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Relation of organic contaminant equilibrium sorption and kinetic uptake in plants

Plant uptake is one of the environmental processes that influence contaminant fate. Understanding the magnitude and rate of plant uptake is critical to assessing potential crop contamination and the development of phytoremediation technologies. We determined (1) the partition-dominated equilibrium sorption of lindane (LDN) and hexachlorobenzene (HCB) by roots and shoots of wheat seedlings, (2) the kinetic uptake of LDN and HCB by roots and shoots of wheat seedlings, (3) the kinetic uptake of HCB, tetrachloroethylene (PCE), and trichloroethylene (TCE) by roots and shoots of ryegrass seedlings, and (4) the lipid, carbohydrate, and water contents of the plants. Although the determined sorption and the plant composition together suggest the predominant role of plant lipids for the sorption of LDN and HCB, the predicted partition with lipids of LDN and HCB using the octanol-water partition coefficients is notably lower than the measured sorption, due presumably to underestimation of the plant lipid contents and to the fact that octanol is less effective as a partition medium than plant lipids. The equilibrium sorption or the estimated partition can be viewed as the kinetic uptake limits. The uptakes of LDN, PCE, and TCE from water at fixed concentrations increased with exposure time in approach to steady states. The uptake of HCB did not reach a plateau within the tested time because of its exceptionally high partition coefficient. In all of the cases, the observed uptakes were lower than their respective limits, due presumably to contaminant dissipation in and limited water transpiration by the plants. ?? 2005 American Chemical Society.

Environmental Science & Technology

Foreward: Geology Field Trips in and around the U.S. Capital

The first annual meeting of the Geological Society of America (GSA) was held in 1888 in Ithaca, New York (Fairchild, 1932), but official Sections of GSA formed much later. During the spring of 1949, a symposium in Knoxville, Tennessee, on mineral resources of the southeastern United States became the catalyst for the creation of the Southeastern Section of the Geological Society of America (King, 1964), and the first annual meeting of the Southeastern Section was held in 1952 in Roanoke, Virginia (Wilson, 1954). The Northeastern Section formed much later, and its first annual meeting was held in 1966 in Philadelphia, Pennsylvania (Socolow, 1968). At all of these section meetings, field trips have been important venues for geologists and especially students to gather together, examine rocks in the field, and discuss ideas. These field trips have been especially important at combined section meetings because they provide settings for geologists who are experienced in one geographic region to examine and compare the geology of other regions. The first combined meeting of the Southeastern and Northeastern sections occurred in 1976 in Arlington, Virginia. Since then, the Southeastern and Northeastern sections have met together on numerous occasions, including 1982 in Washington, DC; 1991 in Baltimore, Maryland; 2004 in Tysons Corner, Virginia; and 2010 in Baltimore, Maryland. Since the first combined section meeting in 1976, there has been a gradual increase in the role of technology in geology field studies. In fact, during the past several decades there has been an increase in emphasis in our society on the instrumental component of science, the goal of which is operational techniques to do or control things, and a corresponding decrease in emphasis on the natural philosophy component of science, the goal of which is a greater understanding of the natural world (Dear, 2006). The modern education acronym STEM (Science, Technology, Engineering, and Mathematics), for example, is often used as a catch-all term that implies that science and technology are relatively synonymous, and implies that greater technology leads automatically to greater understanding of the natural world. This assumption, however, is not always valid (Dear, 2006), and technology should not be promoted as a substitute for field experiences. Technology can be a tool that leads to greater understanding of the natural world, but not all Science uses technology as a means of providing greater understanding. The benefits of new technologies include: (1) data of greater resolution; and (2) greater efficiency of capturing, storing, and visualizing data. The risks of new technologies include: (1) an overabundance of data, some of which may be of little value; (2) less time available for analysis of data, if geologists become occupied primarily with capturing and storing data; and (3) errors that arise from complacency and the perception that field-checking may not be necessary. In other words, there is a risk that a glut of data and vast amounts of time devoted to the capturing and storing of data may result in a reduced interest and (or) willingness to field-check data. In the spirit of the early GSA section meetings, we feel that there are still enormous advantages to conducting geology field trips in conjunction with traditional meeting presentations and posters. In 2020, with this current combined Southeastern and Northeastern section meeting in Reston, Virginia, we have assembled eight different field trips that cover a wide range of territory in and around the Nation’s capital. These field trip localities include the immediate vicinity of Washington, DC, as well as various locations in nearby areas of Virginia, Maryland, and West Virginia. The physiographic provinces include Mesozoic Rift Basins, the Piedmont, the Blue Ridge, the Valley and Ridge, and the Allegheny Plateau of the Appalachian Basin. The field trip sites exhibit a wide range of igneous, metamorphic, and sedimentary rocks, as well as rocks with a wide range of geologic ages from the Mesoproterozoic to the Holocene. We hope that this guidebook provides new motivation for geologists to examine rocks in the field, to discuss ideas with colleagues in the field, and to avoid becoming complacent. The editors of this volume would like to thank the authors of the different field trip guides, the field trip leaders, and all of the reviewers who made suggestions for improving the field trip manuscripts. The editors would also like to thank Elle Derwent of GSA for her logistical help and guidance regarding the field trips, and April Leo and the staff of the GSA Publications Department for seeing this book through to publication.

