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At least 937 records · Page 52Linked to original sources
USGS1998

Carbon isotopic comparisons of oil products used in the developmental history of Alaska

Studies of the fate of oil released into Prince William Sound, AK, as a result of the 1989 Exxon Valdez oil spill, have led to an unexpected discovery. In addition to oil-like residues attributed to the spill, the ubiquitous presence of flattened tar balls, the carbon isotopic compositions of which fall within a surprisingly narrow range [??13C(PDB) = -23.7 ?? 0.3??? (n = 65)], were observed on the shorelines of the northern and western parts of the sound. These compositions are similar to those of some oil products [-23.7 ?? 0.7??? (n = 35)] that were shipped from California and used in Alaska for fuel, lubrication, construction, and paving before ~ 1970. These products include fuel oil, asphalt, and lubricants [-23.8 ?? 0.5??? (n = 11)], caulking, sealants, and roofing tar [-23.7 ?? 0.7??? (n = 16)], and road pavements and airport runways [-23.5 ?? 0.9??? (n = 8)]. Fuel oil and asphalt [-23.5 ?? 0.1??? (n = 3)], stored at the old Valdez town site and spilled during the 1964 Alaskan earthquake, appear to be the source of most of the beached tar balls. Oil products with lighter carbon isotopic compositions, between -25 and -30??? (n = 18), appear to have been used more recently in Alaska, that is, after ~ 1970. The source of some of the products used for modern pavement and runways [-29.3 ?? 0.2??? (n = 6)] is likely Alaskan North Slope crude oil, an example of which was spilled in the 1989 oil spill [-29.2??? (n = 1)].

Chemical Geology↗
USGS2001

Quality of selected coal seams from Indiana: Implications for carbonization

The chemical properties of two high-volatile bituminous coals, the Danville Coal Member of the Dugger Formation and the Lower Block Coal Member of the Brazil Formation from southern Indiana, were compared to understand the differences in their coking behavior. It was determined that of the two, the Lower Block has better characteristics for coking. Observed factors that contribute to the differences in the coking behavior of the coals include carbon content, organic sulfur content, and oxygen/carbon (O/C) ratios. The Lower Block coal has greater carbon content than the Danville coal, leading to a lower O/C ratio, which is more favorable for coking. Organic sulfur content is higher in the Lower Block coal, and a strong correlation was found between organic sulfur and plasticity. The majority of the data for both seams plot in the Type III zone on a van Krevelen diagram, and several samples from the Lower Block coal plot into the Type II zone, suggesting a perhydrous character for those samples. This divergence in properties between the Lower Block and Danville coals may account for the superior coking behavior of the Lower Block coal. ?? 2001 Elsevier Science B.V. All rights reserved.

International Journal of Coal Geology↗
USGS2003

Kinetic dissolution of carbonates and Mn oxides in acidic water: Measurement of in situ field rates and reactive transport modeling

The kinetics of carbonate and Mn oxide dissolution under acidic conditions were examined through the in situ exposure of pure phase samples to acidic ground water in Pinal Creek Basin, Arizona. The average long-term calculated in situ dissolution rates for calcite and dolomite were 1.65??10-7 and 3.64??10-10 mmol/(cm2 s), respectively, which were about 3 orders of magnitude slower than rates derived in laboratory experiments by other investigators. Application of both in situ and lab-derived calcite and dolomite dissolution rates to equilibrium reactive transport simulations of a column experiment did not improve the fit to measured outflow chemistry: at the spatial and temporal scales of the column experiment, the use of an equilibrium model adequately simulated carbonate dissolution in the column. Pyrolusite (MnO2) exposed to acidic ground water for 595 days increased slightly in weight despite thermodynamic conditions that favored dissolution. This result might be related to a recent finding by another investigator that the reductive dissolution of pyrolusite is accompanied by the precipitation of a mixed Mn-Fe oxide species. In PHREEQC reactive transport simulations, the incorporation of Mn kinetics improved the fit between observed and simulated behavior at the column and field scales, although the column-fitted rate for Mn-oxide dissolution was about 4 orders of magnitude greater than the field-fitted rate. Remaining differences between observed and simulated contaminant transport trends at the Pinal Creek site were likely related to factors other than the Mn oxide dissolution rate, such as the concentration of Fe oxide surface sites available for adsorption, the effects of competition among dissolved species for available surface sites, or reactions not included in the model.

