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R.L. Wershaw

Publications and source records attributed to R.L. Wershaw.

At least 19 recordsLinked to original sources
USGS2008

Distinguishing black carbon from biogenic humic substances in soil clay fractions

Most models of soil humic substances include a substantial component of aromatic C either as the backbone of humic heteropolymers or as a significant component of supramolecular aggregates of degraded biopolymers. We physically separated coarse (0.2–2.0 μm e.s.d.), medium (0.02–0.2 μm e.s.d.), and fine (> 0.02 μm e.s.d.) clay subfractions from three Midwestern soils and characterized the organic material associated with these subfractions using 13 C-CPMAS-NMR, DTG, SEM-EDX, incubations, and radiocarbon age. Most of the C in the coarse clay subfraction was present as discrete particles (0.2–5 μm as seen in SEM images) of black carbon (BC) and consisted of approximately 60% aromatic C, with the remainder being a mixture of aliphatic, anomeric and carboxylic C. We hypothesize that BC particles were originally charcoal formed during prairie fires. As the BC particles aged in soil their surfaces were oxidized to form carboxylic groups and anomeric and aliphatic C accumulated in the BC particles either by adsorption of dissolved biogenic compounds from the soil solution or by direct deposition of biogenic materials from microbes living within the BC particles. The biogenic soil organic matter was physically separated with the medium and fine clay subfractions and was dominated by aliphatic, anomeric, and carboxylic C. The results indicate that the biogenic humic materials in our soils have little aromatic C, which is inconsistent with the traditional heteropolymer model of humic substances.

Geoderma↗
USGS2003

Formation and loss of humic substances during decomposition in a pine forest floor

Since twice as much C is sequestered in soils as is contained in the atmosphere, the factors controlling the decomposition rate of soil C are important to the assessment of the effects of climatic change. The formation of chemically resistant humic substances might be an important process controlling recycling of CO 2 to the atmosphere. Our objectives were to measure the rate of formation and loss of humic substances during 13 yr of litter decomposition . We placed nets on the floor of a white pine (Pinus strobus) forest to separate each annual layer of litter for 13 yr and measured humic substance concentration using NaOH extraction followed by chromatographic fractionation. The humic acid fraction increased from 2.1% of the C in litterfall to 15.7% after 1 yr. On a grams per square meter (g m -2 ) basis the humic substance fraction increased during the first year and then declined, with a half decay time (t 1/2 ) of 5.1 yr, which was significantly slower than the bulk litter (t 1/2 = 3.9 yr). The carboxylic C concentration estimated from 13 C nuclear magnetic resonance (NMR) increased in the litter over time, though total mass of carboxylic acid C in the forest floor also declined over the 13-yr period (t 1/2 = 4.6 yr). While humic substances in the forest floor decomposed at a somewhat slower rate than bulk litter during Years 1 to 13, they decomposed much faster than has been calculated from 14 C dating of the refractory fraction of organic matter in the mineral soil.

Soil Science Society of America Journal↗
USGS2003

Environmental fate of roxarsone in poultry litter. I. Degradation of roxarsone during composting

Roxarsone, 3-nitro-4-hydroxyphenylarsonic acid, is an organoarsenic compound that is used extensively in the feed of broiler poultryto control coccidial intestinal parasites, improve feed efficiency, and promote rapid growth. Nearly all the roxarsone in the feed is excreted unchanged in the manure. Poultry litter composed of the manure and bedding material has a high nutrient content and is used routinely as a fertilizer on cropland and pasture. Investigations were conducted to determine the fate of poultrylitter roxarsone in the environment. Experiments indicated that roxarsone was stable in fresh dried litter; the primary arsenic species extracted with water from dried litter was roxarsone. However, when water was added to litter at about 50 wt % and the mixture was allowed to compost at 40 o C, the speciation of arsenic shifted from roxarsone to primarily arsenate in about 30 days. Increasing the amount of water increased the rate of degradation. Experiments also suggested that the degradation process most likely was biotic in nature. The rate of degradation was directly proportional to the incubation temperature; heat sterilization eliminated the degradation. Biotic degradation also was supported by results from enterobacteriaceae growth media that were inoculated with litter slurry to enhance the biotic processes and to reduce the concomitant abiotic effects from the complex litter solution. Samples collected from a variety of litter windrows in Arkansas, Oklahoma, and Maryland also showed that roxarsone originally present had been converted to arsenate.

