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At least 829 records · Page 46Linked to original sources
USGS2001

Progression of natural attenuation processes at a crude-oil spill site . I. Geochemical evolution of the plume

A 16-year study of a hydrocarbon plume shows that the extent of contaminant migration and compound-specific behavior have changed as redox reactions, most notably iron reduction, have progressed over time. Concentration changes at a small scale, determined from analysis of pore-water samples drained from aquifer cores, are compared with concentration changes at the plume scale, determined from analysis of water samples from an observation well network. The small-scale data show clearly that the hydrocarbon plume is growing slowly as sediment iron oxides are depleted. Contaminants, such as ortho -xylene that appeared not to be moving downgradient from the oil on the basis of observation well data, are migrating in thin layers as the aquifer evolves to methanogenic conditions. However, the plume-scale observation well data show that the downgradient extent of the Fe 2+ and BTEX plume did not change between 1992 and 1995. Instead, depletion of the unstable Fe (III) oxides near the subsurface crude-oil source has caused the maximum dissolved iron concentration zone within the plume to spread at a rate of approximately 3 m/year. The zone of maximum concentrations of benzene, toluene, ethylbenzene and xylene (BTEX) has also spread within the anoxic plume. In monitoring the remediation of hydrocarbon-contaminated ground water by natural attenuation, subtle concentration changes in observation well data from the anoxic zone may be diagnostic of depletion of the intrinsic electron-accepting capacity of the aquifer. Recognition of these subtle patterns may allow early prediction of growth of the hydrocarbon plume.

Journal of Contaminant Hydrology↗
USGS1995

Population recovery and natural recruitment of lake trout at Gull Island Shoal, Lake Superior, 1964-1992

We documented an increase in the abundance of wild lake trout ( Salvelinus namaycush ) at Gull Island Shoal in western Lake Superior and examined the relationship between parental-stock size and recruitment of age-0 fish in 1964–1992. Abundance of adult wild female lake trout and densities of age-0 fish both increased during the 28-year period. A significant positive, linear relationship (P = 0.0002) was found between the abundance of wild females on the spawning reef in the fall and density of age-0 lake trout on adjacent nursery grounds in August and September of the following year. The abundance of hatchery-origin females did not explain significant amounts (P = 0.107) of variation in recruitment. We concluded that most recruitment in 1965–1992 was the result of natural reproduction of wild females. After 28 years of recovery the Gull Island Shoal lake trout population appears to have additional capacity to increase because the stock-recruitment relationship is still linear. Therefore, restoration periods on the order of 30 years may be needed for other lake trout populations in the Great Lakes. We recommend that the refuge established to protect this population be maintained to allow further study of the relationship between parental stock and recruitment, and to provide a major source of recruitment to the lake trout population in the surrounding waters

Journal of Great Lakes Research↗
USGS1997

Environmental geochemistry of shale-hosted Ag-Pb-Zn massive sulfide deposits in northwest Alaska: Natural background concentrations of metals in water from mineralized areas

Red Dog, Lik and Drenchwater are shale-hosted stratiform Ag-Pb-Zn massive sulfide deposits in the northwestern Brooks Range. Natural background concentrations of metals in waters from the undisturbed (unmined) Drenchwater prospect and Lik deposit were compared to pre-mining baseline studies conducted at Red Dog. The primary factors affecting water chemistry are the extent of exposure of the deposits, the grade of mineralization, the presence of carbonate reeks in the section, and the proportion of Fe-sulfide in the ore. Surface water samples from the Drenchwater prospect, which has pyrite-dominant mineralization exposed in outcrop, have pH values as low as 2.8 and high dissolved concentrations of metals including as much as 95 mg 1-1 Al, 270 mg 1-1 Fe, 8 ??1-1 Cd, 10 ??1-1 Pb, and 2600 ??1-1 Zn, with As up to 26 ??g1-1. Surface waters from the Red Dog deposit prior to mining were also acidic and metal-rich, however, dissolved metal concentrations in Red Dog waters were many times greater. The higher metal concentrations in Red Dog waters reflect the high Zn grades and the abundant sphalerite, pyrite, and galena that were present in outcrop prior to mining. In contrast, despite significant mineralization at the Lik deposit, carbonate rocks in the section buffer the system, resulting in less acidic, mostly near-neutral pH values with low concentrations of most metals except Zn.

