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At least 73 records · Page 4Linked to original sources

A gel probe equilibrium sampler for measuring arsenic porewater profiles and sorption gradients in sediments: II. Field application to Haiwee reservoir sediment

Arsenic (As) geochemistry and sorption behavior were measured in As- and iron (Fe)-rich sediments of Haiwee Reservoir by deploying undoped (clear) polyacrylamide gels and hydrous ferric oxide (HFO)-doped gels in a gel probe equilibrium sampler, which is a novel technique for directly measuring the effects of porewater composition on As adsorption to Fe oxides phases in situ. Arsenic is deposited at the sediment surface as As(V) and is reduced to As(III) in the upper layers of the sediment (0-8 cm), but the reduction of As(V) does not cause mobilization into the porewater. Dissolved As and Fe concentrations increased at depth in the sediment column driven by the reductive dissolution of amorphous Fe(III) oxyhydroxides and conversion to a mixed Fe(II, III) green rust-type phase. Adsorption of As and phosphorous (P) onto HFO-doped gels was inhibited at intermediate depths (10-20 cm), possibly due to dissolved organic or inorganic carbon, indicating that dissolved As concentrations were at least partially controlled by porewater composition rather than surface site availability. In sediments that had been recently exposed to air, the region of sorption inhibition was not observed, suggesting that prior exposure to air affected the extent of reductive dissolution, porewater chemistry, and As adsorption behavior. Arsenic adsorption onto the HFO-doped gels increased at depths >20 cm, and the extent of adsorption was most likely controlled by the competitive effects of dissolved phosphate. Sediment As adsorption capacity appeared to be controlled by changes in porewater composition and competitive effects at shallower depths, and by reductive dissolution and availability of sorption sites at greater burial depths. ?? 2008 American Chemical Society.

Environmental Science & Technology↗

Potential health effects of contaminant mixtures from point and nonpoint sources on fish and frogs in the New Jersey Pinelands

Aquatic ecosystems convey complex contaminant mixtures from anthropogenic pollution on a global scale. Point (e.g., municipal wastewater) and nonpoint sources (e.g., stormwater runoff) are both drivers of contaminant mixtures in aquatic habitats. The objectives of this study were to identify the contaminant mixtures present in surface waters impacted by both point and nonpoint sources, to determine if aquatic biota (amphibian and fish) health effects (testicular oocytes and parasites) occurred at these sites, and to understand if differences in biological and chemical measures existed between point (on-stream) and nonpoint sources (off-stream). To accomplish this, water chemistry, fishes, and frogs were collected from 21 sites in the New Jersey Pinelands, United States. Off-stream sites consisted of 3 reference and 10 degraded wetlands. On-stream sites consisted of two reference lakes and six degraded steams/lakes (four sites above and two sites below wastewater outfalls). Surface water was collected 4 times at each site and analyzed for 133 organic and inorganic contaminants. One native and five non-native fish species were collected from streams/lakes and native green frogs from wetlands (ponds and stormwater basins). Limited differences in contaminant concentrations were observed in reference and degraded wetlands but for streams/lakes, results indicated that landscape alteration, (upland agricultural and developed land) was the primary driver of contaminant concentrations rather than municipal wastewater. Incidence of estrogenic endocrine disruption (intersex) was species dependent with the highest prevalence observed in largemouth bass and black crappie and the lowest prevalence observed in green frogs and tessellated darters. Parasite prevalence was site and species dependent. Prevalence of eye parasites increased with increasing concentrations of industrial, mycotoxin, and cumulative inorganic contaminants. These findings are critical to support the conservation, protection, and management of a wide range of aquatic species in the Pinelands and elsewhere as habitat loss, alteration, and fragmentation increase with increasing development.

New Jersey↗

Numerical ages of Holocene tributary debris fans inferred from dissolution pitting on carbonate boulders in the Grand Canyon of Arizona