Applied Geochemistry↗
USGS1997

Effects of carbon dioxide variations in the unsaturated zone on water chemistry in a glacial-outwash aquifer

The research site at Otis Air Base, Cape Cod, Massachusetts, has been developed for hydrogeological and geochemical studies of sewage-effluent contaminated groundwater since 1982. Research of hydrologic properties, transport, and chemical and biological processes is ongoing, but the origin of background water chemistry has not been determined. The principal geochemical process giving rise to the observed background water chemistry is CO2-controlled hydrolysis of Na feldspar. Geochemical modeling demonstrated that CO2 sources could vary over the project area. Analyses of unsaturated zone gases showed variations in CO2 which were dependent on land use and vegetative cover in the area of groundwater recharge. Measurements of CO2 in unsaturated-zone gases showed that concentrations of total inorganic C in recharge water should range from about 0.035 to 1.0 mmoles/L in the vicinity of Otis Air Base. Flux of CO2 from the unsaturated zone varied for a principal land uses, ranging from 86 gC/m2/yr for low vegetated areas to 1630 gC/m2/yr for a golf course. Carbon dioxide flux from woodlands was 220 gC/m2/yr, lower than reported fluxes of 500 to 600 gC/m2/yr for woodlands in a similar climate. Carbon dioxide flux from grassy areas was 540 gC/m2/yr, higher than reported fluxes of 230 to 490 gC/m2/yr for grasslands in a similar climate.

Applied Geochemistry↗
USGS2015

Extraction of hydrocarbons from high-maturity Marcellus Shale using supercritical carbon dioxide

Shale is now commonly exploited as a hydrocarbon resource. Due to the high degree of geochemical and petrophysical heterogeneity both between shale reservoirs and within a single reservoir, there is a growing need to find more efficient methods of extracting petroleum compounds (crude oil, natural gas, bitumen) from potential source rocks. In this study, supercritical carbon dioxide (CO 2 ) was used to extract n -aliphatic hydrocarbons from ground samples of Marcellus shale. Samples were collected from vertically drilled wells in central and western Pennsylvania, USA, with total organic carbon (TOC) content ranging from 1.5 to 6.2 wt %. Extraction temperature and pressure conditions (80°C and 21.7 MPa, respectively) were chosen to represent approximate in situ reservoir conditions at sample depth (1920–2280 m). Hydrocarbon yield was evaluated as a function of sample matrix particle size (sieve size) over the following size ranges: 1000–500 μm, 250–125 μm, and 63–25 μm. Several methods of shale characterization including Rock-Eval II pyrolysis, organic petrography, Brunauer–Emmett–Teller surface area, and X-ray diffraction analyses were also performed to better understand potential controls on extraction yields. Despite high sample thermal maturity, results show that supercritical CO 2 can liberate diesel-range ( n -C 11 through n -C 21 ) n -aliphatic hydrocarbons. The total quantity of extracted, resolvable n -aliphatic hydrocarbons ranges from approximately 0.3 to 12 mg of hydrocarbon per gram of TOC. Sieve size does have an effect on extraction yield, with highest recovery from the 250–125 μm size fraction. However, the significance of this effect is limited, likely due to the low size ranges of the extracted shale particles. Additional trends in hydrocarbon yield are observed among all samples, regardless of sieve size: 1) yield increases as a function of specific surface area ( r 2 = 0.78); and 2) both yield and surface area increase with increasing TOC content ( r 2 = 0.97 and 0.86, respectively). Given that supercritical CO 2 is able to mobilize residual organic matter present in overmature shales, this study contributes to a better understanding of the extent and potential factors affecting the extraction process.