Applied Geochemistry↗
USGS1997

Natural radionuclides and plutonium in sediments from the western Arctic Ocean: Sedimentation rates and pathways of radionuclides

Sediment cores collected during R.V. Polar Sea AOS94 expedition from the Chukchi Shelf to the North Poke were analyzed for several decay-series natural radionuclides and Pu isotopes to study sedimentation rates and pathways of radionuclides in the western Arctic Ocean. The measured sedimentation rates vary by more than three orders of magnitude along the transect, from 210Pb based rates of 200-700 cm kyr-1 over the Chukchi Shelf and 89 cm kyr-1 at the Chukchi Slope to 230Th-based rates of 0.02-0.3 cm kyr-1 at various settings in the deep basin. 230Th(ex) profiles in the central western Arctic Basin are characterized by a cyclic pattern and a pronounced sub-surface maximum superimposed on an overall decrease with depth. Sediment inventories of excess 210Pb and 230Th in the deep basin as a whole cannot account for their in situ production and 2610Pb fall-out. The opposite is true at the slope and shallower waters. We contend that, as with other ocean basins, boundary scavenging also exists in the Arctic Ocean. The broad continental shelves and the slope region may have the potential of removing all or moat of the particle-reactive radionuclides unaccounted for in the deep basin. The Pu isotope data are consistent with the notion of boundary scavenging. Sediment inventories and concentrations of Pu decrease rapidly offshore. Isotopic composition of Pu suggests mixing of fall-out Pu, which decreases with increasing latitudes, and fuels reprocessing Pu derived from the Russian and Atlantic sides of the Arctic Ocean. Although fuel reprocessing Pu has impinged on the Chukchi Slope, its existence over the Chukchi Shelf is not evident and probably overshadowed by fall-out Pu.

Deep-Sea Research Part II: Topical Studies in Ocea↗
USGS2012

Maximizing the utility of monitoring to the adaptive management of natural resources

Data collection is an important step in any investigation about the structure or processes related to a natural system. In a purely scientific investigation (experiments, quasi-experiments, observational studies), data collection is part of the scientific method, preceded by the identification of hypotheses and the design of any manipulations of the system to test those hypotheses. Data collection and the manipulations that precede it are ideally designed to maximize the information that is derived from the study. That is, such investigations should be designed for maximum power to evaluate the relative validity of the hypotheses posed. When data collection is intended to inform the management of ecological systems, we call it monitoring. Note that our definition of monitoring encompasses a broader range of data-collection efforts than some alternative definitions – e.g. Chapter 3. The purpose of monitoring as we use the term can vary, from surveillance or “thumb on the pulse” monitoring (see Nichols and Williams 2006), intended to detect changes in a system due to any non-specified source (e.g. the North American Breeding Bird Survey), to very specific and targeted monitoring of the results of specific management actions (e.g. banding and aerial survey efforts related to North American waterfowl harvest management). Although a role of surveillance monitoring is to detect unanticipated changes in a system, the same result is possible from a collection of targeted monitoring programs distributed across the same spatial range (Box 4.1). In the face of limited budgets and many specific management questions, tying monitoring as closely as possible to management needs is warranted (Nichols and Williams 2006). Adaptive resource management (ARM; Walters 1986, Williams 1997, Kendall 2001, Moore and Conroy 2006, McCarthy and Possingham 2007, Conroy et al. 2008a) provides a context and specific purpose for monitoring: to evaluate decisions with respect to achievement of specific management objectives; and to evaluate the relative validity of predictive system models. This latter purpose is analogous to the role of data collection within the scientific method, in a research context.

Book chapter↗
USGS2024

When and where can coastal wetland restoration increase carbon sequestration as a natural climate solution?

