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Investigating the potential role of persistent organic pollutants in Hawaiian green sea turtle fibropapillomatosis
It has been hypothesized for decades that environmental pollutants may contribute to green sea turtle fibropapillomatosis (FP), possibly through immunosuppression leading to greater susceptibility to the herpesvirus, the putative causative agent of this tumor-forming disease. To address this question, we measured concentrations of 164 persistent organic pollutants (POPs) and halogenated phenols in 53 Hawaiian green turtle ( Chelonia mydas ) plasma samples archived by the Biological and Environmental Monitoring and Archival of Sea Turtle Tissues (BEMAST) project at the National Institute of Standards and Technology Marine Environmental Specimen Bank. Four groups of turtles were examined: free-ranging turtles from Kiholo Bay (0% FP, Hawaii), Kailua Bay (low FP, 8%, Oahu), and Kapoho Bay (moderate FP, 38%, Hawaii) and severely tumored stranded turtles that required euthanasia (high FP, 100%, Main Hawaiian Islands). Four classes of POPs and seven halogenated phenols were detected in at least one of the turtles, and concentrations were low (often <200 pg/g wet mass). The presence of halogenated phenols in sea turtles is a novel discovery; their concentrations were higher than most man-made POPs, suggesting that the source of most of these compounds was likely natural (produced by the algal turtle diet) rather than metabolites of man-made POPs. None of the compounds measured increased in concentration with increasing prevalence of FP across the four groups of turtles, suggesting that these 164 compounds are not likely primary triggers for the onset of FP. However, the stranded, severely tumored, emaciated turtle group ( n = 14) had the highest concentrations of POPs, which might suggest that mobilization of contaminants with lipids into the blood during late-stage weight loss could contribute to the progression of the disease. Taken together, these data suggest that POPs are not a major cofactor in causing the onset of FP.
A universal method for the simultaneous determination of environmental pollutants in marine biological samples: Per- and polyfluoroalkyl substances and antibiotics as a case study
Conventional detection technologies for environmental contaminants have primarily focused on providing accurate qualitative and quantitative evaluations for single pollutant types, leading to increased costs and an inability to satisfy the growing demand for detecting a broader spectrum of pollutants. Here, we introduced a novel analytical method to simultaneously measure the concentration levels of diverse environmental pollutants, characterized by their distinct properties, across complex biological samples. Per- and polyfluoroalkyl substances (PFAS) and antibiotics were used as a case study due to their frequency of detection in the environment and known impacts Our method harnesses the salting-out effect of sodium chloride on proteins within the muscle tissues of 178 marine species, which significantly reduces the addition of extraneous substances, mitigates matrix interference, and avoids reliance on solid-phase extraction or dispersive extraction agents. The method provides a simultaneous pretreatment for the detection of several compounds, with detection limits from 0.002 to 0.41 ng/g dry weight, which are substantially lower than conventional methods. Overall, this method streamlines efficiency, decreases costs, lessens matrix effects, and sets a solid groundwork for future applications in the concurrent detection of a broader spectrum of environmentally pertinent pollutants with varied characteristics.
Development of high surface area organosilicate nanoparticulate thin films for use in sensing hydrophobic compounds in sediment and water
The scope of this study was to apply advances in materials science, specifically the use of organosilicate nanoparticles as a high surface area platform for passive sampling of chemicals or pre-concentration for active sensing in multiple-phase complex environmental media. We have developed a novel nanoporous organosilicate (NPO) film as an extraction phase and proof of concept for application in adsorbing hydrophobic compounds in water and sediment. We characterized the NPO film properties and provided optimization for synthesis and coatings in order to apply the technology in environmental media. NPO films in this study had a very high surface area, up to 1325 m 2 /g due to the high level of mesoporosity in the film. The potential application of the NPO film as a sorbent phase for sensors or passive samplers was evaluated using a model hydrophobic chemical, polychlorinated biphenyls (PCB), in water and sediment. Sorption of PCB to this porous high surface area nanoparticle platform was highly correlated with the bioavailable fraction of PCB measured using whole sediment chemistry, porewater chemistry determined by solid-phase microextraction fiber methods, and the Lumbriculus variegatus bioaccumulation bioassay. The surface-modified NPO films in this study were found to highly sorb chemicals with a log octanol-water partition coefficient (K ow ) greater than four; however, surface modification of these particles would be required for application to other chemicals.
