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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↗

Biogeochemical controls on diel cycling of stable isotopes of dissolved 02 and dissolved inorganic carbon in the Big Hole River, Montana

Rivers with high biological productivity typically show substantial increases in pH and dissolved oxygen (DO) concentration during the day and decreases at night, in response to changes in the relative rates of aquatic photosynthesis and respiration. These changes, coupled with temperature variations, may impart diel (24-h) fluctuations in the concentration of trace metals, nutrients, and other chemical species. A better understanding of diel processes in rivers is needed and will lead to improved methods of data collection for both monitoring and research purposes. Previous studies have used stable isotopes of dissolved oxygen (DO) and dissolved inorganic carbon (DIC) as tracers of geochemical and biological processes in streams, lakes, and marine systems. Although seasonal variation in δ 18 O of DO in rivers and lakes has been documented, no study has investigated diel changes in this parameter. Here, we demonstrate large (up to 13‰) cycles in δ 18 O-DO for two late summer sampling periods in the Big Hole River of southwest Montana and illustrate that these changes are correlated to variations in the DO concentration, the C-isotopic composition of DIC, and the primary productivity of the system. The magnitude of the diel cycle in δ 18 O-DO was greater in August versus September because of the longer photoperiod and warmer water temperatures. This study provides another biogeochemical tool for investigating the O 2 and C budgets in rivers and may also be applicable to lake and groundwater systems.

Montana↗

Differential effects of dissolved organic carbon upon re-entrainment and surface properties of groundwater bacteria and bacteria-sized microspheres during transport through a contaminated, sandy aquifer

Injection-and-recovery studies involving a contaminated, sandy aquifer (Cape Cod, Massachusetts) were conducted to assess the relative susceptibility for in situ re-entrainment of attached groundwater bacteria ( Pseudomonas stuzeri ML2, and uncultured, native bacteria) and carboxylate-modified microspheres (0.2 and 1.0 μm diameters). Different patterns of re-entrainment were evident for the two colloids in response to subsequent injections of groundwater (hydrodynamic perturbation), deionized water (ionic strength alteration), 77 μM linear alkylbenzene sulfonates (LAS, anionic surfactant), and 76 μM Tween 80 (polyoxyethylene sorbitan monooleate, a very hydrophobic nonionic surfactant). An injection of deionized water was more effective in causing detachment of micrsopheres than were either of the surfactants, consistent with the more electrostatic nature of microsphere’s attachment, their extreme hydrophilicity (hydrophilicity index, HI, of 0.99), and negative charge (zeta potentials, ζ, of −44 to −49 mv). In contrast, Tween 80 was considerably more effective in re-entraining the more-hydrophobic native bacteria. Both the hydrophilicities and zeta potentials of the native bacteria were highly sensitive to and linearly correlated with levels of groundwater dissolved organic carbon (DOC), which varied modestly from 0.6 to 1.3 mg L −1 . The most hydrophilic (0.52 HI) and negatively charged (ζ −38.1 mv) indigenous bacteria were associated with the lowest DOC. FTIR spectra indicated the latter community had the highest average density of surface carboxyl groups. In contrast, differences in groundwater (DOC) had no measurable effect on hydrophilicity of the bacteria-sized microspheres and only a minor effect on their ζ. These findings suggest that microspheres may not be very good surrogates for bacteria in field-scale transport studies and that adaptive (biological) changes in bacterial surface characteristics may need to be considered where there is longer-term exposure to contaminant DOC.

Environmental Science & Technology↗

Effect of dissolved organic carbon on the transport and attachment behaviors of Cryptosporidium parvum oocysts and carboxylate-modified microspheres advected through temperate humic and tropical volcanic agricultural soil

Transport of Cryptosporidium parvum oocysts and microspheres in two disparate (a clay- and Fe-rich, volcanic and a temperate, humic) agricultural soils were studied in the presence and absence of 100 mg L –1 of sodium dodecyl benzene sulfonate (SDBS), and Suwannee River Humic Acid (SRHA) at pH 5.0–6.0. Transport of carboxylate-modified, 1.8 μm microspheres in soil columns was highly sensitive to the nature of the dissolved organic carbon (DOC), whereas oocysts transport was more affected by soil mineralogy. SDBS increased transport of microspheres from 48% to 87% through the tropical soil and from 43% to 93% in temperate soil. In contrast, SRHA reduced transport of microspheres from 48% to 28% in tropical soil and from 43% to 16% in temperate soil. SDBS also increased oocysts transport through the temperate soil 5-fold, whereas no oocyst transport was detected in tropical soil. SRHA had only a nominal effect in increasing oocysts transport in tropical soil, but caused a 6-fold increase in transport through the temperate soil. Amendments of only 4 mg L –1 SRHA and SDBS decreased oocyst hydrophobicity from 66% to 20% and from 66% to 5%, respectively. However, SDBS increased microsphere hydrophobicity from 16% to 33%. Soil fines, which includes clays, and SRHA, both caused the oocysts zeta potential (ζ) to become more negative, but caused the highly hydrophilic microspheres to become less negatively charged. The disparate behaviors of the two colloids in the presence of an ionic surfactant and natural organic matter suggest that microspheres may not be suitable surrogates for oocysts in certain types of soils. These results indicate that whether or not DOC inhibits or promotes transport of oocysts and microspheres in agricultural soils and by how much, depends not only on the surface characteristics of the colloid, but the nature of the DOC and the soil mineralogy.