Coastal wetlands are hotspots of carbon sequestration, and their conservation and restoration can help to mitigate climate change. However, there remains uncertainty on when and where coastal wetland restoration can most effectively act as a Natural Climate Solution (NCS). Here, we synthesize current understanding to illustrate the requirements for coastal wetland restoration to benefit climate, and discuss potential paths forward that address key uncertainties impeding implementation. To be effective as NCS, coastal wetland restoration projects will accrue climate cooling benefits that would not occur without management action (additionality), will be implementable (feasibility), and will persist over management-relevant timeframes (permanence). Several issues add uncertainty to understanding if these minimum requirements are met. First, coastal wetlands serve as both a landscape source and sink of carbon for other habitats, increasing uncertainty in additionality. Second, coastal wetlands can potentially migrate outside of project footprints as they respond to sea-level rise, increasing uncertainty in permanence. To address these first two issues, a system-wide approach may be necessary, rather than basing cooling benefits only on changes that occur within project boundaries. Third, the need for NCS to function over management-relevant decadal timescales means methane responses may be necessary to include in coastal wetland restoration planning and monitoring. Finally, there is uncertainty on how much data is required to justify restoration action. We summarize the minimum data required to make a decision on whether there is a net cooling benefit from a management action, noting that these data are more readily available than the data required to quantify the magnitude of cooling benefits for carbon crediting purposes. By reducing uncertainty, coastal wetland restoration can be implemented at the scale required to significantly contribute to addressing the current climate crisis.

Coastal Futures↗
USGS2002

Isolation of nonvolatile, organic solutes from natural waters by zeotrophic distillation of water from N,N-dimethylformamide

Nonvolatile, organic solutes that comprise the dissolved organic carbon (DOC) in saline waters were isolated by removal of the water by distillation from a N,N-dimethylformamideformic acid-acetonitrile mixture. Salts isolated with the DOC were removed by crystallization of sodium chloride and sodium sulfate from the solvent mixture, removal of silicic acid by acidification and precipitation, removal of boric acid by methylation and volatilization, and removal of phosphate by zinc acetate precipitation. Chemical alteration of the organic solutes was minimized during evaporative concentration steps by careful control of acid concentrations in the solvent mixture and was minimized during drying by conversion of the samples to pyridinium and sodium salts. Recoveries of various hydrophilic organic standards from aqueous salt solutions and recoveries of natural organic solutes from various water samples varied from 60 to 100%. Losses of organic solutes during the isolation procedure were nonselective and related to the number of salt- and precipitate-washing cycles in the procedure.

Analytical Chemistry↗
USGS2002

Determination of lithium isotopes at natural abundance levels by atomic absorption spectrometry

The relationships of the absorption of 6Li and 7Li hollow cathode lamp emissions are used to determine lithium isotopic composition in the natural abundance range of geologic materials. Absorption was found to have a nonlinear dependence upon total lithium concentration and isotopic composition. A method using nonlinear equations to describe the relationship of the absorption of 6Li and 7Li lamp radiation is proposed as a means of calculating isotopic composition that is independent of total lithium concentration.

Analytical Chemistry↗
USGS2002

Quantitative radiochemical method for determination of major sources of natural radioactivity in ores and minerals

When an ore sample contains radioactivity other than that attributable to the uranium series in equilibrium, a quantitative analysis of the other emitters must be made in order to determine the source of this activity. Thorium-232, radon-222, and lead-210 have been determined by isolation and subsequent activity analysis of some of their short-lived daughter products. The sulfides of bismuth and polonium are precipitated out of solutions of thorium or uranium ores, and the α -particle activity of polonium-214, polonium-212, and polonium-210 is determined by scintillation-counting techniques. Polonium-214 activity is used to determine radon-222, polonium-212 activity for thorium-232, and polonium-210 for lead-210. The development of these methods of radiochemical analysis will facilitate the rapid determination of some of the major sources of natural radioactivity.