Coal-Quality Information - Key to the Efficient and Environmentally Sound Use of Coal
The rock that we refer to as coal is derived principally from decomposed organic matter (plants) consisting primarily of the element carbon. When coal is burned, it produces energy in the form of heat, which is used to power machines such as steam engines or to drive turbines that produce electricity. Almost 60 percent of the electricity produced in the United States is derived from coal combustion. Coal is an extraordinarily complex material. In addition to organic matter, coal contains water (up to 40 or more percent by weight for some lignitic coals), oils, gases (such as methane), waxes (used to make shoe polish), and perhaps most importantly, inorganic matter (fig. 1). The inorganic matter--minerals and trace elements--cause many of the health, environmental, and technological problems attributed to coal use (fig. 2). 'Coal quality' is the term used to refer to the properties and characteristics of coal that influence its behavior and use. Among the coal-quality characteristics that will be important for future coal use are the concentrations, distribution, and forms of the many elements contained in the coal that we intend to burn. Knowledge of these quality characteristics in U.S. coal deposits may allow us to use this essential energy resource more efficiently and effectively and with less undesirable environmental impact.
Water security-National and global issues
Potable or clean freshwater availability is crucial to life and economic, environmental, and social systems. The amount of freshwater is finite and makes up approximately 2.5 percent of all water on the Earth. Freshwater supplies are small and randomly distributed, so water resources can become points of conflict. Freshwater availability depends upon precipitation patterns, changing climate, and whether the source of consumed water comes directly from desalination, precipitation, or surface and (or) groundwater. At local to national levels, difficulties in securing potable water sources increase with growing populations and economies. Available water improves living standards and drives urbanization, which increases average water consumption per capita. Commonly, disruptions in sustainable supplies and distribution of potable water and conflicts over water resources become major security issues for Government officials. Disruptions are often influenced by land use, human population, use patterns, technological advances, environmental impacts, management processes and decisions, transnational boundaries, and so forth.
Rare earth elements in sedimentary phosphate deposits: Solution to the global REE crisis?
The critical role of rare earth elements (REEs), particularly heavy REEs (HREEs), in high-tech industries has created a surge in demand that is quickly outstripping known global supply and has triggered a worldwide scramble to discover new sources. The chemical analysis of 23 sedimentary phosphate deposits (phosphorites) in the United States demonstrates that they are significantly enriched in REEs. Leaching experiments using dilute H 2 SO 4 and HCl, extracted nearly 100% of their total REE content and show that the extraction of REEs from phosphorites is not subject to the many technological and environmental challenges that vex the exploitation of many identified REE deposits. Our data suggest that phosphate rock currently mined in the United States has the potential to produce a significant proportion of the world's REE demand as a byproduct. Importantly, the size and concentration of HREEs in some unmined phosphorites dwarf the world's richest REE deposits. Secular variation in phosphate REE contents identifies geologic time periods favorable for the formation of currently unrecognized high-REE phosphates. The extraordinary endowment, combined with the ease of REE extraction, indicates that such phosphorites might be considered as a primary source of REEs with the potential to resolve the global REE (particularly for HREE) supply shortage.
Investigating different mechanisms for biogenic selenite transformations: Geobacter sulfurreducens , Shewanella oneidensis and Veillonella atypica
The metal-reducing bacteria Geobacter sulfurreducens, Shewanella oneidensis and Veillonella atypica, use different mechanisms to transform toxic, bioavailable sodium selenite to less toxic, non-mobile elemental selenium and then to selenide in anaerobic environments, offering the potential for in situ and ex situ bioremediation of contaminated soils, sediments, industrial effluents, and agricultural drainage waters. The products of these reductive transformations depend on both the organism involved and the reduction conditions employed, in terms of electron donor and exogenous extracellular redox mediator. The intermediary phase involves the precipitation of elemental selenium nanospheres and the potential role of proteins in the formation of these structures is discussed. The bionanomineral phases produced during these transformations, including both elemental selenium nanospheres and metal selenide nanoparticles, have catalytic, semiconducting and light-emitting properties, which may have unique applications in the realm of nanophotonics. This research offers the potential to combine remediation of contaminants with the development of environmentally friendly manufacturing pathways for novel bionanominerals. ?? 2009 Taylor & Francis.