Environmental Science & Technology↗

Effects of sediment-associated extractable metals, degree of sediment grain sorting, and dissolved organic carbon upon Cryptosporidium parvum removal and transport within riverbank filtration sediments, Sonoma County, California

Oocysts of the protozoan pathogen Cryptosporidium parvum are of particular concern for riverbank filtration (RBF) operations because of their persistence, ubiquity, and resistance to chlorine disinfection. At the Russian River RBF site (Sonoma County, CA), transport of C. parvum oocysts and oocyst-sized (3 μm) carboxylate-modified microspheres through poorly sorted (sorting indices, σ 1 , up to 3.0) and geochemically heterogeneous sediments collected between 2 and 25 m below land surface (bls) were assessed. Removal was highly sensitive to variations in both the quantity of extractable metals (mainly Fe and Al) and degree of grain sorting. In flow-through columns, there was a log–linear relationship ( r 2 = 0.82 at p < 0.002) between collision efficiency (α, the probability that colloidal collisions with grain surfaces would result in attachment) and extractable metals, and a linear relationship ( r 2 = 0.99 at p < 0.002) between α and σ 1 . Collectively, variability in extractable metals and grain sorting accounted for ∼83% of the variability in α (at p < 0.0002) along the depth profiles. Amendments of 2.2 mg L –1 of Russian River dissolved organic carbon (DOC) reduced α for oocysts by 4–5 fold. The highly reactive hydrophobic organic acid (HPOA) fraction was particularly effective in re-entraining sediment-attached microspheres. However, the transport-enhancing effects of the riverine DOC did not appear to penetrate very deeply into the underlying sediments, judging from high α values (∼1.0) observed for oocysts being advected through unamended sediments collected at ∼2 m bls. This study suggests that in evaluating the efficacy of RBF operations to remove oocysts, it may be necessary to consider not only the geochemical nature and size distribution of the sediment grains, but also the degrees of sediment sorting and the concentration, reactivity, and penetration of the source water DOC.

California↗

Tidally driven export of dissolved organic carbon, total mercury, and methylmercury from a mangrove-dominated estuary

The flux of dissolved organic carbon (DOC) from mangrove swamps accounts for 10% of the global terrestrial flux of DOC to coastal oceans. Recent findings of high concentrations of mercury (Hg) and methylmercury (MeHg) in mangroves, in conjunction with the common co-occurrence of DOC and Hg species, have raised concerns that mercury fluxes may also be large. We used a novel approach to estimate export of DOC, Hg, and MeHg to coastal waters from a mangrove-dominated estuary in Everglades National Park (Florida, USA). Using in situ measurements of fluorescent dissolved organic matter as a proxy for DOC, filtered total Hg, and filtered MeHg, we estimated the DOC yield to be 180 (±12.6) g C m –2 yr –1 , which is in the range of previously reported values. Although Hg and MeHg yields from tidal mangrove swamps have not been previously measured, our estimated yields of Hg species (28 ± 4.5 μg total Hg m –2 yr –1 and 3.1 ± 0.4 μg methyl Hg m –2 yr –1 ) were five times greater than is typically reported for terrestrial wetlands. These results indicate that in addition to the well documented contributions of DOC, tidally driven export from mangroves represents a significant potential source of Hg and MeHg to nearby coastal waters.