Pennsylvania↗
USGS2019

Methane emissions from artificial waterbodies dominate the carbon footprint of irrigation: A study of transitions in the food-energy-water-climate nexus (Spain, 1900-2014)

Irrigation in the Mediterranean region has been used for millennia and has greatly expanded with industrialization. Irrigation is critical for climate change adaptation, but it is also an important source of greenhouse gas emissions. This study analyzes the carbon (C) footprint of irrigation in Spain, covering the complete historical process of mechanization. A 21-fold total, 6-fold area-based, and 4-fold product-based increase in the carbon footprint was observed during the 20th century, despite an increase in water use efficiency. CH 4 emissions from waterbodies, which had not previously been considered in the C footprint of irrigation systems, dominated the emission budget during most of the analyzed period. Technologies to save water and tap new water resources greatly increased energy and infrastructure demand, while improvements in power generation efficiency had a limited influence on irrigation emissions. Electricity production from irrigation dams may contribute to climate change mitigation, but the amount produced in relation to that consumed in irrigation has greatly declined. High uncertainty in CH 4 emission estimates from waterbodies stresses a need for more spatially resolved data and an improved empirical knowledge of the links between water quality, water level fluctuations, and emissions at the regional scale.

Environmental Science & Technology↗
USGS2022

Using carbon, nitrogen, and mercury isotope values to distinguish mercury sources to Alaskan lake trout

Lake trout ( Salvelinus namaycush ), collected from 13 remote lakes located in southwestern Alaska, were analyzed for carbon, nitrogen, and mercury (Hg) stable isotope values to assess the importance of migrating oceanic salmon, volcanic activity, and atmospheric deposition to fish Hg burden. Methylmercury (MeHg) bioaccumulation in phytoplankton (5.0–6.9 kg L –1 ) was also measured to quantify the basal uptake of MeHg to these aquatic food webs. Hg isotope values in lake trout revealed that while the extent of precipitation-delivered Hg was similar across the entire study area, volcanic Hg is likely an important additional source to lake trout in proximate lakes. In contrast, migratory salmon ( Oncorhynchus nerka ) deliver little MeHg to lake trout directly, although indirect delivery processes via decay could exist. A high level of variability in carbon, nitrogen, and Hg isotope values indicates niche partitioning in lake trout populations within each lake and that a complex suite of ecological interactions is occurring, complicating the conceptually linear assessment of the contaminant source to the receiving organism. Without connecting energy and contaminant isotope axes, we would not have understood why lake trout from these pristine lakes have highly variable Hg burdens despite consistently low water Hg and comparable age-length dynamics.

Alaska↗
USGS2003

Evaluation of specific ultraviolet absorbance as an indicator of the chemical composition and reactivity of dissolved organic carbon

Specific UV absorbance (SUVA) is defined as the UV absorbance of a water sample at a given wavelength normalized for dissolved organic carbon (DOC) concentration. Our data indicate that SUVA, determined at 254 nm, is strongly correlated with percent aromaticity as determined by 13C NMR for 13 organic matter isolates obtained from a variety of aquatic environments. SUVA, therefore, is shown to be a useful parameter for estimating the dissolved aromatic carbon content in aquatic systems. Experiments involving the reactivity of DOC with chlorine and tetramethylammonium hydroxide (TMAH), however, show a wide range of reactivity for samples with similar SUVA values. These results indicate that, while SUVA measurements are good predictors of general chemical characteristics of DOC, they do not provide information about reactivity of DOC derived from different types of source materials. Sample pH, nitrate, and iron were found to influence SUVA measurements.

Environmental Science & Technology↗
USGS2008

Relating carbon monoxide photoproduction to dissolved organic matter functionality