Maryland, Virginia, West Virginia

Development of web-based organic petrology photomicrograph atlases and internet resources for professionals and students

With advances in web applications, organic petrography and other related disciplines are in need of updated online resources and educational tools to aid professionals and students in the identification and interpretation of macerals. The U.S. Geological Survey (USGS) Organic Petrology Laboratory along with USGS Eastern Energy Resources Science Center Information Technology staff have developed five web atlases containing images of organic matter in geologic materials: 1. an American Society for Testing and Materials (ASTM) Atlas, 2. an Organic Petrology Taxonomy for International Classification (OPTIC) of Coal Macerals Atlas, 3. an Interactive Gulf Coast Photomicrograph Web Atlas (I-Map), 4. an Organic Material in Shales Atlas (Shale), and 5. an interactive Blue/White/Ultraviolet (UV) Light Atlas (Light). Each web atlas contains images of macerals with associated sample and petrographic data collected by the USGS. These webpages will provide means to preserve and circulate petrographic data collected by the USGS for coal and shale samples from all over the world.

International Journal of Coal Geology

Application of headspace analysis to the study of sorption of hydrophobic organic chemicals to α-Al 2 O 3

The sorption of hydrophobic organic chemicals (HOCs) to ??-Al2O3 was investigated with a headspace analysis method. The semiautomated headspace analyzer gave rapid, precise, and accurate results for a homologous series alkylbenzenes even at low percentages of solute mass sorbed (3-50%). Sorption experiments carried out with benzene alone indicated weak interactions with well-characterized aluminum oxide, and a solids concentration effect was observed. When the sorption coefficients for benzene alone obtained by headspace analysis were extrapolated up to the solids concentrations typically used in batch sorption experiments, the measured sorption coefficients agreed with reported sorption coefficients for HOCs and sediments of low fractional organic carbon content. Sorbed concentrations increased exponentially with aqueous concentration in isotherms with mixtures of alkylbenzenes, indicating solute-solute interactions at the mineral surface. Sorption was, however, greater than predicted for partitioning of a solute between its pure liquid phase and water, indicating additional influences of the surface and/or the structured liquid near the mineral surface. ?? 1993 American Chemical Society.

Environmental Science & Technology

Volatile selenium flux from the great Salt Lake, Utah

The removal mechanisms that govern Se concentrations in the Great Salt Lake are unknown despite this terminal lake being an avian habitat of hemispheric importance. However, the volatilization flux of Se from the Great Salt Lake has not been previously measured due to challenges of analysis in this hypersaline environment This paper presents results from recent field studies examining the spatial distribution of dissolved volatile Se (areally and with depth) in the south arm (main body) of the Great Salt Lake. The analyses involved collection of dissolved volatile Se in a cryofocusing trap system via sparging with helium. The cryotrapped volatile Se was digested with nitric acid and analyzed by inductively coupled plasma mass spectrometry (ICP-MS). Results show concentrations of dissolved volatile Se that increase with depth in the shallow brine, suggesting that phytoplankton in the open waters and bioherms in shallow sites (<4 m in depth) may be responsible for volatile Se production. Volatile Se flux to the atmosphere was determined using mass transport models corrected to simulate the highly saline environment of the south arm of the Great Salt Lake. The estimated annual flux of volatile Se was 1455 kg/year within a range from 560 to 3780 kg Se/year for the 95% confidence interval and from 970 to 2180 kg Se/year within the 68% confidence interval. ?? 2009 American Chemical Society.

