalfield is typical of many coals in the UK in that it has a high sulphur (S) content. Detailed information on the distribution of the forms of S, both laterally and vertically through the seam, was known from previous investigations. In the present work, 38 interval samples from five measured sections of the coal were comprehensively analysed for major, minor and trace elements and the significance of the relationships established using both raw and centered log transformed data. The major elements are used to quantify the variations in the inorganic and organic coal components and determine the trace element associations. Pyrite contains nearly all of the Hg, As, Se, Tl and Pb and is also the major source of the Mo, Ni, Cd and Sb. The clays contain the following elements in decreasing order of association: Rb, Cs, Li, Ga, U, Cr, V, Sc, Y, Bi, Cu, Nb, Sn, Te and Th. Nearly all of the Rb is present in the clay fraction, whereas for elements such as V, Cu and U, a significant amount is thought to be present in the organic matter, based on the K vs trace element regression equations. Only Ge, and possibly Be, would appear to have a dominant organic source. The trace element concentrations are calculated for pyrite, the clay fraction and organic matter. For pyrite it is noted that concentrations agree with published data from the Yorkshire–Nottinghamshire coalfield and also that Tl concentrations (median of 0.33 ppm) in the pyrite are greater than either Hg or Cd. Unlike these elements, Tl has attracted less attention and possibly more information is needed on its anthropogenic distribution and impacts on man and the environment. A seawater source is thought to be responsible for the high concentrations of S, Cl and the non-detrital trace elements in the Parkgate coal. Indicative of the seawater control is the Th/U ratio, which expresses the detrital to non-detrital element contributions. Using other elements, similar ratios can be calculated, which in combination offer greater interpretative value.

Yorkshire–Nottinghamshire coalfield↗
USGS2010

Organic petrology of subbituminous carbonaceous shale samples from Chalāw, Kabul Province, Afghanistan: Considerations for paleoenvironment and energy resource potential

Neogene (?) subbituminous carbonaceous shale deposits from Chalāw, Afghanistan, were investigated through organic petrology techniques and standard coal analyses to determine paleoenvironment and potential for resource utilization. The Chalāw deposit, approximately 30 km southeast of Kabul, currently is exploited for brick making and domestic heating and cooking. Three multiple-bench channel samples of the mined bed at Chalāw were collected and evaluated. The presence of significant huminite (ranging from 0.2 to 59.0 vol.%, mineral-inclusive basis) is suggestive of a terrestrial lignin-rich precursor plant material. Measured reflectance values of 0.38–0.55% indicate subbituminous rank. This rank suggests burial depths of approximately 1500 m and maximum temperatures of approximately 50 °C. Structured liptinite macerals generally are absent except for some fluorescing morphologies interpreted to be poorly-preserved root cork suberinite. Sponge spicule bioliths including gemmoscleres and megascleres are common. These petrographic observations, in addition to high mineral matter content (33 to > 95 vol.%), medium to high sulfur content (2.1–11.5 wt.%, dry basis; db), and the presence of common gastropod? shell fragments and an aragonite-needle chalk bed are consistent with, but not directly indicative of, a marginal marine or estuarine mangrove depositional environment. However, additional data are necessary to confirm this hypothesis and deposition in a freshwater environment cannot be ruled out at this time. Commercial-scale development and utilization of the Chalāw deposit as a thermal fuel resource may be possible using a fluidized bed combustion system which could accept the low-quality mine product currently produced. Samples examined herein contain high-ash yield (45–90 wt.%, db), high total moisture content (17–39 wt.%), low calorific value (980–6860 Btu/lb, m,mmf), and have poor agglomerating properties (FSI = 0), consistent with fuels utilized in fluidized bed combustors. However, delineation of the extent of the deposit through field investigation will be necessary to make a quantified resource estimate for mine planning.

Kabul Province↗
USGS2022

Maturation study of vitrinite in carbonaceous shales and coals: Insights from hydrous pyrolysis

The presence of vitrinite in sedimentary rocks of post-Silurian age allows its reflectance to be used to estimate the thermal maturation of organic matter in petroleum systems. Increasing reflectance of vitrinite, which is primarily driven by aromaticity, depends primarily on the time and temperature attributes of its evolutionary pathway. This study evaluated carbonaceous shales proximal to coal measures and coal samples via isothermal hydrous pyrolysis (HP) to compare differences in the maturation pathways of vitrinite. Sample residues were analysed via vitrinite reflectance (VRo), geochemical screening tests (organic carbon and programmed temperature pyrolysis), and infrared spectroscopy. The study included samples from Indian and North American basins, to observe differences in vitrinite evolution with respect to enclosing mineral matrix, starting degree of aromaticity, organic matter types, stratigraphic age, and depositional environment. The organic content of HP residues shows an intuitive response to the thermal stress of HP, e.g., a general depletion of total organic carbon (TOC) content, pyrolyzate (S2), and hydrogen index with increasing HP temperature. Infrared proxies including C-factor and CH2/CH3 generally decrease with increasing thermal maturity indicating loss of O via CO2 generation and the thermal cracking of aliphatic organic matter. Tmax, production index (PI), and VRo show intuitive increasing values with respect to HP temperature. The least mature sample (0.48 ± 0.05% VRo) generally experienced the maximum change in these parameters during maturation, whereas the most mature sample (0.99 ± 0.06% VRo) generally showed the least change. This observation is consistent with higher kinetic barriers to reaction in more aromatic vitrinite which contains higher bond dissociation energies. Devolatilization of vitrinite during HP causes formation of gas evacuation vacuoles and contraction cracks in the vitrinite grains of both coal and carbonaceous shale. Similarities in vitrinite response to HP between coal and carbonaceous shale suggest that thermal evolution of the vitrinite maceral is principally controlled by inherent rate-limiting kinetic parameters related to its molecular structure. Whereas, the stratigraphic age, sedimentary environment, surrounding organic matter, lithology, and catalysis by mineral composition have less effect. To further improve our understanding of vitrinite aromatization and kinetic parameters, future studies of vitrinite reflectance thermal evolution with temperature should include coal and carbonaceous shale from the same stratigraphic section and extant woody tissue from modern vascular plants.

International Journal of Coal Geology↗
USGS2008

Anatomy of a shoreface sand ridge revisited using foraminifera: False Cape Shoals, Virginia/North Carolina inner shelf

Certain details regarding the origin and evolution of shelf sand ridges remain elusive. Knowledge of their internal stratigraphy and microfossil distribution is necessary to define the origin and to determine the processes that modify sand ridges. Fourteen vibracores from False Cape Shoal A, a well-developed shoreface-attached sand ridge on the Virginia/North Carolina inner continental shelf, were examined to document the internal stratigraphy and benthic foraminiferal assemblages, as well as to reconstruct the depositional environments recorded in down-core sediments. Seven sedimentary and foraminiferal facies correspond to the following stratigraphic units: fossiliferous silt, barren sand, clay to sandy clay, laminated and bioturbated sand, poorly sorted massive sand, fine clean sand, and poorly sorted clay to gravel. The units represent a Pleistocene estuary and shoreface, a Holocene estuary, ebb tidal delta, modern shelf, modern shoreface, and swale fill, respectively. The succession of depositional environments reflects a Pleistocene sea-level highstand and subsequent regression followed by the Holocene transgression in which barrier island/spit systems formed along the Virginia/North Carolina inner shelf ???5.2 ka and migrated landward and an ebb tidal delta that was deposited, reworked, and covered by shelf sand.

Continental Shelf Research↗