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Distribution of light and heavy fractions of soil organic carbon as related to land use and tillage practice

Mass distributions of different soil organic carbon (SOC) fractions are influenced by land use and management. Concentrations of C and N in light- and heavy fractions of bulk soils and aggregates in 0–20 cm were determined to evaluate the role of aggregation in SOC sequestration under conventional tillage (CT), no-till (NT), and forest treatments. Light- and heavy fractions of SOC were separated using 1.85 g mL −1 sodium polytungstate solution. Soils under forest and NT preserved, respectively, 167% and 94% more light fraction than those under CT. The mass of light fraction decreased with an increase in soil depth, but significantly increased with an increase in aggregate size. C concentrations of light fraction in all aggregate classes were significantly higher under NT and forest than under CT. C concentrations in heavy fraction averaged 20, 10, and 8 g kg −1 under forest, NT, and CT, respectively. Of the total SOC pool, heavy fraction C accounted for 76% in CT soils and 63% in forest and NT soils. These data suggest that there is a greater protection of SOC by aggregates in the light fraction of minimally disturbed soils than that of disturbed soil, and the SOC loss following conversion from forest to agriculture is attributed to reduction in C concentrations in both heavy and light fractions. In contrast, the SOC gain upon conversion from CT to NT is primarily attributed to an increase in C concentration in the light fraction.

Soil and Tillage Research↗

Influence of organic carbon loading, sediment associated metal oxide content and sediment grain size distributions upon Cryptosporidium parvum removal during riverbank filtration operations, Sonoma County, CA

This study assessed the efficacy for removing Cryptosporidium parvum oocysts of poorly sorted, Fe- and Al-rich, subsurface sediments collected from 0.9 to 4.9 and 1.7–13.9 m below land surface at an operating riverbank filtration (RBF) site (Russian River, Sonoma County, CA). Both formaldehyde-killed oocysts and oocyst-sized (3 μm) microspheres were employed in sediment-packed flow-through and static columns. The degree of surface coverage of metal oxides on sediment grain surfaces correlated strongly with the degrees of oocyst and microsphere removals. In contrast, average grain size ( D 50 ) was not a good indicator of either microsphere or oocyst removal, suggesting that the primary mechanism of immobilization within these sediments is sorptive filtration rather than physical straining. A low specific UV absorbance (SUVA) for organic matter isolated from the Russian River, suggested that the modest concentration of the SUVA component (0.8 mg L −1 ) of the 2.2 mg L −1 dissolved organic carbon (DOC) is relatively unreactive. Nevertheless, an amendment of 2.2 mg L −1 of isolated river DOC to column sediments resulted in up to a 35.7% decrease in sorption of oocysts and (or) oocyst-sized microspheres. Amendments (3.2 μM) of the anionic surfactant, sodium dodecyl benzene sulfonate (SDBS) also caused substantive decreases (up to 31.9 times) in colloid filtration. Although the grain-surface metal oxides were found to have a high colloid-removal capacity, our study suggested that any major changes within the watershed that would result in long-term alterations in either the quantity and (or) the character of the river's DOC could alter the effectiveness of pathogen removal during RBF operations.

Water Research↗

Elevated carbon dioxide flux at the Dixie Valley geothermal field, Nevada; relations between surface phenomena and the geothermal reservoir

In the later part of the 1990s, a large die-off of desert shrubs occurred over an approximately 1 km2 area in the northwestern section of the Dixie Valley (DV) geothermal field. This paper reports results from accumulation-chamber measurements of soil CO2 flux from locations in the dead zone and stable isotope and chemical data on fluids from fumaroles, shallow wells, and geothermal production wells within and adjacent to the dead zone. A cumulative probability plot shows three types of flux sites within the dead zone: Locations with a normal background CO2 flux (7 g m-2 day-1); moderate flux sites displaying "excess" geothermal flux; and high flux sites near young vents and fumaroles. A maximum CO2 flux of 570 g m-2 day-1 was measured at a location adjacent to a fumarole. Using statistical methods appropriate for lognormally distributed populations of data, estimates of the geothermal flux range from 7.5 t day-1 from a 0.14-km2 site near the Stillwater Fault to 0.1 t day-1 from a 0.01 -km2 location of steaming ground on the valley floor. Anomalous CO2 flux is positively correlated with shallow temperature anomalies. The anomalous flux associated with the entire dead zone area declined about 35% over a 6-month period. The decline was most notable at a hot zone located on an alluvial fan and in the SG located on the valley floor. Gas geochemistry indicates that older established fumaroles along the Stillwater Fault and a 2-year-old vent in the lower section of the dead zone discharge a mixture of geothermal gases and air or gases from air-saturated meteoric water (ASMW). Stable isotope data indicate that steam from the smaller fumaroles is produced by ??? 100??C boiling of these mixed fluids and reservoir fluid. Steam from the Senator fumarole (SF) and from shallow wells penetrating the dead zone are probably derived by 140??C to 160??C boiling of reservoir fluid. Carbon-13 isotope data suggest that the reservoir CO2 is produced mainly by thermal decarbonation of hydrothermal calcite in veins that cut reservoir rocks. Formation of the dead zone is linked to the reservoir pressure decline caused by continuous reservoir drawdown from 1986 to present. These reservoir changes have restricted flow and induced boiling in a subsurface hydrothermal outflow plume extending from the Stillwater Fault southeast toward the DV floor. We estimate that maximum CO2 flux in the upflow zone along the Stillwater Fault in 1998 was roughly seven to eight times greater than the pre-production flux in 1986. The eventual decline in CO2 flux reflects the drying out of the outflow plume. Published by Elsevier Science B.V.