Environmental Science & Technology

Importance of microscopy in durability studies of solidified and stabilized contaminated soils

Solidification/stabilization (S/S) is recognized by the U.S. EPA as a best demonstrated available technology for the containment of contaminated soils and other hazardous wastes that cannot be destroyed by chemical, thermal, or biological means. Despite the increased use of S/S technologies, little research has been conducted on the weathering and degradation of solidified and stabilized wastes once the treated materials have been buried. Published data to verify the performance and durability of landfilled treated wastes over time are rare. In this preliminary study, optical and electron microscopy (scanning electron microscopy [SEM], transmission electron microscopy [TEM] and electron probe microanalyses [EPMA]) were used to evaluate weathering features associated with metal-bearing contaminated soil that had been solidified and stabilized with Portland cement and subsequently buried on site, stored outdoors aboveground, or achieved in a laboratory warehouse for up to 6 yr. Physical and chemical alteration processes identified include: freeze-thaw cracking, cracking caused by the formation of expansive minerals such as ettringite, carbonation, and the movement of metals from waste aggregates into the cement micromass. Although the extent of degradation after 6 yr is considered slight to moderate, results of this study show that the same environmental concerns that affect the durability of concrete must be considered when evaluating the durability and permanence of the solidification and stabilization of contaminated soils with cement. In addition, such evaluations cannot be based on leaching and chemical analyses alone. The use of all levels of microscopic analyses must be incorporated into studies of the long-term performance of S/S technologies.Solidification/stabilization (S/S) is recognized by the U.S. EPA as a best demonstrated available technology for the containment of contaminated soils and other hazardous wastes that cannot be destroyed by chemical, thermal, or biological means. Despite the increased use of S/S technologies, little research has been conducted on the weathering and degradation of solidified and stabilized wastes once the treated materials have been buried. Published data to verify the performance and durability of landfilled treated wastes over time are rare. In this preliminary study, optical and electron microscopy (scanning electron microscopy [SEM], transmission electron microscopy [TEM] and electron probe microanalyses [EPMA]) were used to evaluate weathering features associated with metal-bearing contaminated soil that had been solidified and stabilized with Portland cement and subsequently buried on site, stored outdoors aboveground, or archived in a laboratory, warehouse for up to 6 yr. Physical and chemical alteration processes identified include: freeze-thaw cracking, cracking caused by the formation of expansive minerals such as ettringite, carbonation, and the movement of metals from waste aggregates into the cement micromass. Although the extent of degradation after 6 yr is considered slight to moderate, results of this study show that the same environmental concerns that affect the durability of concrete must be considered when evaluating the durability and permanence of the solidification and stabilization of contaminated soils with cement. In addition, such evaluations cannot be based on leaching and chemical analyses alone. The use of all levels of microscopic analyses must be incorporated into studies of the long-term performance of S/S technologies.

Soil Science Society of America Journal

Effects of Regulation and Technology on End Uses of Nonfuel Mineral Commodities in the United States

The regulatory system and advancement of technologies have shaped the end-use patterns of nonfuel minerals used in the United States. These factors affected the quantities and types of materials used by society. Environmental concerns and awareness of possible negative effects on public health prompted numerous regulations that have dramatically altered the use of commodities like arsenic, asbestos, lead, and mercury. While the selected commodities represent only a small portion of overall U.S. materials use, they have the potential for harmful effects on human health or the environment, which other commodities, like construction aggregates, do not normally have. The advancement of technology allowed for new uses of mineral materials in products like high-performance computers, telecommunications equipment, plasma and liquid-crystal display televisions and computer monitors, mobile telephones, and electronic devices, which have become mainstream products. These technologies altered the end-use pattern of mineral commodities like gallium, germanium, indium, and strontium. Human ingenuity and people?s demand for different and creative services increase the demand for new materials and industries while shifting the pattern of use of mineral commodities. The mineral commodities? end-use data are critical for the understanding of the magnitude and character of these flows, assessing their impact on the environment, and providing an early warning of potential problems in waste management of products containing these commodities. The knowledge of final disposition of the mineral commodity allows better decisions as to how regulation should be tailored.

