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At least 811 records · Page 45Linked to original sources

USGS2005

Dissolution of cinnabar (HgS) in the presence of natural organic matter

Cinnabar (HgS) dissolution rates were measured in the presence of 12 different natural dissolved organic matter (DOM) isolates including humic, fulvic, and hydrophobic acid fractions. Initial dissolution rates varied by 1.3 orders of magnitude, from 2.31 × 10 −13 to 7.16 × 10 −12 mol Hg (mg C) −1 m −2 s −1 . Rates correlate positively with three DOM characteristics: specific ultraviolet absorbance (R 2 = 0.88), aromaticity (R 2 = 0.80), and molecular weight (R 2 = 0.76). Three experimental observations demonstrate that dissolution was controlled by the interaction of DOM with the cinnabar surface: (1) linear rates of Hg release with time, (2) significantly reduced rates when DOM was physically separated from the surface by dialysis membranes, and (3) rates that approached constant values at a specific ratio of DOM concentration to cinnabar surface area, suggesting a maximum surface coverage by dissolution-reactive DOM. Dissolution rates for the hydrophobic acid fractions correlate negatively with sorbed DOM concentrations, indicating the presence of a DOM component that reduced the surface area of cinnabar that can be dissolved. When two hydrophobic acid isolates that enhanced dissolution to different extents were mixed equally, a 20% reduction in rate occurred compared to the rate with the more dissolution-enhancing isolate alone. Rates in the presence of the more dissolution-enhancing isolate were reduced by as much as 60% when cinnabar was prereacted with the isolate that enhanced dissolution to a lesser extent. The data, taken together, imply that the property of DOM that enhances cinnabar dissolution is distinct from the property that causes it to sorb irreversibly to the cinnabar surface.

Geochimica et Cosmochimica Acta↗

USGS2008

Natural radionuclide mobility and its influence on U-Th-Pb dating of secondary minerals from the unsaturated zone at Yucca Mountain, Nevada

Extreme U and Pb isotope variations produced by disequilibrium in decay chains of 238U and 232Th are found in calcite, opal/chalcedony, and Mn-oxides occurring as secondary mineral coatings in the unsaturated zone at Yucca Mountain, Nevada. These very slowly growing minerals (mm my-1) contain excess 206Pb and 208Pb formed from excesses of intermediate daughter isotopes and cannot be used as reliable 206Pb/238U geochronometers. The presence of excess intermediate daughter isotopes does not appreciably affect 207Pb/235U ages of U-enriched opal/chalcedony, which are interpreted as mineral formation ages. Opal and calcite from outer (younger) portions of coatings have 230Th/U ages from 94.6 ?? 3.7 to 361.3 ?? 9.8 ka and initial 234U/238U activity ratios (AR) from 4.351 ?? 0.070 to 7.02 ?? 0.12, which indicate 234U enrichment from percolating water. Present-day 234U/238U AR is ???1 in opal/chalcedony from older portions of the coatings. The 207Pb/235U ages of opal/chalcedony samples range from 0.1329 ?? 0.0080 to 9.10 ?? 0.21 Ma, increase with microstratigraphic depth, and define slow long-term average growth rates of about 1.2-2.0 mm my-1, in good agreement with previous results. Measured 234U/238U AR in Mn-oxides, which pre-date the oldest calcite and opal/chalcedony, range from 0.939 ?? 0.006 to 2.091 ?? 0.006 and are >1 in most samples. The range of 87Sr/86Sr ratios (0.71156-0.71280) in Mn-oxides overlaps that in the late calcite. These data indicate that Mn-oxides exchange U and Sr with percolating water and cannot be used as a reliable dating tool. In the U-poor calcite samples, measured 206Pb/207Pb ratios have a wide range, do not correlate with Ba concentration as would be expected if excess Ra was present, and reach a value of about 1400, the highest ever reported for natural Pb. Calcite intergrown with opal contains excesses of both 206Pb and 207Pb derived from Rn diffusion and from direct ??-recoil from U-rich opal. Calcite from coatings devoid of opal/chalcedony contains 206Pb and 208Pb excesses, but no appreciable 207Pb excesses. Observed Pb isotope anomalies in calcite are explained by Rn-produced excess Pb. The Rn emanation may strongly affect 206Pb-238U ages of slow-growing U-poor calcite, but should be negligible for dating fast-growing U-enriched speleothem calcite.