Chemical Geology↗

Carbon dioxide from coal combustion: Variation with rank of US coal

Carbon dioxide from combustion of US coal systematically varies with ASTM rank indices, allowing the amount of CO2 produced per net unit of energy to be predicted for individual coals. No single predictive equation is applicable to all coals. Accordingly, we provide one equation for coals above high volatile bituminous rank and another for lower rank coals. When applied to public data for commercial coals from western US mines these equations show a 15% variation of kg CO2 (net GJ)-1. This range of variation suggests reduction of US CO2 emissions is possible by prudent selection of coal for combustion. Maceral and mineral content are shown to slightly affect CO2 emissions from US coal. We also suggest that CO2 emissions increased between 6 and 8% in instances where Midwestern US power plants stopped burning local, high-sulfur bituminous coal and started burning low-sulfur, subbituminous C rank coal from the western US.

Fuel↗

Uranium-series dating of pedogenic silica and carbonate, Crater Flat, Nevada

A 230Th-234U-238U dating study on pedogenic silica-carbonate clast rinds and matrix laminae from alluvium in Crater Flat, Nevada was conducted using small-sample thermal-ionization mass spectrometry (TIMS) analyses on a large suite of samples. Though the 232Th content of these soils is not particularly low (mostly 0.1-9 ppm), the high U content of the silica component (mostly 4-26 ppm) makes them particularly suitable for 230Th/U dating on single, 10 to 200 mg totally-digested samples using TIMS. We observed that (1) both micro- (within-rind) and macro-stratigraphic (mappabe deposit) order of the 230Th/U ages were preserved in all cases; (2) back-calculated initial 234U/238U fall in a restricted range (typically 1.67??0.19), so that 234U/238U ages with errors of about 100 kyr (2??) could be reliably determined for the oldest, 400 to 1000 ka rinds: and (3) though 13 of the samples were >350 ka, only three showed evidence for an open-system history, even though the sensitivity of such old samples to isotopic disruption is very high. An attempt to use leach-residue techniques to separate pedogenic from detrital U and Th failed, yielding corrupt 230Th/U ages. We conclude that 230Th/U ages determined from totally dissolved, multiple sub-mm size subsamples provide more reliable estimates of soil chronology than methods employing larger samples, chemical enhancement of 238U/232Th, or isochrons. Copyright ?? 2002 Elsevier Science Ltd.

Geochimica et Cosmochimica Acta↗

Loading capacity and chromatographic behavior of a porous graphitic carbon column for polychlorinated biphenyls

A porous graphitic carbon column (Hypercarb) was used for the fractionation of polychlorinated biphenyls (PCBs) into classes of 2-4 ortho chlorines, 1 ortho chlorine and 0 ortho chlorine congeners. A method was developed that combined the fractionation of PCBs, polychlorinated dibenzo- p -dioxins and dibenzofurans in a variety of biotic environmental samples. Many of these samples have high concentrations of PCBs which cause fractionation problems as adsorption sites on the graphitic surface are occupied. The loading capacity of the column for PCBs was determined by injecting up to 1 mg of total PCBs and monitoring changes in chromatographic behavior of tetra-/di- ortho , mono- ortho and non- ortho substituted PCBs. Effective loading capacities were 1 mg for tetra-/di- ortho PCBs, but only 3–5 μg for non- ortho PCBs and about 2 μg for mono- ortho PCBs. Loading capacity of the PGC column for environmental fish and avian egg samples was determined to depend on the mono- ortho and non- ortho PCB levels found in these samples.