Carbonate boulders transported down steep tributary channels by debris flow came to rest on Holocene debris fans beside the Colorado River in Grand Canyon National Park. Weakly acidic rainfall and the metabolic activity of blue-green algae have produced roughly hemispheric dissolution pits as much as 2-cm deep on the initially smooth surfaces of the boulders. The average depth of dissolution pits increases with relative age of fan surfaces. The deepening rate averages 2.4 mm/1000 yr (standard error = 0.2 mm/1000 yr), as calculated from several radiometrically dated surfaces and an archeological structure. This linear rate, which appears constant over at least the past 3000 yr, is consistent with field relations limiting the maximum age of the fans and with the physical chemistry of limestone dissolution. Dissolution-pit measurements (n = 6973) were made on 617 boulders on 71 fan surfaces at the 26 largest debris fans in Grand Canyon. Among these fan surfaces, the average pit depth ranges from 1.2 to 17.4 mm, and the resulting pit dissolution ages range from 500 to 7300 cal yr B.P. Most (75%) surfaces are younger than 3000 yr, probably because of removal of older debris fans by the Colorado River. Many of the ages are close to 800, 1600, 2300, 3100, or 4300 cal yr B.P. If not the result of differential preservation of fan surfaces, this clustering implies periods of heightened debris-flow activity and increased precipitation.

Quaternary Research↗

Evidence for hydraulic heterogeneity and anisotropy in the mostly carbonate Prairie du Chien Group, southeastern Minnesota, USA

In southeastern Minnesota, Paleozoic bedrock aquifers have typically been represented in groundwater flow simulations as isotropic, porous media. To obtain a more accurate hydrogeologic characterization of the Ordovician Prairie du Chien Group, a new approach was tested, combining detailed geologic observations, particularly of secondary porosity, with hydraulic data. Lithologic observations of the depositional and erosional history of the carbonate-dominated bedrock unit constrained characterization of both primary (matrix) and secondary porosity from outcrops and core. Hydrostratigraphic data include outcrop and core observations along with core plug permeability tests. Hydrogeologic data include discrete interval aquifer tests, borehole geophysics, water chemistry and isotope data, and dye trace studies. Results indicate that the Prairie du Chien Group can be subdivided into the Shakopee aquifer at the top, consisting of interbedded dolostone, sandstone and shale, and the underlying Oneota confining unit consisting of thickly bedded dolostone. The boundary between these two hydrogeologic units does not correspond to lithostratigraphic boundaries, as commonly presumed. Groundwater flow in the Shakopee aquifer is primarily through secondary porosity features, most commonly solution-enlarged bedding planes and sub-horizontal and vertical fractures. Regional scale preferential development of cavernous porosity and permeability along specific stratigraphic intervals that correspond to paleokarst were also identified, along with a general depiction of the distribution of vertical and horizontal fractures. The combination of outcrop and core investigations, along with borehole geophysics, discrete interval aquifer tests, water chemistry and isotope data and dye trace studies show that the Prairie du Chien Group is best represented hydrogeologically as heterogeneous and anisotropic. Furthermore, heterogeneity and anisotropy within the Prairie du Chien Group is mappable at a regional scale (>15,000 km2). ?? 2005 Elsevier B.V. All rights reserved.

Sedimentary Geology↗

Gas hydrates in sustainable chemistry

Gas hydrates have received considerable attention due to their important role in flow assurance for the oil and gas industry, their extensive natural occurrence on Earth and extraterrestrial planets, and their significant applications in sustainable technologies including but not limited to gas and energy storage, gas separation, and water desalination. Given not only their inherent structural flexibility depending on the type of guest gas molecules and formation conditions, but also the synthetic effects of a wide range of chemical additives on their properties, these variabilities could be exploited to optimise the role of gas hydrates. This includes increasing their industrial applications, understanding and utilising their role in Nature, identifying potential methods for safely extracting natural gases stored in naturally occurring hydrates within the Earth, and for developing green technologies. This review summarizes the different properties of gas hydrates as well as their formation and dissociation kinetics and then reviews the fast-growing literature reporting their role and applications in the aforementioned fields, mainly concentrating on advances during the last decade. Challenges, limitations, and future perspectives of each field are briefly discussed. The overall objective of this review is to provide readers with an extensive overview of gas hydrates that we hope will stimulate further work on this riveting field.

Chemical Society Reviews↗

Brucite microbialites in living coral skeletons: Indicators of extreme microenvironments in shallow-marine settings

Brucite [Mg(OH)2] microbialites occur in vacated interseptal spaces of living scleractinian coral colonies (Acropora, Pocillopora, Porites) from subtidal and intertidal settings in the Great Barrier Reef, Australia, and subtidal Montastraea from the Florida Keys, United States. Brucite encrusts microbial filaments of endobionts (i.e., fungi, green algae, cyanobacteria) growing under organic biofilms; the brucite distribution is patchy both within interseptal spaces and within coralla. Although brucite is undersaturated in seawater, its precipitation was apparently induced in the corals by lowered pCO 2 and increased pH within microenvironments protected by microbial biofilms. The occurrence of brucite in shallow-marine settings highlights the importance of microenvironments in the formation and early diagenesis of marine carbonates. Significantly, the brucite precipitates discovered in microenvironments in these corals show that early diagenetic products do not necessarily reflect ambient seawater chemistry. Errors in environmental interpretation may arise where unidentified precipitates occur in microenvironments in skeletal carbonates that are subsequently utilized as geochemical seawater proxies. ?? 2005 Geological Society of America.