Environmental Science & Technology↗
USGS2003

Photodegradation of roxarsone in poultry litter leachates

Arsenic compounds have been used extensively in agriculture in the US for applications ranging from cotton herbicides to animal feed supplements. Roxarsone (3-nitro-4-hydroxyphenylarsonic acid), in particular, is used widely in poultry production to control coccidial intestinal parasites. It is excreted unchanged in the manure and introduced into the environment when litter is applied to farmland as fertilizer. Although the toxicity of roxarsone is less than that of inorganic arsenic, roxarsone can degrade, biotically and abiotically, to produce more toxic inorganic forms of arsenic, such as arsenite and arsenate. Experiments were conducted on aqueous litter leachates to test the stability of roxarsone under different conditions. Laboratory experiments have shown that arsenite can be cleaved photolytically from the roxarsone moiety at pH 4-8 and that the degradation rate increases with increasing pH. Furthermore, the rate of photodegradation increases with nitrate and natural organic matter concentration, reactants that are commonly found in poultry-litter-water leachates. Additional photochemical reactions rapidly oxidize the cleaved arsenite to arsenate. The formation of arsenate is not entirely undesirable, because it is less mobile in soil systems and less toxic than arsenite. A possible mechanism for the degradation of roxarsone in poultry litter leachates is proposed. The results suggest that poultry litter storage and field application practices could affect the degradation of roxarsone and subsequent mobilization of inorganic arsenic species. ?? 2002 Elsevier Science B.V. All rights reserved.

Science of the Total Environment↗
USGS2003

Characterization and diagenesis of strong-acid carboxyl groups in humic substances

A small fraction of carboxylic acid functional groups in humic substances are exceptionally acidic with pKa values as low as 0.5. A review of acid-group theory eliminated most models and explanations for these exceptionally acidic carboxyl groups. These acidic carboxyl groups in Suwannee River fulvic acid were enriched by a 2-stage fractionation process and the fractions were characterized by elemental, molecular-weight, and titrimetric analyses, and by infrared and 13C- and 1H-nuclear magnetic resonance spectrometry. An average structural model of the most acidic fraction derived from the characterization data indicated a high density of carboxyl groups clustered on oxygen-heterocycle alicyclic rings. Intramolecular H-bonding between adjacent carboxyl groups in these ring structures enhanced stabilization of the carboxylate anion which results in low pKa1 values. The standard, tetrahydrofuran tetracarboxylic acid, was shown to have similar acidity characteristics to the highly acidic fulvic acid fraction. The end products of 3 known diagenetic pathways for the formation of humic substances were shown to result in carboxyl groups clustered on oxygen-heterocycle alicyclic rings.

Applied Geochemistry↗
USGS2003

Environmental fate of roxarsone in poultry litter. Part II. Mobility of arsenic in soils amended with poultry litter

Poultry litter often contains arsenic as a result of organo-arsenical feed additives. When the poultry litter is applied to agricultural fields, the arsenic is released to the environment and may result in increased arsenic in surface and groundwater and increased uptake by plants. The release of arsenic from poultry litter, litter-amended soils, and soils without litter amendment was examined by extraction with water and strong acids (HCI and HN03). The extracts were analyzed for As, C, P, Cu, Zn, and Fe. Copper, zinc, and iron are also poultry feed additives. Soils with a known history of litter application and controlled application rate of arsenic-containing poultry litter were obtained from the University of Maryland Agricultural Experiment Station. Soils from fields with long-term application of poultry litter were obtained from a tilled field on the Delmarva Peninsula (MD) and an untilled Oklahoma pasture. Samples from an adjacent forest or nearby pasture that had no history of litter application were used as controls. Depth profiles were sampled for the Oklahoma pasture soils. Analysis of the poultry litter showed that 75% of the arsenic was readily soluble in water. Extraction of soils shows that weakly bound arsenic mobilized by water correlates positively with C, P, Cu, and Zn in amended fields and appears to come primarily from the litter. Strongly bound arsenic correlates positively with Fe in amended fields and suggests sorption or coprecipitation of As and Fe in the soil column.