Characterization of humic acid fractions by C-13 nuclear magnetic resonance spectroscopy
Soil humic acids from different environments were fractionated by adsorption chromatography on Sephadex and characterized by C‐13 nuclear magnetic resonance (NMR) spectroscopy. The C‐13 NMR spectra of the fractions consist of some sharp, well‐resolved lines and some broad bands in contrast to the spectra of the unfractionated humic acids, where the bands are broader and less well‐resolved. The marked increase in resolution is apparently due to increased homogeneity of the fractions. These spectra are compared to the spectra of model compounds.
A semiquantitative X-ray diffraction method to determine mineral composition in stream sediments with similar mineralogy
A semiquantitative X‐ray diffraction procedure has been developed that can be used to acquire reproducible mineralogic data from geographically unrelated stream‐sediment samples having similar mineralogy. Weight percentages for quartz, total‐feldspar, and total‐clay can be determined by direct comparison of intensities with standard‐mineral mixtures of known weight percent. Matrix effects and mass‐absorption differences are circumvented by taking the ratio of peak‐intensity, in counts per second, for quartz relative to that of other minerals being quantified. Mineral percentages generally are reproducible to within 10 percent.
Hybrid analysis of multiaxis electromagnetic data for discrimination of munitions and explosives of concern
The remediation of land containing munitions and explosives of concern, otherwise known as unexploded ordnance, is an ongoing problem facing the U.S. Department of Defense and similar agencies worldwide that have used or are transferring training ranges or munitions disposal areas to civilian control. The expense associated with cleanup of land previously used for military training and war provides impetus for research towards enhanced discrimination of buried unexploded ordnance. Towards reducing that expense, a multiaxis electromagnetic induction data collection and software system, called ALLTEM, was designed and tested with support from the U.S. Department of Defense Environmental Security Technology Certification Program. ALLTEM is an on-time time-domain system that uses a continuous triangle-wave excitation to measure the target-step response rather than traditional impulse response. The system cycles through three orthogonal transmitting loops and records a total of 19 different transmitting and receiving loop combinations with a nominal spatial data sampling interval of 20 cm. Recorded data are pre-processed and then used in a hybrid discrimination scheme involving both data-driven and numerical classification techniques. The data-driven classification scheme is accomplished in three steps. First, field observations are used to train a type of unsupervised artificial neural network, a self-organizing map (SOM). Second, the SOM is used to simultaneously estimate target parameters (depth, azimuth, inclination, item type and weight) by iterative minimization of the topographic error vectors. Third, the target classification is accomplished by evaluating histograms of the estimated parameters. The numerical classification scheme is also accomplished in three steps. First, the Biot–Savart law is used to model the primary magnetic fields from the transmitter coils and the secondary magnetic fields generated by currents induced in the target materials in the ground. Second, the target response is modelled by three orthogonal dipoles from prolate, oblate and triaxial ellipsoids with one long axis and two shorter axes. Each target consists of all three dipoles. Third, unknown target parameters are determined by comparing modelled to measured target responses. By comparing the rms error among the self-organizing map and numerical classification results, we achieved greater than 95 per cent detection and correct classification of the munitions and explosives of concern at the direct fire and indirect fire test areas at the UXO Standardized Test Site at the Aberdeen Proving Ground, Maryland in 2010.