Journal of Chromatography A↗

Development of small carbonate banks on the south Florida platform margin: Response to sea level and climate change

Geophysical and coring data from the Dry Tortugas, Tortugas Bank, and Riley&rsquo;s Hump on the southwest Florida margin reveal the stratigraphic framework and growth history of these carbonate banks. The Holocene reefs of the Dry Tortugas and Tortugas Bank are approximately 14 and 10 m thick, respectively, and are situated upon Pleistocene reefal edifices. Tortugas Bank consists of the oldest Holocene corals in the Florida Keys with earliest coral recruitment occurring at &sim;9.6 cal ka. Growth curves for the Tortugas Bank reveal slow growth (<1 mm/yr) until 6.2 cal ka, then a rapid increase to 3.4 mm/yr, until shallow reef demise at &sim;4.2 cal ka. Coral reef development at the Dry Tortugas began at &sim;6.4 cal ka. Aggradation at the Dry Tortugas was linear, and rapid (&sim;3.7 mm/yr) and kept pace with sea-level change. The increase in aggradation rate of Tortugas Bank at 6.2 cal ka is attributed to the growth of the Dry Tortugas reefs, which formed a barrier to inimical shelf water. Termination of shallow (<15 m below sea level) reef growth at Tortugas Bank at &sim;4.2 cal ka is attributed to paleoclimate change in the North American interior that increased precipitation and fluvial discharge. Reef growth rates and characteristics are related to the rate of sea-level rise relative to the position of the reef on the shelf margin, and are additionally modified by hydrographic conditions related to climate change.

Florida↗

Ordovician meteoric carbon and oxygen isotopic values: Implications for the latitudinal variations of ancient stable isotopic values

Columnar and clear blocky calcite cement from a Middle Ordovician carbonate succession in east Tennessee is interpreted as meteoric in origin. Columnar and clear blocky calcite from this succession does not show extremely large 13C depletions reported from meteoric phases of younger rocks. Meteoric fluid ??18O values calculated from clear blocky calcite are ??? 2 to 3??? more negative than approximately coeval sea water; a relationship typical of modern, low-latitude, coastal meteoric water. Comparison with meteoric ??18O values from Ordovician units elsewhere suggests that the geographic distribution of these values may be broadly similar to that observed today. Therefore, we tentatively suggest that geographic distribution of meteoric ??18O values during both icehouse and greenhouse eras are similar.

Palaeogeography, Palaeoclimatology, Palaeoecology↗

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↗

Carbon dynamics and land-use choices: building a regional-scale multidisciplinary model

Policy enabling tropical forests to approach their potential contribution to global-climate-change mitigation requires forecasts of land use and carbon storage on a large scale over long periods. In this paper, we present an integrated modeling methodology that addresses these needs. We model the dynamics of the human land-use system and of C pools contained in each ecosystem, as well as their interactions. The model is national scale, and is currently applied in a preliminary way to Costa Rica using data spanning a period of over 50 years. It combines an ecological process model, parameterized using field and other data, with an economic model, estimated using historical data to ensure a close link to actual behavior. These two models are linked so that ecological conditions affect land-use choices and vice versa. The integrated model predicts land use and its consequences for C storage for policy scenarios. These predictions can be used to create baselines, reward sequestration, and estimate the value in both environmental and economic terms of including C sequestration in tropical forests as part of the efforts to mitigate global climate change. The model can also be used to assess the benefits from costly activities to increase accuracy and thus reduce errors and their societal costs.

Journal of Environmental Management↗

Uncertainty and sensitivity issues in process-based models of carbon and nitrogen cycles in terrestrial ecosystems