Scientific Investigations Report

Atmospheric deposition of current-use and historic-use pesticides in snow at National Parks in the Western United States

The United States (U.S.) National Park Service has initiated research on the atmospheric deposition and fate of semi-volatile organic compounds in its alpine, sub-Arctic, and Arctic ecosystems in the Western U.S. Results for the analysis of pesticides in seasonal snowpack samples collected in spring 2003 from seven national parks are presented herein. From a target analyte list of 47 pesticides and degradation products, the most frequently detected current-use pesticides were dacthal, chlorpyrifos, endosulfan, and ??- hexachlorocyclohexane, whereas the most frequently detected historic-use pesticides were dieldrin, ??-hexachlorocyclohexane, chlordane, and hexachlorobenzene. Correlation analysis with latitude, temperature, elevation, particulate matter, and two indicators of regional pesticide use reveal that regional current and historic agricultural practices are largely responsible for the distribution of pesticides in the national parks in this study. Pesticide deposition in the Alaskan parks is attributed to long-range transport because there are no significant regional pesticide sources. The percentage of total pesticide concentration due to regional transport (%RT) was calculated for the other parks. %RT was highest at parks with higher regional cropland intensity and for pesticides with lower vapor pressures and shorter half-lives in air. ?? 2006 American Chemical Society.

Environmental Science & Technology

Spectroscopic evidence for uranium bearing precipitates in vadose zone sediments at the Hanford 300-area site

Uranium (U) solid-state speciation in vadose zone sediments collected beneath the former North Process Pond (NPP) in the 300 Area of the Hanford site (Washington) was investigated using multi-scale techniques. In 30 day batch experiments, only a small fraction of total U (???7.4%) was released to artificial groundwater solutions equilibrated with 1% pCO2. Synchrotron-based micro-X-ray fluorescence spectroscopy analyses showed that U was distributed among at least two types of species: (i) U discrete grains associated with Cu and (ii) areas with intermediate U concentrations on grains and grain coatings. Metatorbernite (Cu[UO2]2[PO 4]2??8H2O) and uranophane (Ca[UO 2]2[SiO3(OH)]2?? 5H 2O) at some U discrete grains, and muscovite at U intermediate concentration areas, were identified in synchrotron-based micro-X-ray diffraction. Scanning electron microscopy/energy dispersive X-ray analyses revealed 8-10 ??m size metatorbernite particles that were embedded in C-, Al-, and Si-rich coatings on quartz and albite grains. In ??- and bulk-X-ray absorption structure (??-XAS and XAS) spectroscopy analyses, the structure of metatorbernite with additional U-C and U-U coordination environments was consistently observed at U discrete grains with high U concentrations. The consistency of the ??- and bulk-XAS analyses suggests that metatorbernite may comprise a significant fraction of the total U in the sample. The entrapped, micrometer-sized metatorbernite particles in C-, Al-, and Si-rich coatings, along with the more soluble precipitated uranyl carbonates and uranophane, likely control the long-term release of U to water associated with the vadose zone sediments. ?? 2007 American Chemical Society.

Environmental Science & Technology

A fresh look at road salt: Aquatic toxicity and water-quality impacts on local, regional, and national scales

A new perspective on the severity of aquatic toxicity impact of road salt was gained by a focused research effort directed at winter runoff periods. Dramatic impacts were observed on local, regional, and national scales. Locally, samples from 7 of 13 Milwaukee, Wisconsin area streams exhibited toxicity in Ceriodaphnia dubia and Pimephales promelas bioassays during road-salt runoff. Another Milwaukee stream was sampled from 1996 to 2008 with 72% of 37 samples exhibiting toxicity in chronic bioassays and 43% in acute bioassays. The maximum chloride concentration was 7730 mg/L. Regionally, in southeast Wisconsin, continuous specific conductance was monitored as a chloride surrogate in 11 watersheds with urban land use from 6.0 to 100%. Elevated specific conductance was observed between November and April at all sites, with continuing effects between May and October at sites with the highest specific conductance. Specific conductance was measured as high as 30 800 ??S/cm (Cl = 11 200 mg/L). Chloride concentrations exceeded U.S. Environmental Protection Agency (USEPA) acute (860 mg/L) and chronic (230 mg/L) water-quality criteria at 55 and 100% of monitored sites, respectively. Nationally, U.S. Geological Survey historical data were examined for 13 northern and 4 southern metropolitan areas. Chloride concentrations exceeded USEPA water-quality criteria at 55% (chronic) and 25% (acute) of the 168 monitoring locations in northern metropolitan areas from November to April. Only 16% (chronic) and 1% (acute) of sites exceeded criteria from May to October. At southern sites, very few samples exceeded chronic water-quality criteria, and no samples exceeded acute criteria. ?? 2010 American Chemical Society.

