Photoproduction of hydrated electrons from natural organic solutes in aquatic environments
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A recent article presented geochemical and microbial evidence establishing metabolic adaptation to and in-situ reductive dechlorination of trichloroethene (TCE) in a fractured dolomite aquifer. This study was designed to further explore site conditions and microbial populations and to explain previously reported enhancement of reductive dechlorination by the addition of pulverized dolomite to laboratory microcosms. A survey of groundwater geochemical parameters (chlorinated ethenes, ethene, H2, CH4, DIC, DOC, and ??13C values for CH4, DIC, and DOC) indicated that in situ reductive dechlorination was ongoing and that an unidentified pool of organic carbon was contributing, likely via microbial respiration, to the large and relatively light onsite DIC pool. Petroleum hydrocarbons associated with the dolomite rock were analyzed by GC/MS and featured a characteristically low ??13C value. Straight chain hydrocarbons were extracted from the dolomite previously found to stimulate reductive dechlorination; these were particularly depleted in hexadecane (HD). Thus, we hypothesized that HD and related hydrocarbons might be anaerobically respired and serve both as the source of onsite DIC and support reductive dechlorination of TCE. Microcosms amended with pulverized dolomite demonstrated reductive dechlorination, whereas a combusted dolomite amendment did not. HD-amended microcosms were also inactive. Therefore, the stimulatory factor in the pulverized dolomite was heat labile, but that component was not HD. Amplified Ribosomal DNA Restriction Analysis (ARDRA) of the microbial populations in well waters indicated that a relatively low diversity, sulfur-transforming community outside the plume was shifted toward a high diversity community including Dehalococcoides ethenogenes-type microorganisms inside the zone of contamination. These observations illustrate biogeochemical intricacies of in situ reductive dechlorination reactions.
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The transport and fate of pollutants is often governed by both their tendency to sorb as well as their susceptibility to biodegradation. We have evaluated these parameters for 2,4,6-trinitrotoluene (TNT) and several biodegradation products. Slurries of aquifer sediment and groundwater depleted TNT at rates of 27, 7.7 and 5.9 μM day −1 under methanogenic, sulfate-reducing and nitrate-reducing conditions, respectively. Abiotic losses of TNT were determined in autoclaved controls. Abiotic TNT loss and subsequent transformation of the products was also observed. These transformations were especially important during the first step in the reduction of TNT. Subsequent abiotic reactions could account for all of the transformations observed in bottles which were initially nitrate-reducing. Other controls removed TNT reduction products at much slower rates than slurries containing live organisms. 2-Amino-4,6-dinitrotoluene was produced in all slurries but disappeared in methanogenic and in sulfate-reducing slurries within several weeks. This compound was converted to 2,4-diamino-6-nitrotoluene in all slurries with subsequent removal of the latter from methanogenic and sulfate-reducing slurries, while it persisted in autoclaved controls and in the nitrate-reducing slurries. Aquifer slurries incubated with either 2,4- or 2,6-diaminotoluene showed losses of these compounds relative to autoclaved controls under nitrate-reducing conditions but not under sulfate-reducing or methanogenic conditions. These latter compounds are important as reduced intermediates in the biodegradation of dinitrotoluenes and as industrial chemicals. In experiments to examine sorption, exposure to landfill sediment resulted in losses of approximately 15% of diaminotoluene isomers and 25% of aminodinitrotoluene isomers from initial solution concentrations within 24 h. Isotherms confirmed that the diaminotoluenes were least strongly sorbed and the amino-dinitrotoluenes most strongly sorbed to this sediment, while TNT sorption capacity was intermediate. In our studies, 2,4,6-triaminotoluene sorption capacity was indeterminate due to its chemical instability. Coupled with biodegradation information, isotherms help describe the likelihood of contaminant removal, persistence, and movement at impacted sites.
Context. Effective wildlife management requires information on habitat and resource needs, which can be estimated with movement information and modelling energetics. One necessary component of avian models is flight speeds at multiple temporal scales. Technology has limited the ability to accurately assess flight speeds, leading to estimates of questionable accuracy, many of which have not been updated in almost a century. Aims. We aimed to update flight speeds of ducks, and differentiate between migratory and non-migratory flight speeds, a detail that was unclear in previous estimates. We also analysed the difference in speeds of migratory and non-migratory flights, and quantified how data collected at different temporal intervals affected estimates of flight speed. Methods. We tracked six California dabbling duck species with high spatio-temporal resolution GPS–GSM transmitters, calculated speeds of different flight types, and modelled how estimates varied by flight and data interval (30 min to 6 h). Key results. Median migratory speeds were faster (but non-significant) for the larger mallard (Anas platyrhynchos; 82.5 km h–1), northern pintail (Anas acuta; 79.0 km h–1) and gadwall (Mareca strepera; 70.6 km h–1), than the smaller-bodied northern shoveler (Spatula clypeata; 65.7 km h–1), cinnamon teal (Spatula cyanoptera; 63.5 km h–1) and American wigeon (Mareca Americana; 52 km h–1). Migratory flights were faster than non-migratory flights for all species and speeds were consistently slower with an increasing data interval. Implications. The need to balance time and energy requirements may drive different speeds for migratory and non-migratory flights. Lower speeds at longer intervals are likely to be due to a greater proportion of ‘loafing’ time included in flighted segments, demonstrating that data acquired at different intervals provide a means to evaluate and estimate behaviours that influence speed estimation. Shorter-interval data should be the most accurate, but longer-interval data may be easier to collect over lengthier timeframes, so it may be expedient to trade-off a degree of accuracy in broad-scale studies for the larger dataset. Our updated flight speeds for dabbling duck species can be used to parameterise and validate energetics models, guide management decisions regarding optimal habitat distribution, and, ultimately, improve conservation management of wetlands for waterfowl.
