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S. R. Silva

Publications and source records attributed to S. R. Silva.

11 recordsLinked to original sources
USGS2002

Oxygen isotope corrections for online δ34S analysis

Elemental analyzers have been successfully coupled to stable-isotope-ratio mass spectrometers for online measurements of the δ34S isotopic composition of plants, animals and soils. We found that the online technology for automated δ34S isotopic determinations did not yield reproducible oxygen isotopic compositions in the SO2 produced, and as a result calculated δ34S values were often 1–3‰ too high versus their correct values, particularly for plant and animal samples with high C/S ratio. Here we provide empirical and analytical methods for correcting the S isotope values for oxygen isotope variations, and further detail a new SO2-SiO2 buffering method that minimizes detrimental oxygen isotope variations in SO2.

Rapid Communications in Mass Spectrometry↗
USGS2002

Forensic applications of nitrogen and oxygen isotopes in tracing nitrate sources in urban environments

Ground and surface waters in urban areas are susceptible to nitrate contamination from septic systems, leaking sewer lines, and fertilizer applications. Source identification is a primary step toward a successful remediation plan in affected areas. In this respect, nitrogen and oxygen isotope ratios of nitrate, in conjunction with hydrologic data and water chemistry, have proven valuable in urban studies from Austin, Texas, and Tacoma, Washington. In Austin, stream water was sampled during stremflow and baseflow conditions to assess surface and subsurface sources of nitrate, respectively. In Tacoma, well waters were sampled in adjacent sewered and un-sewered areas to determine if locally high nitrate concentrations were caused by septic systems in the un-sewered areas. In both studies, sewage was identified as a nitrate source and mixing between sewage and other sources of nitrate was apparent. In addition to source identification, combined nitrogen and oxygen isotopes were important in determining the significance of denitrification, which can complicate source assessment by reducing nitrate concentrations and increasing ??15N values. The two studies illustrate the value of nitrogen and oxygen isotopes of nitrate for forensic applications in urban areas. ?? Published by Elsevier Science Ltd. on behalf of AEHS.

Environmental Forensics↗
USGS2001

Linking hyporheic flow and nitrogen cycling near the Willamette River: A large river in Oregon, USA

Several approaches were used to characterize ground water/surface water interactions near the Willamette River - A large (ninth order) river in Oregon, USA. A series of potentiometric surface maps demonstrated the presence of highly dynamic hydraulic gradients between rivers and the adjacent aquifer. Hyporheic zone gradients extended on the order of hundreds of meters. River gains and losses at the river stretch scale (tens of kilometers) were consistent with fluxes implied by the potentiometric surface maps, and apparently reflect regional ground water/surface water interactions. Gains and losses of up to 5-10% of streamflow were observed at this scale. On the river reach scale (1-2 km), gains and losses on the order of 5% of streamflow were interpreted as representing primarily local hyporheic exchange. Isotopic and chemical data collected from shallow hyporheic zone wells demonstrated interaction between regional ground water and river water. The origin of sampled hyporheic zone water ranged from a mixture dominated by regional ground water to water containing 100% river water. The common assumption that ground and river water mix primarily in the river channel is not applicable in this system. Isotopic and chemical data also indicated that significant (nearly complete) vegetative nitrate uptake and/or nitrate reduction occurred in water from 4 of 12 hyporheic zone sites. In these cases, it was primarily nitrate transported to the hyporheic zone in regional ground water that was removed from solution. Isotopes of water and nitrate indicated that hyporheic zone water sampled at two sites was composed of water originating as river water and demonstrated that significant vegetative nitrate uptake and nitrate reduction occurred along these hyporheic zone flowpaths. Thus, the hyporheic zone may, in some instances, serve to remove nitrate from river water. Additional investigations with chemical tools and microbial enzyme assays were conducted at one hyporheic site. A strong vertical redox gradient was observed, with nitrate-limited denitrification potential in deeper sediment and both nitrification and denitrification potential in shallower sediment. Since nitrogen cycling is strongly affected by redox conditions, nitrogen cycling in the hyporheic zone of this large-river system likely is affected by dynamics of ground water/surface water interactions that control fluxes of nitrogen and other redox species to hyporheic zone sediment.

Oregon↗
USGS2001

Compound-specific carbon isotope analysis of a contaminant plume in Kingsford, Michigan, USA

Compound-specific isotope analysis was used to study a contaminated site near Kingsford, Michigan, USA. Organic compounds at three of the sites studied had similar 13C values indicating that the contaminant source is the same for all sites. At a fourth site, chemical and 13C values had evolved due to microbial degradation of organics, with the 13C being much heavier than the starting materials. A microcosm experiment was run to observe isotopic changes with time in the methane evolved and in compounds remaining in the water during degradation. The 13C values of the methane became heavier during the initial period of the run when volatile fatty acids were being consumed. There was an abrupt decrease in the 13C values when fatty acids had been consumed and phenols began to be utilized. The 13C value of the propionate remaining in solution also increased, similar to the results found in the field.