Geology↗

Monitoring marine eruptions

Introduction Submarine volcanoes produce much of the same seismicity and eruptive activity as subaerial volcanoes and can pose hazards to society. Although they can be monitored with similar techniques and methods as described in other chapters of this volume, their submerged location brings unique challenges. This chapter addresses these challenges and provides recommendations for monitoring volcanoes fully or partly in marine environments to meet the capabilities described in other chapters of this volume. The United States and its territories host dozens of submarine volcanoes with most (around 60) in the Commonwealth of the Northern Mariana Islands. Approximately 20 of the Northern Mariana Islands submarine volcanoes are known to be hydrothermally active, and 10 have confirmed eruptions since the 1950s (for example, Baker and others, 2008; Tepp and others, 2019a). Nine of those volcanoes were considered by the National Volcanic Threat Assessment (Ewert and others, 2018) to have a combination of eruptive type and summit depth that poses a higher risk of hazardous eruptions, although only one was listed as a moderate (level 3) threat. Other notable submarine volcanoes of interest to the United States that have historically erupted are Axial Seamount off the Washington State coast, Kamaʻehuakanaloa in Hawaiʻi, and Vailuluʻu seamount in American Samoa. All of these, however, have a low risk of hazards because of their depth (greater than 600 meters below sea level) and eruptive type and so are not included in the National Volcanic Threat Assessment. In addition to submarine volcanoes, the submerged flanks of island volcanoes can also be a source of hazardous submarine eruptions—for example, the 1877 eruption of Mauna Loa, Hawai‘i, in Kealakekua Bay (Wanless and others, 2006). The most notable submarine eruption in recent times was the 2022 eruption of Hunga Tonga–Hunga Haʻapai in Tonga, which was one of the largest eruptions on Earth in the past 100 years. It created a massive volcanic plume, unprecedented shock waves, and far-reaching tsunami (Lynett and others, 2022). Other recent submarine eruptions in the Pacific Ocean Basin have produced subaerial plumes that reached aircraft heights (Carey and others, 2014) and large pumice rafts that can affect marine traffic and harbors (for example, Jutzeler and others, 2014; Kornei, 2019). These examples illustrate the potential hazards of major submarine eruptions. Yet, submarine volcanoes are largely unmonitored, and many eruptions occur that are unnoticed or only identified hours or days afterward. Within U.S. territory, submarine volcanoes in the Northern Mariana Islands have been known to produce eruptive activity that can affect society. Reports from fishermen and other marine vessels in the Northern Mariana Islands have noted underwater explosions, sea-surface discoloration, and bubbling water, all of which are known to be signs of submarine volcanic activity. South Sarigan seamount, located about 160 kilometers (km) north of Saipan, erupted in 2010 from greater than 150 meters below the sea surface, resulting in a gas and ash plume that reached more than 11.9 km into the atmosphere (for example, Searcy, 2013; Embley and others, 2014), high enough to affect international air traffic. Precursory and co-eruptive seismicity was detected on the regional Northern Mariana Islands seismic network (Searcy, 2013) and on global monitoring instruments (Green and others, 2013). Monitoring of submarine volcanoes is best accomplished with marine-based instrumentation, which is also useful for monitoring small island volcanoes that may not have the land area necessary for comprehensive subaerial monitoring. The primary marine-based instrumentation used for submarine volcanoes includes ocean-bottom pressure sensors to assess sea-floor deformation, ocean-bottom seismometers (OBSs) to detect seismicity, and both moored and ocean-bottom hydrophones to detect submarine explosions. Other sensors offer important monitoring data, such as turbidity, temperature, and chemistry of hydrothermal emissions. Marine-based instruments are typically deployed in campaign-style networks with no real-time telemetry owing to cost considerations and technical limitations. However, when necessary, marine instruments can be operated in real time using cables to transmit data to land-based facilities; other technologies for this purpose are in use or in development, such as acoustic transmission from the instrument to a moored buoy (Matsumoto and others, 2016) and a winch-based system with a satellite antenna that is part of the instrument mooring (Matsumoto and others, 2019). Emerging technologies for marine-based monitoring may be considered as part of a future monitoring plan. These technologies include ocean gliders and floats with on-board hydrophones that have been used to record earthquakes and submarine eruptions (for example, Matsumoto and others, 2013; Sukhovich and others, 2015) and fiber-optic cables that have been used as strainmeters to detect earthquakes (for example, Marra and others, 2018; Lindsey and others, 2019). Land-based instruments and satellites can also provide some capability for monitoring submarine volcanoes, but they provide more limited observations than marine-based instrumentation.