Geochimica et Cosmochimica Acta↗

USGS2010

Rate of formation and dissolution of mercury sulfide nanoparticles: The dual role of natural organic matter

Mercury is a global contaminant of concern due to its transformation by microorganisms to form methylmercury, a toxic species that accumulates in biological tissues. The effect of dissolved organic matter (DOM) isolated from natural waters on reactions between mercury(II) (Hg) and sulfide (S(-II)) to form HgS (s) nanoparticles across a range of Hg and S(-II) concentrations was investigated. Hg was equilibrated with DOM, after which S(-II) was added. Dissolved Hg (Hg aq ) was periodically quantified using ultracentrifugation and chemical analysis following the addition of S(-II). Particle size and identity were determined using dynamic light scattering and X-ray absorption spectroscopy. S(-II) reacts with Hg to form 20 to 200nm aggregates consisting of 1-2 nm HgS (s) subunits that are more structurally disordered than metacinnabar in the presence of 2 x 10 -9 to 8 x 10 -6 M Hg and 10 (mg C)L -1 DOM. Some of the HgS(s) nanoparticle aggregates are subsequently dissolved by DOM and (re)precipitated by S(-II) over periods of hours to days. At least three fractions of Hg-DOM species were observed with respect to reactivity toward S(-II): 0.3 μmol reactive Hg per mmol C (60 percent), 0.1 μmol per mmol C (20 percent) that are kinetically hindered, and another 0.1 μmol Hg per mmol C (20 percent) that are inert to reaction with S(-II). Following an initial S(-II)-driven precipitation of HgS (s) , HgS (s) was dissolved by DOM or organic sulfur compounds. HgS (s) formation during this second phase was counterintuitively favored by lower S(-II) concentrations, suggesting surface association of DOM moieties that are less capable of dissolving HgS (s) . DOM partially inhibits HgS(s) formation and mediates reactions between Hg and S(-II) such that HgS (s) is susceptible to dissolution. These findings indicate that Hg accessibility to microorganisms could be controlled by kinetic (intermediate) species in the presence of S(-II) and DOM, undermining the premise that equilibrium Hg species distributions should correlate to the extent or rate of Hg methylation in soils and sediments.

Geochimica et Cosmochimica Acta↗

USGS2006

The behavior of rare earth elements in naturally and anthropogenically acidified waters

In this paper, the behavior of rare earth elements (REE) in a watershed impacted by acid-mine drainage (Fisher Creek, Montana) is compared to that in a volcanically acidified watershed (Rio Agrio and Lake Caviahue, Argentina). The REE behave conservatively in acidic waters with pH values less than approximately 5.5. However, above pH 5.5, REE concentrations are controlled by adsorption onto or co-precipitation with a variety of Fe or Al oxyhydroxides. The heavy REE partition to a greater extent into the solid phase than the light REE as pH rises above 6. Concentrations of REE exhibit diel (24-h) cycling in waters that were initially acidic, but have become neutralized downstream. In Fisher Creek, at the most downstream sampling station investigated (pH 6.8), concentrations of dissolved REE were 190–840% higher in the early morning versus the late afternoon. This cycling can be related to temperature-dependent, cyclic adsorption–desorption of REE onto hydrous ferric or aluminum oxide or both. Similar but gentler diel cycling of the REE was found at Rio Agrio. The existence of such cycling has important ramifications for the study of REE in natural waters.

Journal of Alloys and Compounds↗

USGS2021

Environmental factors predicting the orientation of sea turtle hatchlings on a naturally lighted beach: A baseline for light-management goals

On sea turtle nesting beaches, artificial lighting associated with human development interferes with hatchling orientation from nest to sea. Although hatchling disorientation has been documented for many beaches, data that managers can use in understanding, predicting, and managing the issue are of limited detail. The present study provides baseline hatchling orientation data that can be compared to those from beaches with artificial lighting to prioritize light-management efforts there. In 2014, the precision of hatchling orientation was quantified for 87 nests on a naturally lighted beach that had little to no artificial lighting. Precision of hatchling orientation was regressed against seven environmental variables: beach slope, distance from nest to dune, dune height, apparent dune silhouette height relative to nest site, moon illumination percentage, cloud cover percentage, and relative humidity. Results favored a regression model that included distance from nest to dune, with shorter distances from the dune predicting a narrower angular range (i.e., greater precision) of hatchling orientation. The study confirmed findings of an earlier laboratory experiment that highlighted the importance to accurate hatchling orientation of a dark silhouette (dune) on the side of the nest site opposite the ocean side. Reducing artificial light and promoting the planting of pioneer plants that assist dune formation can increase hatchling survival.