Michigan↗
USGS2000

Use of isotopically labeled fertilizer to trace nitrogen fertilizer contributions to surface, soil, and ground water

The fate and transport of a single N fertilizer application through plants, soil, runoff, and the unsaturated and saturated zones was determined for four years at a field site under continuous corn (Zea mays L.) management. Claypan soils, which underlie the site, were hypothesized to restrict the movement of agrichemicals from the soil surface to ground water. However, N fertilizer moved rapidly through preferential flow paths in the soil and into the underlying glacial till aquifer. Most N transport occurred during the fall and winter when crops were not available to use excess N. Forty months after application, 33 percent of the fertilizer had been removed by grain harvests, 30 percent had been transpired to the atmosphere, and 33 percent had migrated to ground water. Although runoff volumes were 50 percent greater than infiltration, less than 2 percent of the fertilizer was lost to runoff. Small measured denitrification rates and large measured dissolved oxygen concentrations in ground water favor the long-term stability of NO3-1 in ground water. Successive fertilizer applications, in areas that lack the ability to moderate N concentrations through consumptive N reactions, risk the potential of N-saturated ecosystems.

Journal of Environmental Hydrology↗
USGS1999

Carbon isotopic constraints on the contribution of plant material to the natural precursors of trihalomethanes

The δ 13 C values of individual trihalomethanes (THM) formed on reaction of chlorine with dissolved organic carbon (DOC) leached from maize (corn; Zea maize L. ) and Scirpus acutus (an aquatic bulrush), and with DOC extracted from agricultural drainage waters were determined using purge and trap introduction into a gas chromatograph-combustion-isotope ratio monitoring mass spectrometer. We observed a 16.8‰ difference between the δ 13 C values of THM produced from the maize and Scirpus leachates, similar to the isotopic difference between the whole plant materials. Both maize and Scirpus formed THM 12‰ lower in 13 C than whole plant material. We suggest that the low value of the THM relative to the whole plant material is evidence of distinct pools of THM-forming DOC, representing different biochemical types or chemical structures, and possessing different environmental reactivity.

Organic Geochemistry↗
USGS1999

A method for nitrate collection for δ 15 N and δ 18 O analysis from waters with low nitrate concentrations

Recently, methods have been developed to analyze NO3- for δ15N and δ18O, improving our ability to identify NO3- sources and transformations. However, none of the existing methods are suited for waters with low NO3- concentrations (0.7-10 µM). We describe an improved method for collecting and recovering NO3- on exchange columns. To overcome the lengthy collection loading times imposed by the large sample volumes (7-70 L), the sample was prefiltered (0.45 µm) with a large surface area filter. Switching to AG2X anion resin and using a coarser mesh size (100-200) than previous methods also enhanced sample flow. Placement of a cation column in front of the anion column minimized clogging of the anion column by dissolved organic carbon (DOC) accumulation. This also served to minimize transfer of unwanted oxygen atoms from DOC to the 18O portion of the NO3- sample, thereby contaminating the sample and shifting δ18O. The cat-AG2X method is suited for on-site sample collection, making it possible to collect and recover NO3- from low ionic strength waters with modest DOC concentrations (80-800 µM), relieves the investigator of transporting large volumes of water back to the laboratory, and offers a means of sampling rain, snow, snowmelt, and stream samples from access-limited sites.

Canadian Journal of Fisheries and Aquatic Sciences↗
USGS1999

Geochemistry of Florida Bay sediments: Nutrient history at five sites in eastern and central Florida Bay

Recent seagrass dieoff and massive microalgal blooms have focused attention on the health of the Florida Bay ecosystem. Changes in nutrient input and the nutrient dynamics of Florida Bay are hypothesized to be linked to these problems, but crucial baseline information is still lacking. Efforts to restore Florida Bay to its natural condition will require information on the nutrient history of the bay. The purpose of this study was to examine distributions of organic C, total N, and total P in carbonate sediments from sites of continuous and known sedimentation rate (210Pb and 137Cs dated), in eastern and central Florida Bay. These sediments provide a record of historical changes in the C, N, and P load to the eastern and central bay. Analyses were conducted on sediments from cores collected at five sites, and on buried seagrass fragments at two sites. At three of the sites, sediments from seagrass-covered and adjacent barren areas were examined to determine differences in sedimentary geochemistry. Stable isotope analyses (??13C and ??15N) of sedimentary organic C and total N and of buried seagrass fragments were also carried out at two sites to examine possible changes in nutrient sources to the estuary. Results were consistent with recent increases in N and P in eastern Florida Bay, beginning in the early to mid 1980's. The timing of the increase in nutrient load observed in the sediment data directly preceded the first observations of massive microalgal blooms and seagrass dieoff in Florida Bay in 1987. The observed nutrification was greater for P than N, and was most pronounced at the most northeasterly site sampled (Pass Key). Isotope data (??15N) suggested that an increase in algal production accompanied the increase in N load at the Pass Key site. Along record of organic C, total N, and total P distributions from Whipray Basin in central Florida Bay showed historical peaks (mid 1700's and late 1800's) in organic C and total N, but not total P; these enrichments were nearly equivalent to recent inputs to the estuary. Barren areas were observed to have generally lower concentrations of organic C, total N, and total P in near surface sediments compared to seagrass-covered areas, but had generally similar concentrations in deeper sediments. This suggested that barren areas adjacent to seagrass-covered sites were places where relict sediment was physically transported and covered seagrass beds. This dataset provides an historical view of changes in nutrient inputs to Florida Bay, and baseline information needed for nutrient modeling of the bay.

Journal of Coastal Research↗