Environmental Science & Technology

Mercury concentrations in salmonids from western U.S. National Parks and relationships with age and macrophage aggregates

Mercury accumulation in aquatic foodwebs and its effects on aquatic biota are of growing concern both for the health of the fish and the piscivores that prey upon them. This is of particular concern for western U.S. National Parks because it is known that mountainous and Arctic areas are sinks for some contaminants. The Western Airborne Contaminants Assessment Project seeks, in part, to ascertain mercury concentrations and evaluate effects of contaminants on biota in 14 lakes from 8 National Parks or Preserves. In this paper we report that mercury has accumulated to concentrations in trout that may negatively impact some piscivorous wildlife, indicating potential terrestrial ecosystem effects. Additionally, we show that mercury concentrations increase with age in 4 species of trout, providing evidence of bioaccumulation. Finally, we demonstrate that mercury is associated with tissue damage in the kidney and spleen, as indicated by increases in macrophage aggregates. This finding suggests that mercury, and possibly other contaminants, are negatively affecting the trout that inhabit these remote and protected ecosystems. Our results indicate that mercury is indeed a concern for the U.S. National Parks, from an organismic and potentially an ecosystem perspective. ?? 2008 American Chemical Society.

Environmental Science & Technology

Aquatic toxicity of airfield-pavement deicer materials and implications for airport runoff

Concentrations of airfield-pavement deicer materials (PDM) in a study of airport runoff often exceeded levels of concern regarding aquatic toxicity. Toxicity tests on Vibrio fischeri, Pimephales promelas, Ceriodaphnia dubia, and Pseudokirchneriella subcapitata (commonly known as Selenastrum capricornutum) were performed with potassium acetate (K-Ac) PDM, sodium formate (Na-For) PDM, and with freezing- point depressants (K-Ac and Na-For). Results indicate that toxicity in PDM is driven by the freezing-point depressants in all tests except the Vibrio fisheri test for Na-For PDM which is influenced by an additive. Acute toxicity end points for different organisms ranged from 298 to 6560 mg/L (as acetate) for K-Ac PDM and from 1780 to 4130 mg/L (as formate) for Na- For PDM. Chronic toxicity end points ranged from 19.9 to 336 mg/L (as acetate) for K-Ac PDM and from 584 to 1670 mg/L (as formate) for Na-For PDM. Sample results from outfalls at General Mitchell International Airport in Milwaukee, Wl (GMIA) indicated that 40% of samples had concentrations greater than the aquatic-life benchmark for K-Ac PDM. K-Ac has replaced urea during the 1990s as the most widely used PDM at GMIA and in the United States. Results of ammonia samples from airport outfalls during periods when urea-based PDM was used at GMIA indicated that41% of samples had concentrations exceeding the U.S. Environmental Protection Agency (USEPA) 1 -h water-quality criterion. The USEPA 1-h water-quality criterion for chloride was exceeded in 68% of samples collected in the receiving stream, a result of road-salt runoff from urban influence near the airport. Results demonstrate that PDM must be considered to comprehensively evaluate the impact of chemical deicers on aquatic toxicity in water containing airport runoff. ?? 2009 American Chemical Society.