Many process-based models of carbon (C) and nitrogen (N) cycles have been developed for northern forest ecosystems. These models are widely used to evaluate the long-term decisions in forest management dealing with effects like particulate pollution, productivity and climate change. Regarding climate change, one of the key questions that have sensitive political implications is whether northern forests will sequester atmospheric C or not. Whilst many process-based models have been tested for accuracy by evaluating or validating against observed data, few have dealt with the complexity of the incorporated procedures to estimate uncertainties associated with model predictions or the sensitivity of these predictions to input factors in a systematic, inter-model comparison fashion. In general, models differ in their underlying attempts to match natural complexities with assumed or imposed model structure and process formulations to estimate model parameters, to gather data and to address issues on scope, scale and natural variations. Uncertainties may originate from model structure, estimation of model parameters, data input, representation of natural variation and scaling exercises. Model structure relates to the mathematical representation of the processes modelled and the type of state variables that a model contains. The modelling of partitioning among above- and below-ground C and N pools and the interdependence among these pools remain a major source of uncertainty in model structure and error propagation. For example, most soil C models use at least three state variables to represent the different types of soil organic matter (SOM). This approach results in creating three artificial SOM pools, assuming that each one contains C compounds with the same turnover rate. In reality, SOM consists of many different types of C compounds with widely different turnover rates. Uncertainty in data and parameter estimates are closely linked. Data uncertainties are associated with high variations in estimating forest biomass, productivity and soil organic matter and their estimates may be incomplete for model initialisation, calibration, validation and sensitivity analysis of generalised predictor models. The scale at which a model is being used also affects the level of uncertainty, as the errors in the prediction of the C and N dynamics differ from site to landscape levels and across climatic regions. If the spatial or temporal scale of a model application is changed, additional uncertainty arises from neglecting natural variability in system variables in time and space. Uncertainty issues are also intimately related to model validation and sensitivity analysis. The estimation of uncertainties is needed to inform decision processes in order to detect the possible corridor of development. Uncertainty in this context is an essential measure of quality for stakeholder and decision makers.

Book chapter↗

Excessive phosphorus loading contributes to future vulnerability of mangrove ecosystems by reducing net ecosystem exchange of carbon

J.N. “Ding” Darling National Wildlife Refuge (DDNWR) is located on Sanibel Island along the southwestern coast of Florida, USA. There, eutrophication attributed to agricultural discharge along the Caloosahatchee River has affected the area’s aquatic habitat. In anticipation of additional nutrient loading, we experimentally fertilized mangrove forests with nitrogen (+N; NH4) and phosphorus (+P; P2O5) for 3 years, and monitored soil and pneumatophore CO2 fluxes and tree sap flow from two mangrove species. Furthermore, we modeled individual tree and stand water use, from which we developed carbon (C) budgets for +N and + P vs. control simulations based on a novel application of water use efficiency conversion. Many of the measured response variables provided hints of subtle changes in response to +P rather than +N, which were enhanced when scaled. From this, we found that additional P loading is expected to reduce both gross and net primary productivity as well as CO2 uptake via net ecosystem exchange of C, likely pressing the system beyond metabolic capacity and leading to a 48–62% decrease in projected lateral C export. Greater eutrophication will likely compound vulnerabilities to sea-level rise submergence, especially where P concentrations are high and already reducing soil surface elevations.

Florida↗

Automatic photometric titrations of calcium and magnesium in carbonate rocks

Rapid nonsubjective methods have been developed for the determination of calcium and magnesium in carbonate rocks. From a single solution of the sample, calcium is titrated directly, and magnesium is titrated after a rapid removal of R2O3 and precipitation of calcium as the tungstate. A concentrated and a dilute solution of disodium ethylenediamine tetraacetate are used as titrants. The concentrated solution is added almost to the end point, then the weak solution is added in an automatic titrator to determine the end point precisely.

Analytical Chemistry↗

Polymeric nanofiber-carbon nanotube composite mats as fast-equilibrium passive samplers for polar organic pollutants

To improve the performance of polymeric electrospun nanofiber mats (ENMs) for equilibrium passive sampling applications in water, we integrated two types of multiwalled carbon nanotubes (CNTs; with and without surface carboxyl groups) into polyacrylonitrile (PAN) and polystyrene (PS) ENMs. For 11 polar and moderately hydrophobic compounds (−0.07 ≤ log K OW ≤ 3.13), 90% of equilibrium uptake was achieved in under 0.8 days ( t 90% values) in nonmixed ENM-CNT systems. Sorption capacity of ENM-CNTs was between 2- and 50-fold greater than pure polymer ENMs, with equilibrium partition coefficients ( K ENM-W values) ranging from 1.4 to 3.1 log units (L/kg) depending on polymer type (hydrophilic PAN or hydrophobic PS), CNT loading (i.e., values increased with weight percent (wt %) of CNTs), and CNT type (i.e., greater uptake with carboxylated CNTs composites). During field deployment at Muddy Creek in North Liberty, Iowa, optimal ENM-CNTs (PAN with 20 wt % carboxylated CNTs) yielded atrazine concentrations in surface water with a 40% difference relative to analysis of a same-day grab sample. We also observed a mean percent difference of 30 (±20)% when comparing ENM-CNT sampler results to grab sample data collected within 1 week of deployment. With their rapid, high capacity uptake and small material footprint, ENM-CNT equilibrium passive samplers represent a promising alternative to complement traditional integrative passive samplers while offering convenience over large volume grab sampling.