Hydrogeologic framework of fractured sedimentary rock, Newark Basin, New Jersey
The hydrogeologic framework of fractured sedimentary bedrock at the former Naval Air Warfare Center (NAWC), Trenton, New Jersey, a trichloroethylene (TCE)-contaminated site in the Newark Basin, is developed using an understanding of the geologic history of the strata, gamma-ray logs, and rock cores. NAWC is the newest field research site established as part of the U.S. Geological Survey Toxic Substances Hydrology Program, Department of Defense (DoD) Strategic Environmental Research and Development Program, and DoD Environmental Security Technology Certification Program to investigate contaminant remediation in fractured rock. Sedimentary bedrock at the NAWC research site comprises the Skunk Hollow, Byram, and Ewing Creek Members of the Lockatong Formation and Raven Rock Member of the Stockton Formation. Muds of the Lockatong Formation that were deposited in Van Houten cycles during the Triassic have lithified to form the bedrock that is typical of much of the Newark Basin. Four lithotypes formed from the sediments include black, carbon-rich laminated mudstone, dark-gray laminated mudstone, light-gray massive mudstone, and red massive mudstone. Diagenesis, tectonic compression, off-loading, and weathering have altered the rocks to give some strata greater hydraulic conductivity than other strata. Each stratum in the Lockatong Formation is 0.3 to 8 m thick, strikes N65 degrees E, and dips 25 degrees to 70 degrees NW. The black, carbon-rich laminated mudstone tends to fracture easily, has a relatively high hydraulic conductivity and is associated with high natural gamma-ray count rates. The dark-gray laminated mudstone is less fractured and has a lower hydraulic conductivity than the black carbon-rich laminated mudstone. The light-gray and the red massive mudstones are highly indurated and tend to have the least fractures and a low hydraulic conductivity. The differences in gamma-ray count rates for different mudstones allow gamma-ray logs to be used to correlate and delineate the lithostratigraphy from multiple wells. Gamma-ray logs and rock cores were correlated to develop a 13-layer gamma-ray stratigraphy and 41-layer lithostratigraphy throughout the fractured sedimentary rock research site. Detailed hydrogeologic framework shows that black carbon-rich laminated mudstones are the most hydraulically conductive. Water-quality and aquifer-test data indicate that groundwater flow is greatest and TCE contamination is highest in the black, carbon- and clay-rich laminated mudstones. Large-scale groundwater flow at the NAWC research site can be modeled as highly anisotropic with the highest component of permeability occurring along bedding planes.
USGS international activities in coal resources
During the last 30 years the U.S. Geological Survey (USGS) has been engaged in coal exploration and characterization in more that 30 foreign countries, including India, Pakistan, China, Turkey, several Eastern European countries, Russia, and other former Soviet Union countries. Through this work, the USGS has developed an internationally recognized capability for assessing coal resources and defining their geochemical and physical characteristics. More recently, these data have been incorporated into digital databases and Geographic Information System (GIS) digital map products. The USGS has developed a high level of expertise in assessing the technological, economic, environmental, and human health impacts of coal occurrences and utilization based on comprehensive characterization of representative coal samples.
Radioactive Elements in Coal and Fly Ash: Abundance, Forms, and Environmental Significance
Coal is largely composed of organic matter, but it is the inorganic matter in coal—minerals and trace elements— that have been cited as possible causes of health, environmental, and technological problems associated with the use of coal. Some trace elements in coal are naturally radioactive. These radioactive elements include uranium (U), thorium (Th), and their numerous decay products, including radium (Ra) and radon (Rn). Although these elements are less chemically toxic than other coal constituents such as arsenic, selenium, or mercury, questions have been raised concerning possible risk from radiation. In order to accurately address these questions and to predict the mobility of radioactive elements during the coal fuel-cycle, it is important to determine the concentration, distribution, and form of radioactive elements in coal and fly ash.
Demonstration and validation of a regenerated cellulose dialysis membrane diffusion sampler for monitoring ground-water quality and remediation progress at DoD sites (ER-0313)
This final technical report documents the demonstration and validation of regenerated cellulose dialysis membrane diffusion samplers for use in collecting ground water samples for a range of inorganic and organic water-quality parameters. This project, ER-0313, was funded by the Environmental Security Technology Certification Program (ESTCP). The primary objectives of the project were; (1) to determine the usefulness of dialysis samplers in collecting a range of organic and inorganic water quality constituents from ground water, (2) to determine the optimum equilibration times for these constituents to diffuse into the dialysis sampler, (3) to compare water quality results and sampling costs from samples collected with dialysis samplers to samples collected with a low-flow purging technique and polyethylene diffusion bag (PDB) samplers, and (4) to transfer the technology while gaining regulatory acceptance. Field comparisons were conducted at three Department of Defense (DoD) sites: (1) Naval Air Engineering Station (NAES) Lakehurst, NJ, (2) Naval Base Ventura County (NBVC), Port Hueneme and Pt. Mugu, CA, and (3) Naval Air Warfare Center (NAWC) West Trenton, NJ. Dialysis samplers were found to cost significantly less than samples collected with a low-flow purging procedure. Field sampling time was reduced by a factor of more than six times, compared to low-flow purging. The total sampling costs per sample was estimated to be three times less, compared to low-flow purging.