Green sturgeon Acipenser medirostris spend much of their lives outside of their natal rivers, but the details of their migrations and habitat use are poorly known, which limits our understanding of how this species might be affected by human activities and habitat degradation. We tagged 355 green sturgeon with acoustic transmitters on their spawning grounds and in known nonspawning aggregation sites and examined their movement among these sites and other potentially important locations using automated data‐logging hydrophones. We found that green sturgeon inhabit a number of estuarine and coastal sites over the summer, including the Columbia River estuary, Willapa Bay, Grays Harbor, and the estuaries of certain smaller rivers in Oregon, especially the Umpqua River estuary. Green sturgeon from different natal rivers exhibited different patterns of habitat use; most notably, San Francisco Bay was used only by Sacramento River fish, while the Umpqua River estuary was used mostly by fish from the Klamath and Rogue rivers. Earlier work, based on analysis of microsatellite markers, suggested that the Columbia River mixed stock was mainly composed of fish from the Sacramento River, but our results indicate that fish from the Rogue and Klamath River populations frequently use the Columbia River as well. We also found evidence for the existence of migratory contingents within spawning populations. Our findings have significant implications for the management of the threatened Sacramento River population of green sturgeon, which migrates to inland waters outside of California where anthropogenic impacts, including fisheries bycatch and water pollution, may be a concern. Our results also illustrate the utility of acoustic tracking to elucidate the migratory behavior of animals that are otherwise difficult to observe.
Information on lake sturgeon ( Acipenser fulvescens ) depth and thermal habitat use during non-spawning periods is unavailable due to the difficulty of observing lake sturgeon away from shallow water spawning sites. In 2002 and 2003, lake sturgeon captured in commercial trap nets near Sarnia, Ontario were implanted with archival tags and released back into southern Lake Huron. Five of the 40 tagged individuals were recaptured and were at large for 32, 57, 286, 301, and 880 days. Temperatures and depths recorded by archival tags ranged from 0 to 23.5 ºC and 0.1 to 42.4 m, respectively. For the three lake sturgeon that were at large for over 200 days, temperatures occupied emulated seasonal fluctuations. Two of these fish occupied deeper waters during winter than summer while the other occupied similar depths during non-spawning periods. This study provides important insight into depth and thermal habitat use of lake sturgeon throughout the calendar year along with exploring the feasibility of using archival tags to obtain important physical habitat attributes during non-spawning periods.
Acoustic and archival tags examined freshwater and marine migrations of postspawn steelhead kelts (Oncorhynchus mykiss) in the Ninilchik River, Alaska, USA. Postspawn steelhead were captured at a weir in 2002-2005. Scale analysis indicated multiple migratory life histories and spawning behaviors. Acoustic tags were implanted in 99 kelts (2002-2003), and an array of acoustic receivers calculated the average speed of outmigration, timing of saltwater entry, and duration of residency in the vicinity of the river mouth. Ocean migration data were recovered from two archival tags implanted in kelts in 2004 (one male and one female). Archival tags documented seasonal differences in maximum depth and behavior with both fish spending 97% of time at sea <6 m depth (day and night). All study fish were double tagged with passive integrated transponder (PIT) tags implanted in the body cavity. Less than 4% of PIT tags were retained in postspawn steelhead. Molecular genetics demonstrated no significant differences in genetic population structure across years or among spawning life history types, suggesting a genetically panmictic population with highly diverse life history characteristics in the Ninilchik River.