Analytical Chemistry↗
USGS2020

Nanoscale molecular composition of solid bitumen from the Eagle Ford Group across a natural thermal maturity gradient

Microscopic solid bitumen is a petrographically defined secondary organic matter residue produced during petroleum generation and subsequent oil transformation. The presence of solid bitumen impacts many reservoir properties including porosity, permeability, and hydrocarbon generation and storage, among others. Furthermore, solid bitumen reflectance is an important parameter for assessing the thermal maturity of formations with little to no vitrinite. While the molecular composition of solid bitumen will strongly impact associated parameters such as the development of organic matter porosity, hydrocarbon generation, and optical reflectance, assessing the molecular composition of solid bitumen in situ within shale reservoirs can be challenging due to the small grain sizes (often ≤1 μm in diameter) and the inherent heterogeneity of shale formations. Here we employ the recently developed atomic force microscopy based infrared spectroscopy (AFM-IR) technique to investigate solid bitumen molecular composition in situ within shale samples from the Late Cretaceous Eagle Ford Group. These samples possess sulfur-rich type II kerogens that span a natural thermal maturity gradient from early oil generation to the dry gas window. The application of AFM-IR allows for the rapid collection of thousands of compositional measurements from solid bitumen with ∼50 nm resolution. Our results indicate that (i) solid bitumen from the lower Eagle Ford displays both intra- and intergranular variation in the relative abundance of CH 2 , C═C, and C═O moieties present; (ii) this molecular variation tends to, but does not always, decrease with an increase in thermal maturity; and (iii) the solid bitumen composition between samples, from an atomic ratio perspective, is more similar than analysis of bulk kerogen isolates would indicate. These findings are discussed with perspective toward understanding the impact of thermal stress on the composition of secondary organic matter within the Eagle Ford Shale and highlight the growing awareness that organic matter heterogeneity within petroliferous mudrocks extends down to the nanoscale regime.

Energy and Fuels↗
USGS2021

Effect of nanoparticle size and natural organic matter composition on the bioavailability of polyvinylpyrrolidone- coated platinum nanoparticles to a model freshwater invertebrate

The bioavailability of dissolved Pt(IV) and polyvinylpyrrolidone-coated platinum nanoparticles (PtNPs) of five different nominal hydrodynamic diameters (20, 30, 50, 75, and 95 nm) was characterized in laboratory experiments using the model freshwater snail Lymnaea stagnalis . Dissolved Pt(IV) and all nanoparticle sizes were bioavailable to L. stagnalis . Platinum bioavailability, inferred from conditional uptake rate constants, was greater for nanoparticulate than dissolved forms and increased with increasing nanoparticle hydrodynamic diameter. The effect of natural organic matter (NOM) composition on PtNP bioavailability was evaluated using six NOM samples at two nanoparticle sizes (20 and 95 nm). NOM suppressed the bioavailability of 95 nm PtNPs in all cases, and DOM reduced sulfur content exhibited a positive correlation with 95 nm PtNP bioavailability. The bioavailability of 20 nm PtNPs was only suppressed by NOM with a low reduced sulfur content. The physiological elimination of Pt accumulated after dissolved Pt(IV) exposure was slow and constant. In contrast, the elimination of Pt accumulated after PtNP exposures exhibited a triphasic pattern likely involving in vivo PtNP dissolution. This work highlights the importance of PtNP size and interfacial interactions with NOM on Pt bioavailability and suggests that in vivo PtNP transformations could yield unexpectedly higher adverse effects to organisms than dissolved exposure alone.

Environ. Sci. Technol.↗
USGS2015

Formation of mercury sulfide from Hg(II)−thiolate complexes in natural organic matter

Methylmercury is the environmental form of neurotoxic mercury that is biomagnified in the food chain. Methylation rates are reduced when the metal is sequestered in crystalline mercury sulfides or bound to thiol groups in macromolecular natural organic matter. Mercury sulfide minerals are known to nucleate in anoxic zones, by reaction of the thiol-bound mercury with biogenic sulfide, but not in oxic environments. We present experimental evidence that mercury sulfide forms from thiol-bound mercury alone in aqueous dark systems in contact with air. The maximum amount of nanoparticulate mercury sulfide relative to thiol-bound mercury obtained by reacting dissolved mercury and soil organic matter matches that detected in the organic horizon of a contaminated soil situated downstream from Oak Ridge, TN, in the United States. The nearly identical ratios of the two forms of mercury in field and experimental systems suggest a common reaction mechanism for nucleating the mineral. We identified a chemical reaction mechanism that is thermodynamically favorable in which thiol-bound mercury polymerizes to mercury–sulfur clusters. The clusters form by elimination of sulfur from the thiol complexes via breaking of mercury–sulfur bonds as in an alkylation reaction. Addition of sulfide is not required. This nucleation mechanism provides one explanation for how mercury may be immobilized, and eventually sequestered, in oxygenated surface environments.