Scientific Investigations Report↗

U.S. Geological Survey and Bureau of Land Management Cooperative Coalbed Methane Project in the Powder River Basin, Wyoming

The Bureau of Land Management (BLM) Wyoming Reservoir Management Group and the U.S. Geological Survey (USGS) began a cooperative project in 1999 to collect technical and analytical data on coalbed methane (CBM) resources and quality of the water produced from coalbeds in the Wyoming part of the Powder River Basin. The agencies have complementary but divergent goals and these kinds of data are essential to accomplish their respective resource evaluation and management tasks. The project also addresses the general public need for information pertaining to Powder River Basin CBM resources and development. BLM needs, which relate primarily to the management of CBM resources, include improved gas content and gas in-place estimates for reservoir characterization and resource/reserve assessment, evaluation, and utilization. USGS goals include a basinwide assessment of CBM resources, an improved understanding of the nature and origin of coalbed gases and formation waters, and the development of predictive models for the assessment of CBM resources that can be used for such purposes in other basins in the United States (for example, the Bighorn, Greater Green River, and Williston Basins) and in other countries throughout the world (for example, Indonesia, New Zealand, and the Philippines). Samples of coal, produced water, and gas from coalbed methane drill holes throughout the Powder River Basin, many of which are adjacent to several active mine areas (figs. 1, 2), have been collected by personnel in the USGS, BLM Reservoir Management Group, and Casper and Buffalo BLM Field Offices. Sampling was done under confidentiality agreements with 29 participating CBM companies and operators. Analyses run on the samples include coal permeability, coal quality and chemistry, coal petrography and petrology, methane desorption and adsorption, produced-water chemistry, and gas composition and isotopes. The USGS has supplied results to the BLM Reservoir Management Group for their resource management needs, and data are released when the terms of the confidentiality agreements are completed and consent is obtained.

Fact Sheet↗

Effects of carbaryl on green frog (Rana clamitans) tadpoles: Timing of exposure versus multiple exposures

The majority of studies on pesticide impacts have evaluated the effects of single exposures. However, multiple exposures to a pesticide may be more prevalent. The objective of our study was to determine how multiple exposures versus single exposure at different times during development affected survival to metamorphosis, tadpole survival, tadpole mass, and tadpole developmental stage of green frog (Rana clamitans) tadpoles reared at low and high density in outdoor cattle tank ponds. Tadpoles were exposed to carbaryl zero, one, two, or three times at 14-d intervals. We applied single doses of carbaryl at one of three times, specifically during early, mid, or late development. Overall, we found that multiple exposures had a greater impact than single exposures during development. More individuals reached metamorphosis in ponds exposed to multiple doses of carbaryl compared with controls, indicating that the presence of carbaryl stimulated metamorphosis. The presence of carbaryl in the aquatic environment also resulted in more developed tadpoles compared with controls. Tadpoles in control ponds did not reach metamorphosis and were less developed than individuals exposed to carbaryl; this effect indicates that, under ideal conditions, green frogs could overwinter in ponds so that greater size could be attained before metamorphosis in the following spring or summer. Our study demonstrated the importance of including realistic application procedures when evaluating the effects of a pesticide and that multiple exposures to a short-lived pesticide are more likely to affect an amphibian population.