Florida↗

Increases in dissolved organic carbon accelerate loss of toxic Al in Adirondack lakes recovering from acidification

Increasing pH and decreasing Al in surface waters recovering from acidification have been accompanied by increasing concentrations of dissolved organic carbon (DOC) and associated organic acids that partially offset pH increases and complicate assessments of recovery from acidification. To better understand the processes of recovery, monthly chemistry from 42 lakes in the Adirondack region, NY, collected from 1994 to 2011, were used to (1) evaluate long-term changes in DOC and associated strongly acidic organic acids and (2) use the base-cation surplus (BCS) as a chemical index to assess the effects of increasing DOC concentrations on the Al chemistry of these lakes. Over the study period, the BCS increased (p < 0.01) and concentrations of toxic inorganic monomeric Al (IMAl) decreased (p < 0.01). The decreases in IMAl were greater than expected from the increases in the BCS. Higher DOC concentrations that increased organic complexation of Al resulted in a decrease in the IMAl fraction of total monomeric Al from 57% in 1994 to 23% in 2011. Increasing DOC concentrations have accelerated recovery in terms of decreasing toxic Al beyond that directly accomplished by reducing atmospheric deposition of strong mineral acids.

Environmental Science & Technology↗

Stable carbon and oxygen isotope record of central Lake Erie sediments

Stable carbon and oxygen isotope data from mollusc aragonite extracted from sediment cores provide new information on the origin and history of sedimentation in the southwestern area of the central basin of Lake Erie. Sediments infilling the Sandusky subbasin consist of three lithologic units overlying glacial deposits. The lowest of these is a soft gray mud overlain by a shell hash layer containing Sphaerium striatinum fragments. A fluid mud unit caps the shell hash layer and extends upwards to the sediment-water interface. New stable isotope data suggest that the soft gray mud unit is of postglacial, rather than proglacial, origin. These data also suggest that the shell hash layer was derived from erosional winnowing of the underlying soft gray mud layer. This winnowing event may have occurred as a result of the Nipissing flood. The Pelee-Lorain moraine, which forms the eastern boundary of the Sandusky subbasin, is an elevated area of till capped by a sand deposit that originated as a beach. The presence of both the shell hash layer and relict beach deposit strengthens the interpretation that the Nipissing flood was a critical event in the development of the southwestern area of the central basin of Lake Erie. This event, which returned drainage from the upper lakes to the Lake Erie basin, was a dominant influence on regional stratigraphy, bathymetry, and depositional setting.

Journal of Paleolimnology↗

Monitoring and verifying changes of organic carbon in soil

Changes in soil and vegetation management can impact strongly on the rates of carbon (C) accumulation and loss in soil, even over short periods of time. Detecting the effects of such changes in accumulation and loss rates on the amount of C stored in soil presents many challenges. Consideration of the temporal and spatial heterogeneity of soil properties, general environmental conditions, and management history is essential when designing methods for monitoring and projecting changes in soil C stocks. Several approaches and tools will be required to develop reliable estimates of changes in soil C at scales ranging from the individual experimental plot to whole regional and national inventories. In this paper we present an overview of soil properties and processes that must be considered. We classify the methods for determining soil C changes as direct or indirect. Direct methods include field and laboratory measurements of total C, various physical and chemical fractions, and C isotopes. A promising direct method is eddy covariance measurement of CO 2 fluxes. Indirect methods include simple and stratified accounting, use of environmental and topographic relationships, and modeling approaches. We present a conceptual plan for monitoring soil C changes at regional scales that can be readily implemented. Finally, we anticipate significant improvements in soil C monitoring with the advent of instruments capable of direct and precise measurements in the field as well as methods for interpreting and extrapolating spatial and temporal information.

Climatic Change↗

Soil organic carbon dynamics as related to land use history in the northwestern Great Plains

Strategies for mitigating the global greenhouse effect must account for soil organic carbon (SOC) dynamics at both spatial and temporal scales, which is usually challenging owing to limitations in data and approach. This study was conducted to characterize the SOC dynamics associated with land use change history in the northwestern Great Plains ecoregion. A sampling framework (40 sample blocks of 10 × 10 km 2 randomly located in the ecoregion) and the General Ensemble Biogeochemical Modeling System (GEMS) were used to quantify the spatial and temporal variability in the SOC stock from 1972 to 2001. Results indicate that C source and sink areas coexisted within the ecoregion, and the SOC stock in the upper 20-cm depth increased by 3.93 Mg ha −1 over the 29 years. About 17.5% of the area was evaluated as a C source at 122 kg C ha −1 yr −1 . The spatial variability of SOC stock was attributed to the dynamics of both slow and passive fractions, while the temporal variation depended on the slow fraction only. The SOC change at the block scale was positively related to either grassland proportion or negatively related to cropland proportion. We concluded that the slow C pool determined whether soils behaved as sources or sinks of atmospheric CO 2 , but the strength depended on antecedent SOC contents, land cover type, and land use change history in the ecoregion.

Global Biogeochemical Cycles↗