Aqueous solutions of humic substances (HSs) and pure monomeric aromatics were irradiated to investigate the chemical controls upon carbon monoxide (CO) photoproduction from dissolved organic matter (DOM). HSs were isolated from lakes, rivers, marsh, and ocean. Inclusion of humic, fulvic, hydrophobic organic, and hydrophilic organic acid fractions from these environments provided samples diverse in source and isolation protocol. In spite of these major differences, HS absorption coefficients (a) and photoreactivities (a bleaching and CO production) were strongly dependent upon HS aromaticity ( r 2 >0.90; n = 11), implying aromatic moieties are the principal chromophores and photoreactants within HSs, and by extension, DOM. Carbonyl carbon and CO photoproduction were not correlated, implying that carbonyl moieties are not quantitatively important in CO photoproduction. CO photoproduction efficiency of aqueous solutions of monomeric aromatic compounds that are common constituents of organic matter varied with the nature of ring substituents. Specifically, electron donating groups increased, while electron withdrawing groups decreased CO photoproductivity, supporting our conclusion that carbonyl substituents are not quantitatively important in CO photoproduction. Significantly, aromatic CO photoproduction efficiency spanned 3 orders of magnitude, indicating that variations in the CO apparent quantum yields of natural DOM may be related to variations in aromatic DOM substituent group chemistry.

Environmental Science and Technology↗
USGS1995

Linear solvation energy relationship of the limiting partition coefficient of organic solutes between water and activated carbon

A linear solvation energy relationship has been found for 353 values of the limiting adsorption coefficients of diverse chemicals: log K = −0.37 + 0.0341 V i − 1.07β + D + 0.65 P with R = 0.951, s = 0.51, n = 353, and F = 818.0, where V i is the intrinsic molar volume; β is a measure of the hydrogen bond acceptor strength of the solute; D is an index parameter for the research group which includes the effects of the different types of carbon used, the temperature, and the length of time allowed for the adsorption equilibrium to be established; and P is an index parameter for the flatness of the molecule. P is defined to be unity if there is an aromatic system in the molecule or if there is a double bond or series of conjugated double bonds with no more that one non-hydrogen atom beyond the double bond and zero otherwise. A slightly better fit is obtained if the two-thirds power of V i is used as a measure of the surface area in place of the volume term: log K = −1.75 + 0.227 V 2/3 − 1.10β + D + 0.60 P with R = 0.954, s = 0.49, n = 353, and F = 895.39. This is the first quantitative measure of the effect of the shape of the molecule on its tendency to be adsorbed on activated carbon.

Environmental Science & Technology↗
USGS1997

Unusual carbon and oxygen isotropic ratios of ostracodal calcite from last interglacial (Sangamon episode) lacustrine sediment in Raymond Basin, Illinois, USA

The stable isotopic records of ostracode valves deposited during the last interglaciation in Raymond Basin, Illinois, have ??13C and ??18O values as high as +16.5??? and +9.2??? respectively, the highest values yet reported from continental ostracodal calcite. Located in south-central Illinois, Raymond, Pittsburgh, Bald Knob, and Hopwood Farm basins collectively have yielded important long pollen and ostracode records that date from about 130 000 years ago to the present. Although fossils from the present-day interglaciation are not well preserved, these records constitute the only described, conformable, fossiliferous successions of this age from the interior of glaciated North America. The high ??13C values from Raymond Basin are attributed to the residual effects of methane loss either by ebullition or by emission through the stems of senescent emergent aquatic vegetation. A mass balance model suggests that an increase in ??13C of dissolved inorganic carbon on the order of +15??? is possible within a few hours given modest rates of methanogenesis of about 0.02 mol m-2 d-1. The ??13C records from other studies of ostracode valves have values approaching, but not exceeding about +14??? suggesting a limiting value to ???13C enrichment due to simultaneous inputs and outputs of dissolved inorganic carbon. Values of ??18O in ostracodal calcite are quite variable (-4 to +9???) in sediment from the late Sangamon subepisode. A model of isotopic enrichment in a desiccating water body implies that a reduction in reservoir volume of 20% could produce this range of isotopic values. High humidity and evaporation probably account for most of the ??18O variability.