Environmental Toxicology and Chemistry↗

Studies of the environmental fate and effect of aircraft deicing fluids: Detection of 5-methyl-1H-benzotriazole in the fathead minnow (Pimephales promelas)

This paper presents the results of a number of field and laboratory studies to evaluate the environmental impact of aircraft deicing and anti-icing fluids (ADAFs) on aquatic systems. Both 5-methyl-1H-benzotriazole (5-MeBt) and 4-methyl-1H-benzotriazole (4-MeBt), known additives to ADAFs, were found in whole-tissue extracts from minnows placed downstream of an effluent outfall that receives ADAF contaminated runoff from General Mitchell International Airport (Milwaukee, WI, USA). Neither of these compounds was detected in tissues from minnows placed upstream from the airport. A toxicity assessment of water collected during the minnow exposure studies utilizing Hyalella azteca, Pimephales promelas, and Ceriodaphnia dubia showed greater toxicity in a secondary airport outfall containing ADAFs when compared to upstream non-ADAF-contaminated samples. In two 28-d static renewal tests using 5-MeBt laboratory-fortified waters, 5-MeBt was detected in whole-tissue extracts of minnows at all concentrations tested. In studies using laboratory water fortified with 5-MeBt, the median lethal concentration (LC50) of 5-MeBt for P. promelas was found to be 22.0 mg/L. The LC50 for C. dubia to 5-MeBt laboratory-fortified water was found to be 81.3 mg/L. The 25% inhibition concentration (IC25) of 5-MeBt for the green alga Selenastrum capricornutum was 23.2 mg/L, and the average median effective concentration (EC50) for Microtox was 4.25 mg/L. The results of these field and lab studies indicate that additives, other than glycols, used in aircraft deicing fluids can be found in aquatic systems and may be of greater risk than previously believed.

Wisconsin↗

TiO 2 as a photocatalyst for control of the aquatic invasive alga, Cladophora, under natural and artificial light

Cladophora, a nuisance and invasive, filamentous algae (Chlorophyta), massively accumulates along the shores of the lower Great Lakes each summer causing great economic damage and compromising recreational opportunity and perhaps public health. In vitro experiments showed that Cladophora samples were physically and biologically degraded when subjected to TiO 2 -mediated photocatalysis. For the most successful photocatalytic process, TiO 2 was immobilized on a glass surface and used in combination with either sunlight or artificial UV light. The loss of vital algal pigments was monitored using UV–vis spectrophotometry, and cell structural changes were determined by microscopic observation. Cladophora, in the presence of TiO 2 -covered glass beads, experienced a loss of chloroplast pigments after 2 h of UV lamp light irradiation. In a separate experiment, sunlight exposure over 4 days (∼24 h) resulted in the complete oxidative degradation of the green chloroplast pigments, verified by the UV spectra of the algal extracts. These results suggest that TiO 2 , mobilized on sunlit silicates may be useful in controlling growth and survival of this alga in the Great Lakes, thus mitigating many of the economic, aesthetic ecological impacts of this invasive alga.

Journal of Photochemistry and Photobiology A: Chem↗

Mercury cycling in stream ecosystems. 3. Trophic dynamics and methylmercury bioaccumulation

Trophic dynamics (community composition and feeding relationships) have been identified as important drivers of methylmercury (MeHg) bioaccumulation in lakes, reservoirs, and marine ecosystems. The relative importance of trophic dynamics and geochemical controls on MeHg bioaccumulation in streams, however, remains poorly characterized. MeHg bioaccumulation was evaluated in eight stream ecosystems across the United States (Oregon, Wisconsin, and Florida) spanning large ranges in climate, landscape characteristics, atmospheric Hg deposition, and stream chemistry. Across all geographic regions and all streams, concentrations of total Hg (THg) in top predator fish and forage fish, and MeHg in invertebrates, were strongly positively correlated to concentrations of filtered THg (FTHg), filtered MeHg (FMeHg), and dissolved organic carbon (DOC); to DOC complexity (as measured by specific ultraviolet absorbance); and to percent wetland in the stream basins. Correlations were strongest for nonurban streams. Although regressions of log[Hg] versus δ 15 N indicate that Hg in biota increased significantly with increasing trophic position within seven of eight individual streams, Hg concentrations in top predator fish (including cutthroat, rainbow, and brown trout; green sunfish; and largemouth bass) were not strongly influenced by differences in relative trophic position. Slopes of log[Hg] versus δ 15 N, an indicator of the efficiency of trophic enrichment, ranged from 0.14 to 0.27 for all streams. These data suggest that, across the large ranges in FTHg (0.14−14.2 ng L −1 ), FMeHg (0.023−1.03 ng L −1 ), and DOC (0.50−61.0 mg L −1 ) found in this study, Hg contamination in top predator fish in streams likely is dominated by the amount of MeHg available for uptake at the base of the food web rather than by differences in the trophic position of top predator fish.