Florida↗

USGS2015

Natural trophic variability in a large, oligotrophic, near-pristine lake

Conclusions drawn from stable isotope data can be limited by an incomplete understanding of natural isotopic variability over time and space. We quantified spatial and temporal variability in fish carbon and nitrogen stable isotopes in Lake Hövsgöl, Mongolia, a large, remote, oligotrophic lake with an unusually species-poor fish community. The fish community demonstrated a high degree of trophic level overlap. Variability in δ 13 C was inversely related to littoral-benthic dependence, with pelagic species demonstrating more δ 13 C variability than littoral-benthic species. A mixed effects model suggested that space (sampling location) had a greater impact than time (collection year) on both δ 13 C and δ 15 N variability. The observed variability in Lake Hövsgöl was generally greater than isotopic variability documented in other large, oligotrophic lakes, similar to isotopic shifts attributed to introduced species, and less than isotopic shifts attributed to anthropogenic chemical changes such as eutrophication. This work complements studies on isotopic variability and changes in other lakes around the world.

Journal of Great Lakes Research↗

USGS2021

Coalescent methods reconstruct contributions of natural colonization and stocking to origins of Michigan inland Cisco (Coregonus artedi)

Fish population structure in previously glaciated regions is often influenced by natural colonization processes and human-mediated dispersal, including fish stocking. Endemic populations are of conservation interest because they may contain rare and unique genetic variation. While coregonines are native to certain Michigan inland lakes, some were stocked with fish from Great Lakes sources, calling into question the origin of extant populations. While most stocking targeted lake whitefish ( Coregonus clupeaformis ), cisco ( C. artedi ) were also stocked from the Great Lakes to inland waterbodies. We used population genetic data (microsatellite genotypes and mitochondrial (mt)DNA sequences), coalescent modeling, and approximate Bayesian computation to investigate the origins of 12 inland Michigan cisco populations. The spatial distribution of mtDNA haplotypes suggests Michigan is an introgression zone for two ancestral cisco lineages associated with separate glacial refugia. Low levels of genetic diversity and high levels of genetic divergence were observed for populations located well inland of the Great Lakes relative to populations occupying waterbodies near the Great Lakes. Estimates of recent Great Lakes gene flow ranged from 27 to 48% for populations near the Great Lakes shoreline but were substantially lower (under 8%) for populations further inland. Inland lakes with elevated recent gene flow estimates may have been recipients of stocked coregonine fry, including cisco. Low levels of genetic diversity paired with a high likelihood of endemism as indicated by strong genetic divergence and low Great Lakes population inputs suggest the analyzed cisco populations occupying southern Michigan kettle lakes are of elevated conservation interest.

Michigan↗

USGS2026

Application of novel encounter and predation models to the natural behavior of slimy sculpin Cottus cognatus

Sculpins play a critical mid-trophic role in lacustrine food webs, converting production by benthic and migrating pelagic invertebrates into biomass available to higher trophic levels. Although sculpin diets and habitat choices are relatively well described, much less is known about their in situ behavior which governs trophic interactions and, in part, prey behavior. We measured the natural behavior of slimy sculpin Cottus cognatus in Lake Champlain using video data originally collected to quantify Mysis diluviana abundance in benthic habitat. After characterizing slimy sculpin movement behaviors according to body size, we incorporated these data into encounter and predation rate models at the individual and population levels, the latter based on bottom trawl data from Lake Champlain. Saltatory movement varied with body length in terms of distance traveled, duration traveled, and duration at rest, but strike distances at prey did not vary across individual sculpins. Slimy sculpin predation rate increased with depth and was limited by pursuit time rather than prey availability, and their populations exerted predation rates on Mysis up to 5 predation events/m 2 /day. Assessment of benthic predation risks affords the opportunity to test hypotheses about the role of predation risk in Mysis diel vertical migration (DVM), and DVM more broadly. Furthermore, the methods we describe here can easily be employed for other benthic fishes such as the invasive round goby Neogobius melanostomus .