Environmental Science & Technology↗
USGS2016

Biogeochemical controls of uranium bioavailability from the dissolved phase in natural freshwaters

To gain insights into the risks associated with uranium (U) mining and processing, we investigated the biogeochemical controls of U bioavailability in the model freshwater species Lymnaea stagnalis (Gastropoda). Bioavailability of dissolved U(VI) was characterized in controlled laboratory experiments over a range of water hardness, pH, and in the presence of complexing ligands in the form of dissolved natural organic matter (DOM). Results show that dissolved U is bioavailable under all the geochemical conditions tested. Uranium uptake rates follow first order kinetics over a range encompassing most environmental concentrations. Uranium uptake rates in L. stagnalis ultimately demonstrate saturation uptake kinetics when exposure concentrations exceed 100 nM, suggesting uptake via a finite number of carriers or ion channels. The lack of a relationship between U uptake rate constants and Ca uptake rates suggest that U does not exclusively use Ca membrane transporters. In general, U bioavailability decreases with increasing pH, increasing Ca and Mg concentrations, and when DOM is present. Competing ions did not affect U uptake rates. Speciation modeling that includes formation constants for U ternary complexes reveals that the aqueous concentration of dicarbonato U species (UO 2 (CO 3 ) 2 –2 ) best predicts U bioavailability to L. stagnalis , challenging the free-ion activity model postulate.

Environmental Science & Technology↗
USGS2009

Comprehensive isolation of natural organic matter from water for spectral characterizations and reactivity testing

A variety of approaches were tested to comprehensively isolate natural organic matter (NOM) from water . For waters with high NOM concentrations such as the Suwannee River, Georgia, approaches that used combinations of membrane concentrations, evaporative concentrations, and adsorption on nonionic XAD resins, ion exchange resins and iron oxide coated sand isolated over 90% of the NOM. However, for waters with low NOM concentrations, losses of half of the NOM were common and desalting of NOM isolates was a problem. A new comprehensive approach was devised and tested on the Seine River, France in which 100 L of filtered water was sodium softened by ion exchange and vacuum evaporated to 100 mL. Colloids (32% of the NOM) were isolated using a 3,500 Dalton membrane by dialysis against 0.1 M HCl and 0.2 M HF to remove salts and silica. On the membrane permeate, hydrophobic NOM (42%) was isolated using XAD-8 resin and hydrophilic NOM (26%) was isolated using a variety of selective desalting precipitations. The colloid fraction was characterized by IR and NMR spectroscopy as N-acetylamino sugars.

Georgia↗
USGS2011

Redox chemistry and natural organic matter (NOM): Geochemists' dream, analytical chemists' nightmare

Natural organic matter (NOM) is an inherently complex mixture of polyfunctional organic molecules. Because of their universality and chemical reversibility, oxidation/reductions (redox) reactions of NOM have an especially interesting and important role in geochemistry. Variabilities in NOM composition and chemistry make studies of its redox chemistry particularly challenging, and details of NOM-mediated redox reactions are only partially understood. This is in large part due to the analytical difficulties associated with NOM characterization and the wide range of reagents and experimental systems used to study NOM redox reactions. This chapter provides a summary of the ongoing efforts to provide a coherent comprehension of aqueous redox chemistry involving NOM and of techniques for chemical characterization of NOM. It also describes some attempts to confirm the roles of different structural moieties in redox reactions. In addition, we discuss some of the operational parameters used to describe NOM redox capacities and redox states, and describe nomenclature of NOM redox chemistry. Several relatively facile experimental methods applicable to predictions of the NOM redox activity and redox states of NOM samples are discussed, with special attention to the proposed use of fluorescence spectroscopy to predict relevant redox characteristics of NOM samples.