Environmental Science & Technology

Transport of sludge-derived organic pollutants to deep-sea sediments at deep water dump site 106

Linear alkylbenzenes (LABs), coprostanol and epi-coprostanol, were detected in sediment trap and bottom sediment samples at the Deep Water Dump Site 106 located 185 km off the coast of New Jersey, in water depths from 2400 to 2900 m. These findings clearly indicate that organic pollutants derived from dumped sludge are transported through the water column and have accumulated on the deep-sea floor. No significant difference in LABs isomeric composition was observed among sludge and samples, indicating little environmental biodegradation of these compounds. LABs and coprostanol have penetrated down to a depth of 6 cm in sediment, indicating the mixing of these compounds by biological and physical processes. Also, in artificially resuspended surface sediments, high concentrations of LABs and coprostanols were detected, implying that sewage-derived organic pollutants initially deposited on the deep-sea floor can be further dispersed by resuspension and transport processes. Small but significant amounts of coprostanol were detected in the sediment from a control site at which no LABs were detected. The coprostanol is probably derived from feces of marine mammals and sea birds and/or from microbial or geochemical transformations of cholesterol. Polcyclic aromatic hydrocarbons (PAHs) in sediment trap samples from the dump site were largely from the sewage sludge and had a mixed petroleum and pyrogenic composition. In contrast, PAHs in sediments in the dump site were mainly pyrogenic; contributed either from sewage sludge or from atmospheric transport to the overlying waters. & 1994 American Chemical Society.

Environmental Science & Technology

Freshwater mussel shells as environmental chronicles: Geochemical and taphonomic signatures of mercury-related extirpations in the North Fork Holston River, Virginia

This study utilized freshwater mussel shells to assess mercury (Hg) contamination in the North Fork Holston River that extirpated (caused local extinctions of) a diverse mussel fauna. Shells (n = 366) were collected from five sites situated upstream (two sites), just below (one site), and downstream (two sites) of the town of Saltville, Virginia, where Hg was used to produce chlorine and caustic soda from 1950 to 1972. Shell samples were used to test the (1) utility of geochemical signatures of shells for assessing the spatial variation in Hg levels in the river relative to the contamination source and (2) value of taphonomy (postmortem shell alteration) for distinguishing sites that differ in extirpation histories. Geochemical signatures of 40 shells, analyzed using atomic absorption spectroscopy, indicated a strong longitudinal pattern. All shells from the two upstream sites had low Hg concentrations (<5-31 ??g/kg), shells directly below Saltville had variable, but dramatically higher concentrations (23-4637 ??g/kg), and shells from the two downstream sites displayed intermediate Hg levels (<5-115 ??g/kg) that declined with distance from Saltville. Two pre-industrial shells, collected at Saltville in 1917, yielded very low Hg estimates (5-6 ??g/kg). Hg signatures were consistent among mussel species, suggesting that Hg concentrations were invariant to species type; most likely, highly variable Hg levels, both across sites and through time, overwhelmed any interspecific differences in Hg acquisition. Also, a notable postmortem incorporation of Hg in mussel shells seemed unlikely, as the Hg content was not correlated with shell taphonomy (r = 0.18; p = 0.28). The taphonomic analysis (n = 366) showed that the degree of shell alteration reliably distinguished sites with different extirpation histories. At Saltville, where live mussels have been absent for at least 30 years, shells were most heavily altered and fragmented. Conversely, fresh-looking shells abounded upstream, where reproducing mussel populations are still present. In summary, relic shells offered valuable spatiotemporal data on Hg concentrations in a polluted ecosystem, and shell taphonomic signatures discriminated sites with different extirpation histories. The shell-based strategies exemplified here do not require sampling live specimens and may augment more standard strategies applied to environmental monitoring. The approach should prove especially useful in areas with unknown extirpation and pollution histories. ?? 2005 American Chemical Society.