New York, Vermont↗

USGS2015

Storage and mobilization of natural and septic nitrate in thick unsaturated zones, California

Mobilization of natural and septic nitrate from the unsaturated zone as a result of managed aquifer recharge has degraded water quality from public-supply wells near Yucca Valley in the western Mojave Desert, California. The effect of nitrate storage and potential for denitrification in the unsaturated zone to mitigate increasing nitrate concentrations were investigated. Storage of water extractable nitrate in unsaturated alluvium up to 160 meters (m) thick, ranged from 420 to 6600 kilograms per hectare (kg/ha) as nitrogen (N) beneath undeveloped sites, from 6100 to 9200 kg/ha as N beneath unsewered sites. Nitrate reducing and denitrifying bacteria were less abundant under undeveloped sites and more abundant under unsewered sites; however, δ 15 N–NO 3 , and δ 18 O–NO 3 data show only about 5–10% denitrification of septic nitrate in most samples—although as much as 40% denitrification occurred in some parts the unsaturated zone and near the top of the water table. Storage of nitrate in thick unsaturated zones and dilution with low-nitrate groundwater are the primary attenuation mechanisms for nitrate from septic discharges in the study area. Numerical simulations of unsaturated flow, using the computer program TOUGH2, showed septic effluent movement through the unsaturated zone increased as the number and density of the septic tanks increased, and decreased with increased layering, and increased slope of layers, within the unsaturated zone. Managing housing density can delay arrival of septic discharges at the water table, especially in layered unsaturated alluvium, allowing time for development of strategies to address future water-quality issues.

California↗

USGS2022

Geochemical characterization of natural gases in the pre-salt section of the Santos Basin (Brazil) focused on hydrocarbons and volatile organic sulfur compounds

The objective of this work is to characterize the geochemistry of a suite of natural gas samples from five fields in order to improve the understanding of the lacustrine petroleum system of the pre-salt section from the Santos Basin (Brazil). Additionally, the distribution of volatile organic sulfur compounds (VOSC) in petroleum reservoirs was examined to investigate possible applications to petroleum systems assessments. The hydrocarbon gases were generated by thermogenic processes associated with the oil window. The 13 C-enriched values for C 1 (>−40‰) were interpreted as an organic source signature rather than an indication of thermal maturity, except for the oil occurrence (Field B), where a different fluid charge mainly composed of methane and CO 2 from a minor external kitchen area in the Santos Basin was identified. The molecular composition and the carbon and hydrogen isotopic data of the hydrocarbon gases, when combined with the VOSC molecular compositional data, allow the identification of four gas families associated with different kitchens and/or migrations pathways. The total VOSC concentrations range from 0.7 to 23.9 ppm by volume (ppmV). The organic sulfides are mainly composed of carbonyl sulfide (COS) and diethyl sulfide. The main thiol compound is ethanethiol. The cyclic VOSC are primarily composed of thiophene, with a negligible amount of branched thiophenes (<0.1 ppmV). H2S showed a strong positive Pearson's correlation with COS and methanethiol (MeSH) concentrations (r = 0.943 and 0.807, respectively). This suggests that COS and MeSH formation was linked to H 2 S generation and/or post-catagenetic interactions between hydrocarbons and H 2 S, mainly related to thermochemical sulfate reduction (TSR). In contrast, the distribution of higher molecular weight VOSC seems to be controlled by source rock facies, rather than H 2 S concentration. Principal component analysis of the VOSC compositional data identified some subgroups within the gas families mainly associated with TSR. The results presented in this work reveal that VOSC can be an important auxiliary tool in petroleum system studies.