Environmental Science & Technology↗

Problems related to water quality and algal control in Lopez Reservoir, San Luis Obispo County, California

Lopez Reservoir is a multipurpose impoundment that was filled during a 30-week period following a series of intense storms during the winter 1968-69. The reservoir is used for flood control, water supply, and recreation, including swimming, fishing, and boating. At full pool Lopez Reservoir has a surface area of 974 acres (394 square hectometres), a maximum depth of 145 feet (44.2 metres), and a shoreline of 22 miles (35.4 kilometres). Nuisance algal blooms have been a frequent occurrence in the reservoir since the first summer after filling (1969). The dominant bloom species was the blue-green alga Anabaena unispora. Cospecies were the diatoms Stephanodiscus astraea and Cyclotella operculata and the green algae Pediastrum duplex and Sphaerocystis schroeteri . During a bloom of A. unispora in May 1972, the total cell count at the lake surface was almost 100,000 cells per millilitre of water. Lopez Reservoir is thermally stratified from April until November. Dissolved-oxygen stratification closely parallels the thermal stratification. Anoxic conditions begin to develop in mid-May, and by early July all water below a depth of 40 feet (12 metres) is oxygen deficient. The application of copper sulfate (CuSO 4 ) to reduce algal production has met with little success. Possible application rates and methods of determining application rates based upon water chemistry are presented.

California↗

Development, evaluation, and application of sediment quality targets for assessing and managing contaminated sediments in Tampa Bay, Florida

Tampa Bay is a large, urban estuary that is located in west central Florida. Although water quality conditions represent an important concern in this estuary, information from numerous sources indicates that sediment contamination also has the potential to adversely affect aquatic organisms, aquatic-dependent wildlife, and human health. As such, protecting relatively uncontaminated areas of the bay from contamination and reducing the amount of toxic chemicals in contaminated sediments have been identified as high-priority sediment management objectives for Tampa Bay. To address concerns related to sediment contamination in the bay, an ecosystem-based framework for assessing and managing sediment quality conditions was developed that included identification of sediment quality issues and concerns, development of ecosystem goals and objectives, selection of ecosystem health indicators, establishment of metrics and targets for key indicators, and incorporation of key indicators, metrics, and targets into watershed management plans and decision-making processes. This paper describes the process that was used to select and evaluate numerical sediment quality targets (SQTs) for assessing and managing contaminated sediments. These SQTs included measures of sediment chemistry, whole-sediment and pore-water toxicity, and benthic invertebrate community structure. In addition, the paper describes how the SQTs were used to develop site-specific concentration-response models that describe how the frequency of adverse biological effects changes with increasing concentrations of chemicals of potential concern. Finally, a key application of the SQTs for defining sediment management areas is discussed.

Florida↗

Major and trace elements in Mahogany zone oil shale in two cores from the Green River Formation, piceance basin, Colorado