Environmental Science & Technology

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

Land cover and land use change

Climate can affect and be affected by changes in land cover (the physical features that cover the land such as trees or pavement) and land use (human management and activities on land, such as mining or recreation). A forest, for instance, would likely include tree cover but could also include areas of recent tree removals currently covered by open grass areas. Land cover and use are inherently coupled: changes in land-use practices can change land cover, and land cover enables specific land uses. Understanding how land cover, use, condition, and management vary in space and time is challenging. Changes in land cover can occur in response to both human and climate drivers. For example, demand for new settlements often results in the permanent loss of natural and working lands, which can result in localized changes in weather patterns, temperature, and precipitation. Aggregated over large areas, these changes have the potential to influence Earth’s climate by altering regional and global circulation patterns, changing the albedo (reflectivity) of Earth’s surface, and changing the amount of carbon dioxide (CO 2 ) in the atmosphere. Conversely, climate change can also influence land cover, resulting in a loss of forest cover from climate-related increases in disturbances, the expansion of woody vegetation into grasslands, and the loss of beaches due to coastal erosion amplified by rises in sea level. Land use is also changed by both human and climate drivers. Land-use decisions are traditionally based on short-term economic factors. Land-use changes are increasingly being influenced by distant forces due to the globalization of many markets. Land use can also change due to local, state, and national policies, such as programs designed to remove cultivation from highly erodible land to mitigate degradation, legislation to address sea level rise in local comprehensive plans, or policies that reduce the rate of timber harvest on federal lands. Technological innovation has also influenced land-use change, with the expansion of cultivated lands from the development of irrigation technologies and, more recently, decreases in demand for agricultural land due to increases in crop productivity. The recent expansion of oil and gas extraction activities throughout large areas of the United States demonstrates how policy, economics, and technology can collectively influence and change land use and land cover. Decisions about land use, cover, and management can help determine society’s ability to mitigate and adapt to climate change.

Report

Surface complexation modeling of U(VI) adsorption by aquifer sediments from a former mill tailings site at Rifle, Colorado

A study of U(VI) adsorption by aquifer sediment samples from a former uranium mill tailings site at Rifle, Colorado, was conducted under oxic conditions as a function of pH, U(VI), Ca, and dissolved carbonate concentration. Batch adsorption experiments were performed using <2mm size sediment fractions, a sand-sized fraction, and artificial groundwater solutions prepared to simulate the field groundwater composition. To encompass the geochemical conditions of the alluvial aquifer at the site, the experimental conditions ranged from 6.8 ?? 10 -8 to 10 -5 M in [U(VI)]tot, 7.2 to 8.0 in pH, 3.0 ?? 10 -3 to 6.0 ?? 10 -3 M in [Ca 2+ ], and 0.05 to 2.6% in partial pressure of carbon dioxide. Surface area normalized U(VI) adsorption Kd values for the sand and <2 mm sediment fraction were similar, suggesting a similar reactive surface coating on both fractions. A two-site two-reaction, nonelectrostatic generalized composite surface complexation model was developed and successfully simulated the U(VI) adsorption data. The model successfully predicted U(VI) adsorption observed from a multilevel sampling well installed at the site. A comparison of the model with the one developed previously for a uranium mill tailings site at Naturita, Colorado, indicated that possible calcite nonequilibrium of dissolved calcium concentration should be evaluated. The modeling results also illustrate the importance of the range of data used in deriving the best fit model parameters. ?? 2009 American Chemical Society.

Environmental Science & Technology

Evaluation of the use of performance reference compounds in an oasis-HLB adsorbent based passive sampler for improving water concentration estimates of polar herbicides in freshwater

Passive samplers such as the Polar Organic Chemical Integrative Sampler (POCIS) are useful tools for monitoring trace levels of polar organic chemicals in aquatic environments. The use of performance reference compounds (PRC) spiked into the POCIS adsorbent for in situ calibration may improve the semiquantitative nature of water concentration estimates based on this type of sampler. In this work, deuterium labeled atrazine-desisopropyl (DIA-d5) was chosen as PRC because of its relatively high fugacity from Oasis HLB (the POCIS adsorbent used) and our earlier evidence of its isotropic exchange. In situ calibration of POCIS spiked with DIA-d5was performed, and the resulting time-weighted average concentration estimates were compared with similar values from an automatic sampler equipped with Oasis HLB cartridges. Before PRC correction, water concentration estimates based on POCIS data sampling ratesfrom a laboratory calibration exposure were systematically lower than the reference concentrations obtained with the automatic sampler. Use of the DIA-d5 PRC data to correct POCIS sampling rates narrowed differences between corresponding values derived from the two methods. Application of PRCs for in situ calibration seems promising for improving POCIS-derived concentration estimates of polar pesticides. However, careful attention must be paid to the minimization of matrix effects when the quantification is performed by HPLC-ESI-MS/MS. ?? 2010 American Chemical Society.

Environmental Science & Technology