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At least 883 records · Page 49Linked to original sources

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↗

USGS2007

Ra and Rn isotopes as natural tracers of submarine groundwater discharge in Tampa Bay, Florida

A suite of naturally occurring radionuclides in the U/Th decay series ( 222 Rn, 223,224,226,228 Ra) were studied during wet and dry conditions in Tampa Bay, Florida, to evaluate their utility as groundwater discharge tracers, both within the bay proper and within the Alafia River/estuary — a prominent free-flowing river that empties into the bay. In Tampa Bay, almost 30% of the combined riverine inputs still remain ungauged. Consequently, groundwater/surface water (hyporheic) exchange in the discharging coastal rivers, as well as submarine groundwater discharge (SGD) within the bay, are still unresolved components of this system's water and material budgets. Based on known inputs and sinks, there exists an excess of 226 Ra in the water column of Tampa Bay, which can be evaluated in terms of a submarine groundwater contribution to the bay proper. Submarine groundwater discharge rates calculated using a mass balance of excess 226 Ra ranged from 2.2 to 14.5 L m − 2 day − 1 , depending on whether the estuarine residence time was calculated using 224 Ra/xs 228 Ra isotope ratios, or whether a long term, averaged model-derived estuarine residence time was used. When extrapolated to the total shoreline length of the bay, such SGD rates ranged from 1.6 to 10.3 m 3 m − 1 day − 1 . Activities of 222 Rn were also elevated in surface water and shallow groundwater of the bay, as well as in the Alafia River estuary, where upstream activities as high as 250 dpm L − 1 indicate enhanced groundwater/surface water exchange, facilitated by an active spring vent. From average nutrient concentrations of 39 shallow, brackish, groundwater samples, rates of nutrient loading into Tampa Bay by SGD rates were estimated, and these ranged from 0.2 to 1.4 × 10 5 mol day − 1 (PO 4 3− ), 0.9–6.2 × 10 5 mol day − 1 (SiO 4 − ), 0.7–5.0 × 10 5 mol day − 1 (dissolved organic nitrogen, DON), and 0.2–1.4 × 10 6 mol day − 1 (total dissolved nitrogen, TDN). Such nutrient loading estimates, when compared to average river discharge estimates (e.g., TDN = 6.9 × 10 5 mol day − 1 ), suggest that SGD-derived nutrient fluxes to Tampa Bay are indeed important components to the overall nutrient economy of these coastal waters.

Florida↗

USGS2008

The last 1000 years of natural and anthropogenic low-oxygen bottom-water on the Louisiana shelf, Gulf of Mexico

The relative abundance of three species of low-oxygen tolerant benthic foraminifers, the PEB index, in foraminiferal assemblages from sediment cores is used to trace the history of low-oxygen bottom-water conditions on the Louisiana shelf. Analyses of a network of box cores indicate that the modern zone of chronic seasonal hypoxia off the Mississippi Delta began to develop around 1920 and was well established by 1960. The pattern of development over the last century is consistent with the interpretation that the formation of modern chronic hypoxia is related to anthropogenic activities resulting in increased transport of nutrients to the Louisiana shelf. The PEB index in two gravity- and box core pairs (MRD05-4 and 05-6) indicates that low-oxygen bottom-water events have occurred periodically on the Louisiana Shelf for at least the last 1000 14C years. The pre-1900 low-oxygen bottom-water events are likely caused by intervals of increased Mississippi River discharge and widespread wetland export. The PEB record in gravity cores indicates that the pre-1900 low-oxygen bottom-water events were not as well developed or as geographically extensive as the modern hypoxia zone. We conclude that the development of low-oxygen bottom-water on the Louisiana shelf is a natural process that has been negatively modified by human activities in the last 100 years.

Louisiana↗

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↗

USGS2004

Field and laboratory arsenic speciation methods and their application to natural-water analysis

The toxic and carcinogenic properties of inorganic and organic arsenic species make their determination in natural water vitally important. Determination of individual inorganic and organic arsenic species is critical because the toxicology, mobility, and adsorptivity vary substantially. Several methods for the speciation of arsenic in groundwater, surface-water, and acid mine drainage sample matrices using field and laboratory techniques are presented. The methods provide quantitative determination of arsenite [As(III)], arsenate [As(V)], monomethylarsonate (MMA), dimethylarsinate (DMA), and roxarsone in 2-8min at detection limits of less than 1??g arsenic per liter (??g AsL-1). All the methods use anion exchange chromatography to separate the arsenic species and inductively coupled plasma-mass spectrometry as an arsenic-specific detector. Different methods were needed because some sample matrices did not have all arsenic species present or were incompatible with particular high-performance liquid chromatography (HPLC) mobile phases. The bias and variability of the methods were evaluated using total arsenic, As(III), As(V), DMA, and MMA results from more than 100 surface-water, groundwater, and acid mine drainage samples, and reference materials. Concentrations in test samples were as much as 13,000??g AsL-1 for As(III) and 3700??g AsL-1 for As(V). Methylated arsenic species were less than 100??g AsL-1 and were found only in certain surface-water samples, and roxarsone was not detected in any of the water samples tested. The distribution of inorganic arsenic species in the test samples ranged from 0% to 90% As(III). Laboratory-speciation method variability for As(III), As(V), MMA, and DMA in reagent water at 0.5??g AsL-1 was 8-13% (n=7). Field-speciation method variability for As(III) and As(V) at 1??g AsL-1 in reagent water was 3-4% (n=3). ?? 2003 Elsevier Ltd. All rights reserved.