Journal of Paleolimnology↗
USGS1999

The carbon cycle and biogeochemical dynamics in lake sediments

The concentrations of organic carbon (OC) and CaCO3 in lake sediments are often inversely related. This relation occurs in surface sediments from different locations in the same lake, surface sediments from different lakes, and with depth in Holocene sediments. Where data on accumulation rates are available, the relation holds for organic carbon and CaCO3 accumulation rates as well. An increase of several percent OC is accompanied by a decrease of several tens of percent CaCO3 indicating that the inverse relation is not due to simple dilution of one component by another. It appears from core data that once the OC concentration in the sediments becomes greater than about 12%, the CO2 produced by decomposition of that OC and production of organic acids lowers the pH of anoxic pore waters enough to dissolve any CaCO3 that reaches the sediment-water interface. In a lake with a seasonally anoxic hypolimnion, processes in the water column also can produce an inverse relation between OC and CaCO3 over time. If productivity of the lake increases, the rain rate of OC from the epilimnion increases. Biogenic removal of CO2 and accompanying increase in pH also may increase the production of CaCO3. However, the decomposition of organic matter in the hypolimnion will decrease the pH of the hypolimnion causing greater dissolution of CaCO3 and therefore a decrease in the rain rate of CaCO3 to the sediment-water interface.

Journal of Paleolimnology↗
USGS2002

Carbon isotope fractionation of methyl bromide during agricultural soil fumigations

The isotopic composition of methyl bromide (CH3Br) has been suggested to be a potentially useful tracer for constraining the global CH3Br budget. In order to determine the carbon isotopic composition of CH3Br emitted from the most significant anthropogenic application (pre-plant fumigation) we directly measured the ??13C of CH3Br released during commercial fumigation. We also measured the isotopic fractionation associated with degradation in agricultural soil under typical field fumigation conditions. The isotopic composition of CH3Br collected in soil several hours after injection of the fumigant was -44.5??? and this value increased to -20.7??? over the following three days. The mean kinetic isotope effect (KIE) associated with degradation of CH3Br in agricultural soil (12???) was smaller than the reported value for methylotrophic bacterial strain IMB-1, isolated from previously fumigated agricultural soil, but was similar to methylotrophic bacterial strain CC495, isolated from a pristine forest litter zone. Using this fractionation associated with the degradation of CH3Br in agricultural soil and the mean ??13C of the industrially manufactured CH3Br (-54.4???), we calculate that the agricultural soil fumigation source has a carbon isotope signature that ranges from -52.8??? to -42.0???. Roughly 65% of industrially manufactured CH3Br is used for field fumigations. The remaining 35% is used for structural and post-harvest fumigations with a minor amount used during industrial chemical manufacturing. Assuming that the structural and post-harvest fumigation sources of CH3Br are emitted without substantial fractionation, we calculate that the ??13C of anthropogenically emitted CH3Br ranges from -53.2??? to -47.5???.

Conference Paper↗
USGS2006

Effect of tree line advance on carbon storage in NW Alaska

We investigated the size, distribution, and temporal dynamics of ecosystem carbon (C) pools in an area of recent tree line advance, northwest Alaska. Repeat aerial photographs show forest cover increased ???10% in our study area since 1949. We sampled C pools of four principal ecosystem types, tussock tundra, shrub tundra, woodland, and forest, all located on a 600-800 year old river terrace. Significant differences between ecosystem C pools, both above ground and below ground existed. Tundra sites store >22.2 kg C/m2, shrub tundra sites and woodland sites store 9.7 kg C/m2 and 14.3 kg C/m2, respectively, and forest sites store 14.4 kg C/m2. Landscape variation of total ecosystem C was primarily due to organic soil C and was secondarily due to C stored in trees. Soil C/N profiles of shrub tundra sites and woodland sites showed similarities with forest site soils at surface and tundra site soils at depth. We hypothesize that tundra systems transformed to forest systems in this area under a progression of permafrost degradation and enhanced drainage. On the basis of C pool estimates for the different ecosystem types, conversion of tundra sites to forest may have resulted in a net loss of > 7.8 kg C/m2, since aboveground C gains were more than offset by belowground C losses to decomposition in the tundra sites. Tree line advance therefore might not increase C storage in high-latitude ecosystems and thus might not, as previously suggested, act as a negative feedback to warming. Key to this hypothesis and to its projection to future climate response is the fate of soil carbon upon warming and permafrost drainage. Copyright 2006 by the American Geophysical Union.