ACS Symposium Series↗
USGS2004

Generation of ethylene tracer by noncatalytic pyrolysis of natural gas at elevated pressure

There is a critical need within the pipeline gas industry for an inexpensive and reliable technology to generate an identification tag or tracer that can be added to pipeline gas to identify gas that may escape and improve the deliverability and management of gas in underground storage fields. Ethylene is an ideal tracer, because it does not exist naturally in the pipeline gas, and because its physical properties are similar to the pipeline gas components. A pyrolysis process, known as the Tragen process, has been developed to continuously convert the ???2%-4% ethane component present in pipeline gas into ethylene at common pipeline pressures of 800 psi. In our studies of the Tragen process, pyrolysis without steam addition achieved a maximum ethylene yield of 28%-35% at a temperature range of 700-775 ??C, corresponding to an ethylene concentration of 4600-5800 ppm in the product gas. Coke deposition was determined to occur at a significant rate in the pyrolysis reactor without steam addition. The ?? 13C isotopic analysis of gas components showed a ?? 13C value of ethylene similar to ethane in the pipeline gas, indicating that most of the ethylene was generated from decomposition of the ethane in the raw gas. However, ?? 13C isotopic analysis of the deposited coke showed that coke was primarily produced from methane, rather than from ethane or other heavier hydrocarbons. No coke deposition was observed with the addition of steam at concentrations of > 20% by volume. The dilution with steam also improved the ethylene yield. ?? 2005 American Chemical Society.

Energy and Fuels↗
USGS1997

Adsorbed natural gas storage with activated carbons made from Illinois coals and scrap tires

Activated carbons for natural gas storage were produced from Illinois bituminous coals (IBC-102 and IBC-106) and scrap tires by physical activation with steam or CO 2 and by chemical activation with KOH, H 3 PO 4 , or ZnCl 2 . The products were characterized for N 2 -BET area, micropore volume, bulk density, pore size distribution, and volumetric methane storage capacity ( V m / V s ). V m / V s values for Illinois coal-derived carbons ranged from 54 to 83 cm 3 /cm 3 , which are 35−55% of a target value of 150 cm 3 /cm 3 . Both granular and pelletized carbons made with preoxidized Illinois coal gave higher micropore volumes and larger V m / V s values than those made without preoxidation. This confirmed that preoxidation is a desirable step in the production of carbons from caking materials. Pelletization of preoxidized IBC-106 coal, followed by steam activation, resulted in the highest V m / V s value. With roughly the same micropore volume, pelletization alone increased V m / V s of coal carbon by 10%. Tire-derived carbons had V m / V s values ranging from 44 to 53 cm 3 /cm 3 , lower than those of coal carbons due to their lower bulk densities. Pelletization of the tire carbons increased bulk density up to 160%. However, this increase was offset by a decrease in micropore volume of the pelletized materials, presumably due to the pellet binder. As a result, V m / V s values were about the same for granular and pelletized tire carbons. Compared with coal carbons, tire carbons had a higher percentage of mesopores and macropores.

Energy and Fuels↗
USGS2002

Influence of natural organic matter on the adsorption of metal ion onto clay particles

The influence of natural organic matter (NOM) on the adsorption of Al, Fe, Zn, and Pb onto clay minerals was investigated. Adsorption experiments were carried out at pH = 5 and pH = 7 in the presence and absence of NOM. In general, the presence of NOM decreased the adsorption of metal ions onto the clay particles. Al and Fe were strongly influenced by NOM, whereas Zn and Pb adsorption was only slightly altered. The interaction of the metal ions with the minerals and the influence of NOM on this interaction was investigated by coupling SdFFF with an inductively coupled plasma mass spectrometer (ICPMS) or an inductively coupled plasma atomic emission spectrometer (ICPAES). Quantitative atomization of the clay particles in the ICP was confirmed by comparing elemental content determined by direct injection of the clay into the ICPMS with values from acid digestion. Particle sizes of the clays were found to be between 0.1 and 1 μm by sedimentation field-flow fractionation (SdFFF) with UV detection. Aggregation of particles due to metal adsorption was observed using SdFFF-ICPMS measurements. This aggregation was dependent on the specific metal ion and decreased in the presence of NOM and at higher pH value.

Environmental Science & Technology↗