Geology topics

R.L. Wershaw

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

At least 37 records · Page 2Linked to original sources

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↗

USGS1992

Humic substances and trace metals associated with Fe and Al oxides deposited in an acidic mountain stream

Hydrous iron and aluminum oxides are deposited on the streambed in the confluence of the Snake River and Deer Creek, two streams in the Colorado Rocky Mountains. The Snake River is acidic and has high concentrations of dissolved Fe and Al. These metals precipitate at the confluence with the pristine, neutral pH, Deer Creek because of the greater pH (4.5-6.0) in the confluence. The composition of the deposited oxides changes consistently with distance downstream, with the most upstream oxide samples having the greatest Fe and organic carbon content. Fulvic acid accounts for most of the organic content of the oxides. Results indicate that streambed oxides in the confluence are not saturated with respect to their capacity to sorb dissolved humic substances from streamwater. The contents of several trace metals (Mn, Zn, Cu, Pb, Ni and Co) also decrease with distance downstream and are correlated with both the Fe and organic carbon contents. Strong metal-binding sites associated with the sorbed fulvic acid are more than sufficient to account for the trace metal content of the oxides. Complexation of trace metals by sorbed fulvic acid may explain the observed downstream decrease in trace metal content.

Science of Total Environment↗

USGS1992

Membrane-micelle model for humus in soils and sediments and its relation to humification

No abstract available.

Open-File Report↗

USGS1989

Aqueous chlorination of resorcinol

An investigation of the aqueous chlorination (NaOCl) of resorcinol is reported. The following intermediates were detected in moderate to high yield at different pH values and varying percentages of chlorination: 2-chloro-, 4-chloro-, 2,4-dichloro-, 4,6-dichloro- and 2,4,6-trichlororesorcinol. Only trace amounts of the intermediates were detected when the chlorination was conducted in the presence of phosphate buffer. This result has significant implications since resorcinol in phosphate buffer has been used as a model compound in several recent studies on the formation of chlorinated hydrocarbons during chlorination of drinking water. Relative rates of chlorination were determined for resorcinol and several of the chlorinated resorcinols. Resorcinol was found to chlorinate only three times faster than 2,4,6-trichlororesorcinol. The structure 2,4,6-trichlororesorcinol was established as a monohydrate even after sublimation. A tetrachloro or pentachloro intermediate was not detected, suggesting that the ring-opening step of such an intermediate must be rapid.

Environmental Toxicology and Chemistry↗

USGS1988

Rapid changes in dissolved humic substances in Spirit Lake and South Fork Castle Lake, Washington

One major effect of the eruption of Mount St. Helens, Washington, was a large increase of dissolved organic material in the lakes of the area devastated near the volcano. Much of this material was aquatic fulvic acid derived from plants and soils from the surrounding watershed. During the 3 yr after the eruption, substantial chemical changes occurred in the aquatic fulvic acid. -from Authors

Limnology and Oceanography↗

USGS1987

The use of variable temperature and magic-angle sample spinning in studies of fulvic acids

Intensity distortions and poor signal to noise in the cross-polarization magic-angle sample spinning NMR of fulvic acids were investigated and attributed to molecular mobility in these ostensibly "solid" materials. We have shown that inefficiencies in cross polarization can be overcome by lowering the sample temperature to about -60??C. These difficulties can be generalized to many other synthetic and natural products. The use of variable temperature and cross-polarization intensity as a function of contact time can yield valuable qualitative information which can aid in the characterization of many materials. ?? 1987.

Journal of Magnetic Resonance↗

USGS1986

A new model for humic materials and their interactions with hydrophobic organic chemicals in soil-water or sediment-water systems

A generalized model of humic materials in soils and sediments, which is consistent with their observed properties, is presented. This model provides a means of understanding the interaction of hydrophobic pollutants with humic materials. In this model, it is proposed that the humic materials in soils and sediments consist of a number of different oligomers and simple compounds which result from the partial degradation of plant remains. These degradation products are stabilized by incorporation into humic aggregates bound together by weak bonding mechanisms, such as hydrogen bonding, pi bonding, and hydrophobic interactions. The resulting structures are similar to micelles or membranes, in which the interiors of the structures are hydrophobic and the exteriors are hydrophilic. Hydrophobic compounds will partition into the hydrophobic interiors of the humic micelles or "membrane-like" structures. ?? 1986.

Journal of Contaminant Hydrology↗

USGS1985

Molecular weight and size measurements of humic substances

No abstract available.

Book chapter↗

USGS1982

Molecular size of aquatic humic substances

Aquatic humic substances, which account for 30 to 50% of the organic carbon in water, are a principal component of aquatic organic matter. The molecular size of aquatic humic substances, determined by small-angle X-ray scattering, varies from 4.7 to 33 Å in their radius of gyration, corresponding to a molecular weight range of 500 to greater than 10,000. The aquatic fulvic acid fraction contains substances with molecular weights ranging from 500 to 2000 and is monodisperse, whereas the aquatic humic acid fraction contains substances with molecular weights ranging from 1000 to greater than 10,000 and is generally polydisperse.

Arizona, Colorado, Hawaii, Florida, Massachusetts,↗

USGS1981

Reconnaissance samplings and characterization of aquatic humic substances at the Yuma Desalting Test Facility, Arizona

Smectite clay minerals were found to be the principal compound on the surface of the cellulose-acetate, reverse-osmosis membranes at the Yuma Desalting Test Facility. These clay minerals were not present in the pumped ground water, but were blown into the conveyance canal from adjacent soils. Humic substances from the water and suspended sediments were associated with the clay films on the membrane, but no definitive results concerning their role in fouling were achieved. Microbial fouling is believed to be only a minor aspect of membrane fouling. Chemical and physical changes in humic substances were extensively studied at four points in the water-treatment process. Humic substances accounted for the largest component (over 25 percent) of organic constituents. Humic substances in the canal source water were similar to other aquatic humic substances present in natural waters. During the treatment process, these substances are brominated and decolorized. The effect of these halogenated humic substances on membrane fouling is unclear, but their presence in the reverse-osmosis product water and reverse-osmosis reject brine, along with volatile trihalomethanes, has led to environmental concerns. (USGS)

Arizona↗

USGS1977

Chemical structure of humic acids - Part 1, a generalized structural model

A new model is proposed for the structure of humic acids. In this model humic acid is pictured as being made up of a hierarchy of structural elements. At the lowest level in this hierarchy are simple phenolic, quinoid, and benzene carboxylic acid groups. These groups are bonded covalently into small particles. Particles of similar chemical structure are linked together by weak bonds to form "homogeneous" aggregates. Two or more different types of aggregates may be linked together to form mixed aggregates. Complexes of humic acid and clay minerals are also formed.