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Sublimates were sampled from high-temperature (up to 800°C) fumaroles at Merapi volcano, Indonesia in January 1984. Sampling is accomplished by inserting silica tubes into high-temperature vents. Volcanic gas flows through the tubes and sublimates precipitate on the inner walls in response to the temperature gradient. With decreasing temperature (800–500°C) in the tubes, there are five sublimate zones: 1) cristobalite, magnetite, and halite; 2) halite, sylvite, K-Ca sulfate (K 2 Ca[SO 4 ] 2 ), acmite, wollastonite, and pyrite; 3) halite, sylvite, galena, Pb-Bi sulfide, aphthitalite, sphalerite, and Cs-K sulfate; 4) halite, sylvite, galena, PbKCl 3 , aphthitalite, and Na-K-Fe sulfate ([Na, K] 2 Fe[SO 4 ]Cl 2 ); and 5) halite, sylvite, galena, PbKCl 3 , and various sulfates of Pb, Cu, and Zn. Texturally, the sublimate phases grade from large, well-formed crystals at their highest-temperature occurrence to more numerous, smaller crystals that are less perfect at lower temperatures. These changes imply that the crystal nucleation and growth rates increase and decrease, respectively, as temperature decreases. Several of the sublimate phases also exhibit highly anisotropic morphologies (whiskers, platelets, spheres), especially below their highest temperature of deposition. Overall, the textural data suggest that the gas is saturated or slightly supersaturated with the phases at their hottest occurrence, but that the gas becomes increasingly supersaturated with the phases at lower temperatures. The anisotropic morphologies probably form because the crystals grow toward more supersaturated conditions in the center of the tube. The gas fails to maintain equilibrium with the precipitating sublimates because the high velocity of the carrier gas prevents complete mass transfer from the gas stream to the tube walls.
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This study, by the U.S. Geological Survey (USGS) in cooperation with the Pennsylvania Department of Environmental Protection (PADEP), provides a compilation of ground-water-quality data for a 25-year period (January 1, 1979, through August 11, 2004) based on water samples from wells. The data are from eight source agencies唯orough of Carroll Valley, Chester County Health Department, Pennsylvania Department of Environmental Protection-Ambient and Fixed Station Network, Montgomery County Health Department, Pennsylvania Drinking Water Information System, Pennsylvania Department of Agriculture, Susquehanna River Basin Commission, and the U.S. Geological Survey. The ground-water-quality data from the different source agencies varied in type and number of analyses; however, the analyses are represented by 12 major analyte groups:biological (bacteria and viruses), fungicides, herbicides, insecticides, major ions, minor ions (including trace elements), nutrients (dominantly nitrate and nitrite as nitrogen), pesticides, radiochemicals (dominantly radon or radium), volatile organic compounds, wastewater compounds, and water characteristics (dominantly field pH, field specific conductance, and hardness). A summary map shows the areal distribution of wells with ground-water-quality data statewide and by major watersheds and source agency. Maps of 35 watersheds within Pennsylvania are used to display the areal distribution of water-quality information. Additional maps emphasize the areal distribution with respect to 13 major geolithologic units in Pennsylvania and concentration ranges of nitrate (as nitrogen). Summary data tables by source agency provide information on the number of wells and samples collected for each of the 35 watersheds and analyte groups. The number of wells sampled for ground-water-quality data varies considerably across Pennsylvania. Of the 8,012 wells sampled, the greatest concentration of wells are in the southeast (Berks, Bucks, Chester, Delaware, Lancaster, Montgomery, and Philadelphia Counties), in the vicinity of Pittsburgh, and in the northwest (Erie County). The number of wells sampled is relatively sparse in south-central (Adams, Cambria, Cumberland, and Franklin Counties), central (Centre, Indiana, and Snyder Counties), and north-central (Bradford, Potter, and Tioga Counties) Pennsylvania. Little to no data are available for approximately one-third of the state. Water characteristics and nutrients were the most frequently sampled major analyte groups; approximately 21,000 samples were collected for each group. Major and minor ions were the next most-frequently sampled major analyte groups; approximately 17,000 and 12,000 samples were collected, respectively. For the remaining eight major analyte groups, the number of samples collected ranged from a low of 307 samples (wastewater compounds) to a high of approximately 3,000 samples (biological). The number of samples that exceeded a maximum contaminant level (MCL) or secondary maximum contaminant level (SMCL) by major analyte group also varied. Of the 2,988 samples in the biological analyte group, 53 percent had water that exceeded an MCL. Almost 2,500 samples were collected and analyzed for volatile organic compounds; 14 percent exceeded an MCL. Other major analyte groups that frequently exceeded MCLs or SMCLs included major ions (17,465 samples and a 33.9 percent exceedence), minor ions (11,905 samples and a 17.1 percent exceedence), and water characteristics (21,183 samples and a 20.3 percent exceedence). Samples collected and analyzed for fungicides, herbicides, insecticides, and pesticides (4,062 samples), radiochemicals (1,628 samples), wastewater compounds (307 samples), and nutrients (20,822 samples) had the lowest exceedences of 0.3, 8.4, 0.0, and 8.8 percent, respectively.
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This report presents approximately 2,100 glass analyses from three tephra units of Kīlauea Volcano: the Keanakākoʻi Tephra, the Kulanaokuaiki Tephra, and the Pāhala Ash. It also includes some new analyses obtained as part of a re-evaluation of the MgO contents of glasses in two of the three original datasets; this re-evaluation was conducted to improve the consistency of glass MgO contents among the three datasets. The glass data are a principal focus of Helz and others (in press), which will appear in the AGU Monograph Hawaiian Volcanoes—From Source to Surface. The report is intended to support this publication, in addition to making the data available to the scientific community.