Environmental Science & Technology↗
USGS2002

Strong-acid, carboxyl-group structures in fulvic acid from the Suwannee River, Georgia. 1. Minor structures

An investigation of the strong-acid characteristics (pKa 3.0 or less) of fulvic acid from the Suwannee River, Georgia, was conducted. Quantitative determinations were made for amino acid and sulfur-containing acid structures, oxalate half-ester structures, malonic acid structures, keto acid structures, and aromatic carboxyl-group structures. These determinations were made by using a variety of spectrometric (13C-nuclear magnetic resonance, infrared, and ultraviolet spectrometry) and titrimetric characterizations on fulvic acid or fulvic acid samples that were chemically derivatized to indicate certain functional groups. Only keto acid and aromatic carboxyl-group structures contributed significantly to the strong-acid characteristics of the fulvic acid; these structures accounted for 43% of the strong-acid acidity. The remaining 57% of the strong acids are aliphatic carboxyl groups in unusual and/or complex configurations for which limited model compound data are available.

Environmental Science & Technology↗
USGS2002

Strong-acid, carboxyl-group structures in fulvic acid from the Suwannee River, Georgia. 2. Major structures

Polycarboxylic acid structures that account for the strong-acid characteristics (pKa1 near 2.0) were examined for fulvic acid from the Suwannee River. Studies of model compounds demonstrated that pKa values near 2.0 occur only if the a-ether or a-ester groups were in cyclic structures with two to three additional electronegative functional groups (carboxyl, ester, ketone, aromatic groups) at adjacent positions on the ring. Ester linkage removal by alkaline hydrolysis and destruction of ether linkages through cleavage and reduction with hydriodic acid confirmed that the strong carboxyl acidity in fulvic acid was associated with polycarboxylic a-ether and a-ester structures. Studies of hypothetical structural models of fulvic acid indicated possible relation of these polycarboxylic structures with the amphiphilic and metal-binding properties of fulvic acid.

Environmental Science & Technology↗
USGS1999

Correlation of soil and sediment organic matter polarity to aqueous sorption of nonionic compounds

Polarities of the soiL/sediment organic matter (SOM) in 19 soil and 9 freshwater sediment sam pies were determined from solid-state 13C-CP/MAS NMR spectra and compared with published partition coefficients (K(oc)) of carbon tetrachloride (CT) from aqueous solution. Nondestructive analysis of whole samples by solid-state NMR permits a direct assessment of the polarity of SOM that is not possible by elemental analysis. The percent of organic carbon associated with polar functional groups was estimated from the combined fraction of carbohydrate and carboxylamide-ester carbons. A plot of the measured partition coefficients (K(oc)) of carbon tetrachloride (CT) vs. percent polar organic carbon (POC) shows distinctly different populations of soils and sediments as well as a roughly inverse trend among the soil/sediment populations. Plots of K(oc) values for CT against other structural group carbon fractions did not yield distinct populations. The results indicate that the polarity of SOM is a significant factor in accounting for differences in K(oc) between the organic matter in soils and sediments. The alternate direct correlation of the sum of aliphatic and aromatic structural carbons with K(oc) illustrates the influence of nonpolar hydrocarbon on solute partition interaction. Additional elemental analysis data of selected samples further substantiate the effect of the organic matter polarity on the partition efficiency of nonpolar solutes. The separation between soil and sediment samples based on percent POC reflects definite differences of the properties of soil and sediment organic matters that are attributable to diagenesis.Polarities of the soil/sediment organic matter (SOM) in 19 soil and 9 freshwater sediment samples were determined from solid-state 13C-CP/MAS NMR spectra and compared with published partition coefficients (Koc) of carbon tetrachloride (CT) from aqueous solution. Nondestructive analysis of whole samples by solid-state NMR permits a direct assessment of the polarity of SOM that is not possible by elemental analysis. The percent of organic carbon associated with polar functional groups was estimated from the combined fraction of carbohydrate and carboxyl-amide-ester carbons. A plot of the measured partition coefficients (Koc) of carbon tetrachloride (CT) vs. percent polar organic carbon (POC) shows distinctly different populations of soils and sediments as well as a roughly inverse trend among the soil/sediment populations. Plots of Koc values for CT against other structural group carbon fractions did not yield distinct populations. The results indicate that the polarity of SOM is a significant factor in accounting for differences in Koc between the organic matter in soils and sediments. The alternate direct correlation of the sum of aliphatic and aromatic structural carbons with Koc illustrates the influence of nonpolar hydrocarbon on solute partition interaction. Additional elemental analysis data of selected samples further substantiate the effect of the organic matter polarity on the partition efficiency of nonpolar solutes. The separation between soil and sediment samples based on percent POC reflects definite differences of the properties of soil and sediment organic matters that are attributable to diagenesis.