The Parachute Creek Member of the lacustrine Green River Formation contains thick sequences of rich oil-shale. The richest sequence and the richest oil-shale bed occurring in the member are called the Mahogany zone and the Mahogany bed, respectively, and were deposited in ancient Lake Uinta. The name "Mahogany" is derived from the red-brown color imparted to the rock by its rich-kerogen content. Geochemical abundance and distribution of eight major and 18 trace elements were determined in the Mahogany zone sampled from two cores, U. S. Geological Survey core hole CR-2 and U. S. Bureau of Mines core hole O1-A (Figure 1). The oil shale from core hole CR-2 was deposited nearer the margin of Lake Uinta than oil shale from core hole O1-A. The major- and trace-element chemistry of the Mahogany zone from each of these two cores is compared using elemental abundances and Q-mode factor modeling. The results of chemical analyses of 44 CR-2 Mahogany samples and 76 O1-A Mahogany samples are summarized in Figure 2. The average geochemical abundances for shale (1) and black shale (2) are also plotted on Figure 2 for comparison. The elemental abundances in the samples from the two cores are similar for the majority of elements. Differences at the 95% probability level are higher concentrations of Ca, Cu, La, Ni, Sc and Zr in the samples from core hole CR-2 compared to samples from core hole O1-A and higher concentrations of As and Sr in samples from core hole O1-A compared to samples from core hole CR-2. These differences presumably reflect slight differences in depositional conditions or source material at the two sites. The Mahogany oil shale from the two cores has lower concentrations of most trace metals and higher concentrations of carbonate-related elements (Ca, Mg, Sr and Na) compared to the average shale and black shale. During deposition of the Mahogany oil shale, large quantities of carbonates were precipitated resulting in the enrichment of carbonate-related elements and dilution of most trace elements as pointed out in several previous studies. Q-mode factor modeling is a statistical method used to group samples on the basis of compositional similarities. Factor end-member samples are chosen by the model. All other sample compositions are represented by varying proportions of the factor end-members and grouped as to their highest proportion. The compositional similarities defined by the Q-mode model are helpful in understanding processes controlling multi-element distributions. The models for each core are essentially identical. A four-factor model explains 70% of the variance in the CR-2 data and 64% of the O1-A data (the average correlation coefficients are 0. 84 and 0. 80, respectively). Increasing the number of factors above 4 results in the addition of unique instead of common factors. Table I groups the elements based on high factor-loading scores (the amount of influence each element has in defining the model factors). Similar elemental associations are found in both cores. Elemental abundances are plotted as a function of core depth using a five-point weighted moving average of the original data to smooth the curve (Figure 3 and 4). The plots are grouped according to the four factors defined by the Q-mode models and show similar distributions for elements within the same factor. Factor 1 samples are rich in most trace metals. High oil yield and the presence of illite characterize the end-member samples for this factor (3, 4) suggesting that adsorption of metals onto clay particles or organic matter is controlling the distribution of the metals. Precipitation of some metals as sulfides is possible (5). Factor 2 samples are high in elements commonly associated with minerals of detrital or volcanogenic origin. Altered tuff beds and lenses are prevalent within the Mahogany zone. The CR-2 end-member samples for this factor contain analcime (3) which is an alteration product within the tuff beds of the Green River Formation. Th

Conference Paper↗

Reach-scale cation exchange controls on major ion chemistry of an Antarctic glacial meltwater stream

McMurdo dry valleys of Antarctica represent the largest of the ice-free areas on the Antarctic continent, containing glaciers, meltwater streams, and closed basin lakes. Previous geochemical studies of dry valley streams and lakes have addressed chemical weathering reactions of hyporheic substrate and geochemical evolution of dry valley surface waters. We examine cation transport and exchange reactions during a stream tracer experiment in a dry valley glacial meltwater stream. The injection solution was composed of dissolved Li + , Na + , K + , and Cl - . Chloride behaved conservatively in this stream, but Li + , Na + , and K + were reactive to varying degrees. Mass balance analysis indicates that relative to Cl - , Li + and K + were taken up in downstream transport and Na + was released. Simulations of conservative and reactive (first-order uptake or generation) solute transport were made with the OTIS (one-dimensional solute transport with inflow and storage) model. Among the four experimental reaches of Green Creek, solute transport simulations reveal that Li + was removed from stream water in all four reaches, K + was released in two reaches, taken up in one reach, and Na + was released in all four reaches. Hyporheic sediments appear to be variable with uptake of Li + in two reaches, uptake of K + in one reach, release of K + in two reaches, and uptake of Na + in one reach. Mass balances of the conservative and reactive simulations show that from 1.05 to 2.19 moles of Li + was adsorbed per reach, but less than 0.3 moles of K + and less than 0.9 moles of Na + were released per reach. This suggests that either (1) exchange of another ion which was not analyzed in this experiment or (2) that both ion exchange and sorption control inorganic solute transport. The elevated cation concentrations introduced during the experiment are typical of initial flows in each flow season, which flush accumulated dry salts from the streambed. We propose that the bed sediments (which compose the hyporheic zone) modulate the flushing of these salts during initial flows each season, due to ion exchange and sorption reactions.

Aquatic Geochemistry↗

Endocrine disrupting activities and geochemistry of water resources associated with unconventional oil and gas activity