Environmental Science & Technology↗

Food matrix reference materials for hydrogen, carbon, nitrogen, oxygen, and sulfur stable isotope-ratio measurements: Collagens, flours, honeys, and vegetable oils

An international project developed, quality-tested, and measured isotope–delta values of 10 new food matrix reference materials (RMs) for hydrogen, carbon, nitrogen, oxygen, and sulfur stable isotope-ratio measurements to support food authenticity testing and food provenance verification. These new RMs, USGS82 to USGS91, will enable users to normalize measurements of samples to isotope–delta scales. The RMs include (i) two honeys from Canada and tropical Vietnam, (ii) two flours from C3 (rice) and C4 (millet) plants, (iii) four vegetable oils from C3 (olive, peanut) and C4 (corn) plants, and (iv) two collagen powders from marine fish and terrestrial mammal origins. An errors-in-variables regression model included the uncertainty associated with the measured and assigned values of the RMs, and it was applied centrally to normalize results and obtain consensus values and measurement uncertainties. Utilization of these new RMs should facilitate mutual compatibility of stable isotope data if accepted normalization procedures are applied and documented.

Journal of Agricultural and Food Chemistry↗

Reductive dehalogenation of hexachloroethane, carbon tetrachloride, and bromoform by anthrahydroquinone disulfonate and humic acid

The reductive dehalogenation of hexachloroethane (C2Cl6), carbon tetrachloride (CCl4), and bromoform (CHBr3) was examined at 50??C in aqueous solutions containing either (1) 500 ??M of 2,6-anthrahydroquinone disulfonate (AHQDS), (2) 250 ??M Fe2+, or (3) 250 ??M HS-. The pH ranged from 4.5 to 11.5 for AHQDS solutions and was 7.2 in the Fe2+ solutions and 7.8 in the HS- solutions. The observed disappearance of C2Cl6 in the presence of AHQDS was pseudo-first-order and fit k??ccl4 = k0[A(OH)2] + k1[A(OH)O-] + k2[A(O)22-] where A(OH)2, A(OH)O-, and A(O)22- represent the concentrations of the three forms of the AHQDS in solution. The values of k0, k1, and k2 were ???0,0.031, and 0.24 M-1 s-1, respectively. The addition of 25 mg of C/L of humic acid or organic matter extracted from Borden aquifer solids to aqueous solutions containing 250 ??M HS- or Fe2+ increased the reduction rate by factors of up to 10. The logarithms of the rate constants for the disappearance of C2Cl6 and CCl4 in seven different experimental systems were significantly correlated; log k???ccl4 = 0-64 log k??? c2cl6 - 0.83 with r2 = 0.80. The observed trend in reaction rates of C2Cl6 > CCl4 > CHBr3 is consistent with a decreasing trend in one-electron reduction potentials. ?? 1994 American Chemical Society.

Environmental Science & Technology↗

Compound-specific carbon and hydrogen isotope analysis of sub-parts per billion level waterborne petroleum hydrocarbons

Compound-specific carbon and hydrogen isotope analysis (CSCIA and CSHIA) has been increasingly used to study the source, transport, and bioremediation of organic contaminants such as petroleum hydrocarbons. In natural aquatic systems, dissolved contaminants represent the bioavailable fraction that generally is of the greatest toxicological significance. However, determining the isotopic ratios of waterborne hydrophobic contaminants in natural waters is very challenging because of their extremely low concentrations (often at sub-parts ber billion, or even lower). To acquire sufficient quantities of polycyclic aromatic hydrocarbons with 10 ng/L concentration for CSHIA, more than 1000 L of water must be extracted. Conventional liquid/liquid or solid-phase extraction is not suitable for such large volume extractions. We have developed a new approach that is capable of efficiently sampling sub-parts per billion level waterborne petroleum hydrocarbons for CSIA. We use semipermeable membrane devices (SPMDs) to accumulate hydrophobic contaminants from polluted waters and then recover the compounds in the laboratory for CSIA. In this study, we demonstrate, under a variety of experimental conditions (different concentrations, temperatures, and turbulence levels), that SPMD-associated processes do not induce C and H isotopic fractionations. The applicability of SPMD-CSIA technology to natural systems is further demonstrated by determining the ??13C and ??D values of petroleum hydrocarbons present in the Pawtuxet River, RI. Our results show that the combined SPMD-CSIA is an effective tool to investigate the source and fate of hydrophobic contaminants in the aquatic environments.

Environmental Science & Technology↗