Environmental Science & Technology↗
USGS1997

Chemical characteristics of particulate, colloidal, and dissolved organic material in Loch Vale Watershed, Rocky Mountain National Park

The chemical relationships among particulate and colloidal organic material and dissolved fulvic acid were examined in an alpine and subalpine lake and two streams in Loch Vale Watershed, Rocky Mountain National Park. The alpine lake, Sky Pond, had the lowest dissolved organic carbon (DOC) (0.37 mgC/L), the highest particulate carbon (POC) (0.13 mgC/L), and high algal biomass. The watershed of Sky Pond is primarily talus slope, and DOC and POC may be autochthonous. Both Andrews Creek and Icy Brook gain DOC as they flow through wet sedge meadows. The subalpine lake, The Loch, receives additional organic material from the surrounding forest and had a higher DOC (0.66 mgC/L). Elemental analysis, stable carbon isotopic compositon, and 13C-NMR characterization showed that: 1) particulate material had relatively high inorganic contents and was heterogeneous in compositon, 2) colloidal material was primarily carbohydrate material with a low inorganic content at all sites; and 3) dissolved fulvic acid varied in compositon among sites. The low concentration and carbohydrate-rich character of the colloidal material suggests that this fraction is labile to microbial degradation and may be turning over more rapidly than particulate fractions or dissolved fulvic acid. Fulvic acid from Andrews Creek had the lowest N content and aromaticity, whereas Sky Pond fulvic acid had a higher N content and lower aromaticity than fulvic acid from The Loch. The UV-visible spectra of the fulvic acids demonstrate that variation in characteristics with sources of organic carbon can explain to some extent the observed nonlinear relationship between UV-B extinction coefficients and DOC concentrations in lakes.

Colorado↗
USGS1996

Use of 13C NMR and ftir for elucidation of degradation pathways during natural litter decomposition and composting I. early stage leaf degradation

Oxidative degradation of plant tissue leads to the formation of natural dissolved organic carbon (DOC) and humus. Infrared (IR) and 13C nuclear magnetic resonance (NMR) spectrometry have been used to elucidate the chemical reactions of the early stages of degradation that give rise to DOC derived from litter and compost. The results of this study indicate that oxidation of the lignin components of plant tissue follows the sequence of O-demethylation, and hydroxylation followed by ring-fission, chain-shortening, and oxidative removal of substituents. Oxidative ring-fission leads to the formation of carboxylic acid groups on the cleaved ends of the rings and, in the process, transforms phenolic groups into aliphatic alcoholic groups. The carbohydrate components are broken down into aliphatic hydroxy acids and aliphatic alcohols.

Soil Science↗
USGS1995

Mechanism of formation of humus coatings on mineral surfaces 1. Evidence for multidentate binding of organic acids from compost leachate on alumina

Measurements of the infrared linear dichroism of carboxylate groups of organic acids from compost leachate adsorbed to an alumina surface and the enthalpy of adsorption of this reaction have been made. The linear dichroism measurements indicated that the carboxylate groups are not free to rotate. This limited rotation probably results from bidentate binding of the carboxylate groups. The molar enthalpy of adsorption of the acids is approximately −100 kJ mol −1 . This high value for enthalpy of adsorption may best be explained by assuming that two or more carboxylate groups on a single dissolved organic carbon (DOC) molecule coordinate to the surficial aluminium ions.