Water Research↗

USGS1978

An automated procedure for the simultaneous determination of specific conductance and pH in natural water samples

An automated, continuous-flow system is utilized to determine specific conductance and pH simultaneously in natural waters. A direct electrometric procedure is used to determine values in the range pH 4–9. The specific conductance measurements are made with an electronically modified, commercially available conductivity meter interfaced to a separate module containing the readout control devices and printer. The system is designed to switch ranges automatically to accommodate optimum analysis of widely varying conductances ranging from a few μmhos cm -1 to 15,000 μmho cm -1 . Thirty samples per hour can be analyzed. Comparison of manual and automated procedures for 40 samples showed that the average differences were 1.3% for specific conductance and 0.07 units for pH. The relative standard deviation for 25 replicate values for each of five samples was significantly less than 1% for the specific conductance determination; the standard deviation for the pH determination was ⩽ 0.06 pH units.

Analytica Chimica Acta↗

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↗

USGS1999

Fractionation of aquatic natural organic matter upon sorption to goethite and kaolinite

Natural organic matter (NOM) consists of a complex mixture of organic molecules; previous studies have suggested that preferential sorption of higher molecular weight, more hydrophobic, and more aromatic components may lead to fractionation of the NOM pool upon passage through porous media. Our work expands upon previous studies by quantifying the change in solution-phase weight average molecular weight (M(w)) upon sorption of bulk (rather than isolated) surface water NOM from the Suwannee River (SR) and the Great Dismal Swamp (GDS) to goethite and kaolinite at different sorption densities and at pH 4, 22??C. High pressure size exclusion chromatography (HPSEC) was used to quantify changes in M(w) upon sorption, and molar absorptivities at ?? = 280 nm were used to approximate changes in solution NOM aromaticity. Two SR water samples were used, with M(w) = 2320 and 2200 Da; a single GDS sample was used, with M(w) = 1890 Da. The SR NOM was slightly more hydrophobic and aromatic. These differences were reflected in greater sorption of SR NOM than GDS NOM. Both surface water NOMs showed a much greater affinity for goethite than for kaolinite. HPSEC analysis of the NOM remaining in solution after 24 h reaction time with geothite revealed that the largest changes in solution phase M(w)s (decreases by 900-1700 Da) occurred at relatively low equilibrium sorbate concentrations (approximately 5-20 mg C 1-1); the decrease in solution M(w) suggested that reactive surface sites were occupied disproportionately by large and intermediate size NOM moieties. At higher equilibrium NOM concentrations (>20 mg C 1-1), as percent adsorption decreased, M(w) in solution was similar to original samples. A smaller decrease in solution NOM M(w) (300-500 Da at 10-20 mg C 1-1 ~ 100 Da at > 20 mg) also occurred upon sorption to kaolinite. Overall, our results showed that factors (as related to NOM composition, clay mineral surface properties, and position along the sorption isotherm) which promote a higher percent sorption lead to the most pronounced decreases in solution M(w).

Chemical Geology↗

USGS2001

Identification of a new degradation product of the antifouling agent Irgarol 1051 in natural samples

A main degradation product of Irgarol [2-(methylthio)-4-(tert-butylamino)-6-(cyclopropylamino)-s-triazine], one of the most widely used compounds in antifouling paints, was detected at trace levels in seawater and sediment samples collected from several marinas on the Mediterranean coast. This degradation product was identified as 2-methylthio-4-tert-butylamino-s-triazine. The unequivocal identification of this compound in seawater samples was carried out by solid-phase extraction (SPE) coupled on-line with liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS). SPE was carried out by passing 150 ml of seawater sample through a cartridge containing a polymeric phase (PLRP-s), with recoveries ranging from 92 to 108% (n=5). Using LC-MS detection in positive ion mode, useful structural information was obtained by increasing the fragmentor voltage, thus permitting the unequivocal identification of this compound in natural samples. Method detection limits were in the range of 0.002 to 0.005 ??g/l. Overall, the combination of on-line SPE and LC-APCI-MS represents an important advance in environmental analysis of herbicide degradation products in seawater, since it demonstrates that trace amounts of new polar metabolites may be determined rapidly. This paper reports the LC-MS identification of the main degradation product of Irgarol in seawater and sediment samples. ?? 2001 Elsevier Science B.V. All rights reserved.

Conference Paper↗

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↗