The rise of hydraulic fracturing and unconventional oil and gas (UOG) exploration in the United States has increased public concerns for water contamination induced from hydraulic fracturing fluids and associated wastewater spills. Herein, we collected surface and groundwater samples across Garfield County, Colorado, a drilling-dense region, and measured endocrine bioactivities, geochemical tracers of UOG wastewater, UOG-related organic contaminants in surface water, and evaluated UOG drilling production (weighted well scores, nearby well count, reported spills) surrounding sites. Elevated antagonist activities for the estrogen, androgen, progesterone, and glucocorticoid receptors were detected in surface water and associated with nearby shale gas well counts and density. The elevated endocrine activities were observed in surface water associated with medium and high UOG production (weighted UOG well score-based groups). These bioactivities were generally not associated with reported spills nearby, and often did not exhibit geochemical profiles associated with UOG wastewater from this region. Our results suggest the potential for releases of low-saline hydraulic fracturing fluids or chemicals used in other aspects of UOG production, similar to the chemistry of the local water, and dissimilar from defined spills of post-injection wastewater. Notably, water collected from certain medium and high UOG production sites exhibited bioactivities well above the levels known to impact the health of aquatic organisms, suggesting that further research to assess potential endocrine activities of UOG operations is warranted.

Science of the Total Environment↗

The metallogeny of Late Triassic rifting of the Alexander terrane in southeastern Alaska and northwestern British Columbia

A belt of unusual volcanogenic massive sulfide (VMS) occurrences is located along the eastern margin of the Alexander terrane throughout southeastern Alaska and northwestern British Columbia and exhibits a range of characteristics consistent with a variety of syngenetic to epigenetic deposit types. Deposits within this belt include Greens Creek and Windy Craggy, the economically most significant VMS deposit in Alaska and the largest in North America, respectively. The occurrences are hosted by a discontinuously exposed, 800-km-long belt of rocks that consist of a 200- to 800-m-thick sequence of conglomerate, limestone, marine elastic sedimentary rocks, and tuff intercalated with and overlain by a distinctive unit of mafic pyroclastic rocks and pillowed flows. Faunal data bracket the age of the host rocks between Anisian (Middle Triassic) and late Norian (late Late Triassic). This metallogenic belt is herein referred to as the Alexander Triassic metallogenic belt. The VMS occurrences show systematic differences in degree of structural control, chemistry, and stratigraphic setting along the Alexander Triassic metallogenic belt that suggest important spatial or temporal changes in the tectonic environment of formation. At the southern end of the belt, felsic volcanic rocks overlain by shallow-water limestones characterize the lower part of the sequence. In the southern and middle portion of the belt, a distinctive pebble conglomerate marks the base of the section and is indicative of high-energy deposition in a near slope or basin margin setting. At the northern end of the belt the conglomerates, limestones, and felsic volcanic rocks are absent and the belt is composed of deep-water sedimentary and mafic volcanic rocks. This northward change in depositional environment and lithofacies is accompanied by a northward transition from epithermal-like structurally controlled, discontinuous, vein- and pod-shaped, Pb-Zn-Ag-Ba-(Cu) occurrences with relatively simple mineralogy, to sulfosalt-enriched VMS occurrences exhibiting characteristics of vein, diagenetic replacement, and exhalative styles of mineralization, and finally to Cu-Zn-(Co-Au) occurrences with larger and more clearly stratiform orebody morphologies. Occurrences in the middle of the belt are transitional in nature between structurally controlled types of mineralization that formed in a shallow-water, near-arc setting, to those having a more stratiform appearance, formed in a deeper water, rift-basin setting. The geologic setting in the south is consistent with shallow subaqueous emplacement on the flanks of the Alexander terrane. Northward, the setting changes to an increasingly deeper back- or intra-arc rift basin. Igneous activity in the Alexander Triassic metallogenic belt is characterized by a bimodal suite of volcanic rocks and a previously unrecognized association with mafic-ultramafic hypabyssal intrusions. Immobile trace and rare earth element (BEE) geochemical data indicate that felsic rocks in the southern portion of the belt are typical calc-alkaline rhyolites, which give way in the middle of the belt to peralkaline rhyolites. Rhyolites are largely absent in the northern part of the belt. Throughout the belt, the capping basaltic rocks have transitional geochemical signatures. Radiogenic isotope data for these rocks are also transitional (basalts and gabbros: ??-Nd = 4-9 and 87Sr/86Sr initial at 215 Ma = 0.7037-0.7074). Together these data are interpreted to reflect variable assimilation of mature island-arc crust by more primitive melts having the characteristics of either mid-ocean ridge (MORB) or intraplate (within-plate) basalts (WPB). The ore and host-rock geochemistry and the sulfosalt-rich mineralogy of the deposits are strikingly similar to recent descriptions of active sea-floor hydrothermal (white smoker) systems in back arcs of the southwest Pacific Ocean. These data, in concert with existing faunal ages, record the formation of a belt of VMS deposits

Conference Paper↗