Journal of Geophysical Research G: Biogeosciences↗
USGS2008

Sediment organic carbon burial in agriculturally eutrophic impoundments over the last century

We estimated organic carbon (OC) burial over the past century in 40 impoundments in one of the most intensively agricultural regions of the world. The volume of sediment deposited per unit time varied as a function of lake and watershed size, but smaller impoundments had greater deposition and accumulation rates per unit area. Annual water storage losses varied from 0.1-20% and were negatively correlated with impoundment size. Estimated sediment OC content was greatest in lakes with low ratios of watershed to impoundment area. Sediment OC burial rates were higher than those assumed for fertile impoundments by previous studies and were much higher than those measured in natural lakes. OC burial ranged from a high of 17,000 g C m-2 a-1 to a low of 148 g C m-2 a-1 and was significantly greater in small impoundments than large ones. The OC buried in these lakes originates in both autochthonous and allochthonous production. These analyses suggest that OC sequestration in moderate to large impoundments may be double the rate assumed in previous analyses. Extrapolation suggests that they may bury 4 times as much carbon (C) as the world's oceans. The world's farm ponds alone may bury more OC than the oceans and 33% as much as the world's rivers deliver to the sea. Copyright 2008 by the American Geophysical Union.

Global Biogeochemical Cycles↗
USGS2007

Increased groundwater to stream discharge from permafrost thawing in the Yukon River basin: Potential impacts on lateral export of carbon and nitrogen

Arctic and subarctic watersheds are undergoing climate warming, permafrost thawing, and thermokarst formation resulting in quantitative shifts in surface water - groundwater interaction at the basin scale. Groundwater currently comprises almost one fourth of Yukon River water discharged to the Bering Sea and contributes 5-10% of the dissolved organic carbon (DOC) and nitrogen (DON) and 35-45% of the dissolved inorganic carbon (DIC) and nitrogen (DIN) loads. Long-term strearnflow records (>30 yrs) of the Yukon River basin indicate a general upward trend in groundwater contribution to streamflow of 0.7-0.9%/yr and no pervasive change in annual flow. We propose that the increases in groundwater contributions were caused predominately by climate warming and permafrost thawing that enhances infiltration and supports deeper flowpaths. The increased groundwater fraction may result in decreased DOC and DON and increased DIC and DIN export when annual flow remains unchanged.

Geophysical Research Letters↗
USGS2009

Utilizing chromophoric dissolved organic matter measurements to derive export and reactivity of dissolved organic carbon exported to the Arctic Ocean: A case study of the Yukon River, Alaska

[1] The quality and quantity of dissolved organic matter (DOM) exported by Arctic rivers is known to vary with hydrology and this exported material plays a fundamental role in the biogeochemical cycling of carbon at high latitudes. We highlight the potential of optical measurements to examine DOM quality across the hydrograph in Arctic rivers. Furthermore, we establish chromophoric DOM (CDOM) relationships to dissolved organic carbon (DOC) and lignin phenols in the Yukon River and model DOC and lignin loads from CDOM measurements, the former in excellent agreement with long‐term DOC monitoring data. Intensive sampling across the historically under‐sampled spring flush period highlights the importance of this time for total export of DOC and particularly lignin. Calculated riverine DOC loads to the Arctic Ocean show an increase from previous estimates, especially when new higher discharge data are incorporated. Increased DOC loads indicate decreased residence times for terrigenous DOM in the Arctic Ocean with important implications for the reactivity and export of this material to the Atlantic Ocean.

Geophysical Research Letters↗
USGS2009

The Mauna Loa carbon dioxide record: lessons for long-term Earth observations

The Mauna Loa carbon dioxide record is an iconic symbol of the human capacity to alter the planet. Yet this record would not have been possible without the remarkable work of one man, Charles David Keeling. We describe three emergent themes that characterized his work: (1) his desire to study and understand the processes that control atmospheric CO 2 and the global carbon cycle, (2) his campaign to identify and minimize systematic measurement error, and (3) his tenacious efforts to maintain continuous funding despite changing government priorities and institutions. In many ways, the story of the Mauna Loa record demonstrates that distinctions between research and “routine” measurements are not very useful in long-term monitoring of Earth properties and processes.

Book chapter↗