Atlantic Ocean, Santos Basin↗

USGS2018

MHC class II DRB diversity predicts antigen recognition and is associated with disease severity in California sea lions naturally infected with Leptospira interrogans

We examined the associations between California sea lion MHC class II DRB (Zaca-DRB) configuration and diversity, and leptospirosis. As Zaca-DRB gene sequences are involved with antigen presentation of bacteria and other extracellular pathogens, we predicted that they would play a role in determining responses to these pathogenic spirochaetes. Specifically, we investigated whether Zaca-DRB diversity (number of genes) and configuration (presence of specific genes) explained differences in disease severity, and whether higher levels of Zaca-DRB diversity predicted the number of specific Leptospira interrogans serovars that a sea lion's serum would react against. We found that serum from diseased sea lions with more Zaca-DRB loci reacted against a wider array of serovars. Specific Zaca-DRB loci were linked to reactions with particular serovars. Interestingly, sea lions with clinical manifestation of leptospirosis that had higher numbers of Zaca-DRB loci were less likely to recover from disease than those with lower diversity, and those that harboured Zaca-DRB.C or –G were 4.5 to 5.3 times more likely to die from leptospirosis, regardless of the infective serovars. We propose that for leptospirosis, a disadvantage of having a wider range of antigen presentation might be increased disease severity due to immunopathology. Ours is the first study to examine the importance of Zaca-DRB diversity for antigen detection and disease severity following natural exposure to infective leptospires.

California↗

USGS2012

Structural stability of coprecipitated natural organic matter and ferric iron under reducing conditions

The objective was to assess the interaction of Fe coprecipitated with dissolved organic matter (DOM) and its effect on Fe (hydr)oxide crystallinity and DOM retention under abiotic reducing conditions. A Fe-based coagulant was reacted with DOM from an agricultural drain and the resulting precipitate (floc) was exposed to S(-II) and Fe(II). Solution concentrations of Fe(II/III) and DOM were monitored, floc crystallinity was determined using X-ray diffraction, and the composition and distribution of functional groups were assessed using scanning transmission X-ray microscopy (STXM) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. Results indicate coprecipitation of Fe(III) with DOM forms a non-crystalline floc that withstands crystallization regardless of change in pH, Fe:DOM ratio and type of reductant added. There was no evidence that exposure to reducing conditions led to release of DOM from the floc, indicating that coprecipitation with complex natural DOM in aquatic environments may stabilize Fe (hydr)oxides against crystallization upon reaction with reduced species and lead to long term sequestration of the DOM. STXM analysis identified spatially distinct regions with remarkable functional group purity, contrary to the model of DOM as a relatively uniform complex polymer lacking identifiable organic compounds. Polysaccharide-like OM was strongly and directly correlated with the presence of Fe but showed different Fe binding strength depending on the presence of carboxylic acid functional groups, whereas amide and aromatic functional groups were inversely correlated with Fe content.

Organic Geochemistry↗

USGS2010

Assessment of multiple sources of anthropogenic and natural chemical inputs to a morphologically complex basin, Lake Mead, USA

Lakes with complex morphologies and with different geologic and land-use characteristics in their sub-watersheds could have large differences in natural and anthropogenic chemical inputs to sub-basins in the lake. Lake Mead in southern Nevada and northern Arizona, USA, is one such lake. To assess variations in chemical histories from 1935 to 1998 for major sub-basins of Lake Mead, four sediment cores were taken from three different parts of the reservoir (two from Las Vegas Bay and one from the Overton Arm and Virgin Basin) and analyzed for major and trace elements, radionuclides, and organic compounds. As expected, anthropogenic contaminant inputs are greatest to Las Vegas Bay reflecting inputs from the Las Vegas urban area, although concentrations are low compared to sediment quality guidelines and to other USA lakes. One exception to this pattern was higher Hg in the Virgin Basin core. The Virgin Basin core is located in the main body of the lake (Colorado River channel) and is influenced by the hydrology of the Colorado River, which changed greatly with completion of Glen Canyon Dam upstream in 1963. Major and trace elements in the core show pronounced shifts in the early 1960s and, in many cases, gradually return to concentrations more typical of pre-1960s by the 1980s and 1990s, after the filling of Lake Powell. The Overton Arm is the sub-basin least effected by anthropogenic contaminant inputs but has a complex 137Cs profile with a series of large peaks and valleys over the middle of the core, possibly reflecting fallout from nuclear tests in the 1950s at the Nevada Test Site. The 137Cs profile suggests a much greater sedimentation rate during testing which we hypothesize results from greatly increased dust fall on the lake and Virgin and Muddy River watersheds. The severe drought in the southwestern USA during the 1950s might also have played a role in variations in sedimentation rate in all of the cores. ?? 2009.