Colloids and Surfaces A: Physicochemical and Engin↗
USGS1994

Comparison of humic substances isolated from peatbog water by sorption on DEAE-cellulose and amberlite XAD-2

Aquatic humic substances (AHS) were isolated from peatbog water by adsorption (1) on diethylaminoethyl cellulose (DEAE-C) and (2) on Amberlite XAD-2 (XAD) to compare yields of the methods and the composition of the isolated AHS. To provide a detailed comparison, the isolates were fractionated using size-exclusion and hydrophobic-interaction chromatography on Sephadex G-50. The fractions were characterized by ultraviolet-visible, infrared and 13C-nuclear magnetic spectroscopies and analyzed for elemental, functional-group, carbohydrate and amino acid compositions. More AHS adsorbed onto DEAE-C than onto XAD-2 (94 and 74%, respectively). However, only 76% of the AHS adsorbed onto DEAE-C was recovered using 0.1 M NaOH, whereas 98% of the AHS adsorbed onto XAD was released by consecutive elution with 1 M NH4OH (91%) and methanol (7%). Four main fractions of different composition were obtained from each of the alkali-desorbed AHS samples by Sephadex-gel chromatography. General agreement was found in relative amounts, spectroscopic characteristics and composition of corresponding fractions of both isolates except nitrogen content, which was significantly higher in AHS isolated with XAD, apparently due to the reaction of AHS with NH4OH used for the desorption from the resin.Aquatic humic substances (AHS) were isolated from peatbog water by adsorption (1) on diethylaminoethyl cellulose (DEAE-C) and (2) on Amberlite XAD-2 (XAD) to compare yields of the methods and the composition of the isolated AHS. To provide a detailed comparison, the isolates were fractionated using size-exclusion and hydrophobic-interaction chromatography on Sephadex G-50. The fractions were characterized by ultraviolet-visible, infrared and 13C-nuclear magnetic spectroscopies and analyzed for elemental, functional-group, carbohydrate and amino acid compositions. More AHS adsorbed onto DEAE-C than onto XAD-2 (94 and 74%, respectively). However, only 76% of the AHS adsorbed onto DEAE-C was recovered using 0.1 M NaOH, whereas 98% of the AHS adsorbed onto XAD was released by consecutive elution with 1 M NH4OH (91%) and methanol (7%). Four main fractions of different composition were obtained from each of the alkali-desorbed AHS samples by Sephadex-gel chromatography. General agreement was found in relative amounts, spectroscopic characteristics and composition of corresponding fractions of both isolates except nitrogen content, which was significantly higher in AHS isolated with XAD, apparently due to the reaction of AHS with NH4OH used for the desorption from the resin.

Water Research↗
USGS1994

Displacement of soil pore water by trichloroethylene

Dense nonaqueous phase liquids (DNAPLS) are important pollutants because of their widespread use as chemical and industrial solvents. An example of the pollution caused by the discharge of DNAPLs is found at the Picatinny Arsenal, New Jersey, where trichloroethylene (TCE) has been discharged directly into the unsaturated zone. This discharge has resulted in the formation of a plume of TCE-contaminated water in the aquifer downgradient of the discharge. A zone of dark-colored groundwater containing a high dissolved organic C content has been found near the point of discharge of the TCE. The colored-water plume extends from the point of discharge at least 30 m (100 feet) downgradient. Fulvic acids isolated from the colored-waters plume, from water from a background well that has not been affected by the discharge of chlorinated solvents, and from soil pore water collected in a lysimeter installed at an uncontaminated site upgradient of the study area have been compared. Nuclear magnetic resonance spectra of the fulvic acids from the colored waters and from the lysimeter are very similar, but are markedly different from the nuclear magnetic resonance spectrum of the fulvic acid from the background well. The three-dimensional fluorescence spectrum and the DOC fractionation profile of the colored groundwater and the soil pore water are very similar to each other, but quite different from those of the background water. It is proposed from these observations that this colored water is soil pore water that has been displaced by a separate DNAPL liquid phase downward to the saturated zone.

Journal of Environmental Quality↗