Demonstration and validation of a regenerated cellulose dialysis membrane diffusion sampler for monitoring groundwater quality and remediation progress at DoD sites: Perchlorate and ordnance compounds
This final technical report documents the demonstration and validation of regenerated cellulose dialysis membrane diffusion samplers (RCDM samplers) for use in collecting groundwater samples for perchlorate and a suite of explosives compounds. This project, ER-0313, was funded by the Environmental Security Technology Certification Program (ESTCP). The primary objectives of the project were; (1) to determine the usefulness of RCDM samplers in collecting perchlorate and a suite of explosives compounds from groundwater, (2) to determine the optimum equilibration times for these constituents to diffuse into the RCDM sampler, (3) to compare water-quality results and sampling costs from samples collected with RCDM samplers to samples collected with a low-flow purging technique, and (4) to transfer the technology while gaining regulatory acceptance. Equilibration times were determined in bench-scale testing for perchlorate and 14 nitroaromatic and nitramine explosives compounds. Field comparisons were conducted at two Department of Defense (DoD) sites: (1) Aberdeen Proving Grounds (APG), Maryland, and, (2) Picatinny Arsenal, New Jersey. Samples collected with the two sampling techniques were compared graphically and statistically to determine the significance of any differences found. RCDM samplers were found to cost significantly less than samples collected with a low-flow purging procedure. Sampling time was reduced by 84%, compared to low-flow purging. The total sampling costs per sample were calculated to be 71% less with an RCDM sampler, compared to low-flow purging.
Measurement of sedimentary interbed hydraulic properties and their hydrologic influence near the Idaho Nuclear Technology and Engineering Center at the Idaho National Engineering and Environmental Laboratory
Disposal of wastewater to unlined infiltration ponds near the Idaho Nuclear Technology and Engineering Center (INTEC), formerly known as the Idaho Chemical Processing Plant, at the Idaho National Engineering and Environmental Laboratory (INEEL) has resulted in the formation of perched water bodies in the unsaturated zone (Cecil and others, 1991). The unsaturated zone at INEEL comprises numerous basalt flows interbedded with thinner layers of coarse- to fine-grained sediments and perched ground-water zones exist at various depths associated with massive basalts, basalt-flow contacts, sedimentary interbeds, and sediment-basalt contacts. Perched ground water is believed to result from large infiltration events such as seasonal flow in the Big Lost River and wastewater discharge to infiltration ponds. Evidence from a large-scale tracer experiment conducted in 1999 near the Radioactive Waste Management Complex (RWMC), approximately 13 km from the INTEC, indicates that rapid lateral flow of perched water in the unsaturated zone may be an important factor in contaminant transport at the INEEL (Nimmo and others, 2002b). Because sedimentary interbeds, and possibly baked-zone alterations at sediment-basalt contacts (Cecil and other, 1991) play an important role in the generation of perched water it is important to assess the hydraulic properties of these units.
Paleomagnetism of basaltic lava flows in coreholes ICPP-213, ICPP-214, ICPP-215, and USGS 128 near the Vadose Zone Research Park, Idaho Nuclear Technology and Engineering Center, Idaho National Engineering and Environmental Laboratory, Idaho
A paleomagnetic study was conducted on basalt from 41 lava flows represented in about 2,300 ft of core from coreholes ICPP-213, ICPP-214, ICPP-215, and USGS 128. These wells are in the area of the Idaho Nuclear Technology and Engineering Center (INTEC) Vadose Zone Research Park within the Idaho National Engineering and Environmental Laboratory (INEEL). Paleomagnetic measurements were made on 508 samples from the four coreholes, which are compared to each other, and to surface outcrop paleomagnetic data. In general, subhorizontal lines of correlation exist between sediment layers and between basalt layers in the area of the new percolation ponds. Some of the basalt flows and flow sequences are strongly correlative at different depth intervals and represent important stratigraphic unifying elements. Some units pinch out, or thicken or thin even over short separation distances of about 1,500 ft. A more distant correlation of more than 1 mile to corehole USGS 128 is possible for several of the basalt flows, but at greater depth. This is probably due to the broad subsidence of the eastern Snake River Plain centered along its topographic axis located to the south of INEEL. This study shows this most clearly in the oldest portions of the cored sections that have differentially subsided the greatest amount.