Palaeogeography, Palaeoclimatology, Palaeoecology↗

USGS2023

Luminescence ages and new interpretations of the timing and deposition of Quaternary sediments at Natural Trap Cave, Wyoming

Natural Trap Cave, located in the Big Horn Mountains of north-central Wyoming, has a history of trapping and preserving a range of North American fauna that plummeted into the deep vertical entrance. These animal remains were buried and preserved within sediments of the main chamber and, in turn, have helped elucidate the procession of faunal dynamics during the latest glacial cycle. The cave location, south of the Laurentide and Cordilleran Ice Sheets, and proximal to Yellowstone, is at an ideal geographical juncture to provide insights to ecological changes in North America. The sediments that the animals are buried in inform us about transport and deposition both inside and outside of the cave that relate to catchment dynamics. We report on a series of optically stimulated luminescence (OSL) ages derived from samples obtained within the cave during excavation work in 2014 and in 2018. We also examine chronology produced by argon, tephrochronology, fission track, and luminescence techniques that have been used for understanding the infilling of the cave. The cave sediment ages and in situ measured gamma spectroscopy as measured in this study helped resolve an improved chronological age model when combined with previous data. The suite of OSL ages is interpreted through the stratigraphic relationships (and vertebrates contained within) which requires the use of an adequate age model; we use either the central age model or minimum age model where appropriate and with justification. Lowest sediments are dated to ∼150 ka with a hiatus at ∼130 to 52 ka. Above this, sediment deposition and entrainment of paleontological materials are representative of Pleistocene and early Holocene times, between 37 ± 6 ka and 7.6 ± 0.5 ka. The stratigraphic architecture suggests that deposition of materials into the cave is episodic and rapid, followed by quiescent periods where hydrologic scour, heavy overland flow , or possibly a cryo-hydrologic process may have altered unit relationships. Thus, the complementary geochronometers and the characteristics of quartz versus feldspar luminescence signals improve temporal interpretations of these complex deposits. This adapted understanding of mixing also sets the stage for future work with the aim to improve our understanding of ages and sources for ash units within these cave deposits. The three ash units recognized in the cave may represent an in-situ reworking of the same ash or may be representative of previously undocumented eruptions from the Yellowstone Caldera.

Wyoming↗

USGS2021

Small atoll fresh groundwater lenses respond to a combination of natural climatic cycles and human modified geology

Freshwater lenses underlying small ocean islands exhibit spatial variability and temporal fluctuations in volume, influencing ecologic management. For example, The Palmyra Atoll National Wildlife Refuge harbors one of the few surviving native stands of Pisonia grandis in the central Pacific Ocean, yet these trees face pressure from groundwater salinization, with little basic groundwater data to guide decision making. Adding to natural complexity, the geology of Palmyra was heavily altered by dredge and fill activities. Our study based at this atoll combines geophysical and hydrological field measurements from 2008 to 2019 with groundwater modeling to study the drivers of observed freshwater lens dynamics. Electromagnetic induction (EMI) field data were collected on the main atoll islands over repeat transects in 2008 following ‘strong’ La Niña conditions (wet) and in 2016 during ‘very strong’ El Niño conditions (dry). Shallow monitoring wells were installed adjacent to the geophysical transects in 2013 and screened within the fresh/saline groundwater transition zone. Temporal EMI and monitoring well data showed a strong contraction of the freshwater lens in response to El Niño conditions, and indicated a thicker lens toward the ocean side, an opposite spatial pattern to that observed for many other Pacific islands. On an outer islet where a stand of mature Pisonia trees exist, EMI surveys revealed only a thin (<3 m from land surface) layer of brackish groundwater during El Niño. Numerical groundwater simulations were performed for a range of permeability distributions and climate conditions at Palmyra. Results revealed that the observed atypical lens asymmetry is likely due to more efficient submarine groundwater discharge on the lagoon side as a result of lagoon dredging and filling with high-permeability material. Simulations also predict large decreases (40%) in freshwater lens volume during dry cycles and highlight threats to the Pisonia trees, yielding insight for atoll ecosystem management worldwide.

Science of the Total Environment↗

USGS2000

Ion exchange separation of chromium from natural water matrix for stable isotope mass spectrometric analysis

A method has been developed for separating the Cr dissolved in natural water from matrix elements and determination of its stable isotope ratios using solid-source thermal-ionization mass spectrometry (TIMS). The separation method takes advantage of the existence of the oxidized form of Cr as an oxyanion to separate it from interfering cations using anion-exchange chromatography, and of the reduced form of Cr as a positively charged ion to separate it from interfering anions such as sulfate. Subsequent processing of the separated sample eliminates residual organic material for application to a solid source filament. Ratios for 53Cr/52Cr for National Institute of Standards and Technology Standard Reference Material 979 can be measured using the silica gel-boric acid technique with a filament-to-filament standard deviation in the mean 53Cr/52Cr ratio for 50 replicates of 0.00005 or less.

Chemical Geology↗

USGS2002

A comparison of surface water natural organic matter in raw filtered water samples, XAD, and reverse osmosis isolates

This research compared raw filtered waters (RFWs), XAD resin isolates (XAD-8 and XAD-4), and reverse osmosis (RO) isolates of several surface water samples from McDonalds Branch, a small freshwater fen in the New Jersey Pine Barrens (USA). RO and XAD-8 are two of the most common techniques used to isolate natural organic matter (NOM) for studies of composition and reactivity; therefore, it is important to understand how the isolates differ from bulk (unisolated) samples and from one another. Although, any comparison between the isolation methods needs to consider that XAD-8 is specifically designed to isolate the humic fraction, whereas RO concentrates a broad range of organic matter and is not specific to humics. The comparison included for all samples: weight average molecular weight ( M w ), number average molecular weight ( M n ), polydispersity ( ρ ), absorbance at 280 nm normalized to moles C ( ε 280 ) (RFW and isolates); and for isolates only: elemental analysis, % carbon distribution by 13 C NMR, and aqueous FTIR spectra. As expected, RO isolation gave higher yield of NOM than XAD-8, but also higher ash content, especially Si and S. M w decreased in the order: RO>XAD-8>RFW>XAD-4. The M w differences of isolates compared with RFW may be due to selective isolation (fractionation), or possibly in the case of RO to condensation or coagulation during isolation. 13 C NMR results were roughly similar for the two methods, but the XAD-8 isolate was slightly higher in ‘aromatic’ C and the RO isolate was slightly higher in heteroaliphatic and carbonyl C. Infrared spectra indicated a higher carboxyl content for the XAD-8 isolates and a higher ester:carboxyl ratio for the RO isolates. The spectroscopic data thus are consistent with selective isolation of more hydrophobic compounds by XAD-8, and also with potential ester hydrolysis during that process, although further study is needed to determine whether ester hydrolysis does indeed occur. Researchers choosing between XAD and RO isolation methods for NOM need to consider first the purpose of the isolation; i.e., whether humic fractionation is desirable. Beyond that, they should consider the C yield and ash content, as well as the potential for alteration of NOM by ester hydrolysis (XAD) or condensation/coagulation (RO). Furthermore, the RO and XAD methods produce different fractions or isolates so that researchers should be careful when comparing the compositions and reactivities of NOM samples isolated by these two different techniques.

Water Research↗

USGS2001

A model for lignin alteration - Part II: Numerical model of natural gas generation and application to the Piceance Basin, Western Colorado

The model presented here simulates a network of parallel and sequential reactions that describe the structural and chemical transformation of lignin-derived sedimentary organic matter (SOM) and the resulting generation of mobile species from shallow burial to approximately low-volatile bituminous rank. The model is calibrated to the Upper Cretaceous Williams Fork Formation coal of the Piceance Basin at the Multi-Well Experiment (MWX) Site, assuming this coal is largely derived from lignin. The model calculates the content of functional groups on the residual molecular species, C, H, and O elemental weight percents of the residual species, and moles of residual molecular species and mobile species (including components of natural gas) through time. The model is generally more sensitive to initial molecular structure of the lignin-derived molecule and the H2O content of the system than to initial temperature, as the former affect the fundamental reaction paths. The model is used to estimate that a total of 314 trillion cubic feet (tcf) of methane is generated by the Williams Fork coal over the basin history. ?? 2001 Elsevier Science Ltd. All rights reserved.

Organic Geochemistry↗