Geology topics

Jerry A. Leenheer

Publications and source records attributed to Jerry A. Leenheer.

14 recordsLinked to original sources

USGS2013

H-binding of size- and polarity-fractionated soil and lignite humic acids after removal of metal and ash components

A fractionation technique, combining dialysis removal of metal and ash components with hydrofluoric acid and pH 10 citrate buffer followed by chromatography of dialysis permeate on XAD-8 resin at decreasing pH values, has been applied to lignite humic acid (lignite-HA) and soil humic acid (soil-HA). H-binding data and non ideal competitive adsorption-Donnan model parameters were obtained for the HA fractions by theoretical analysis of H-binding data which reveal a significant increase of the carboxyl and the phenolic charge for the lignite-HA fractions vs. the parental lignite humic acid (L Parental HA). The fractionated lignite-HA material consisted mainly of permeate fractions, some of which were fulvic acid-like. The fractionated soil-HA material consisted mainly of large macromolecular structures that did not permeate the dialysis membrane during deashing. Chargeable groups had comparable concentrations in soil-HA fractions and parental soil humic acid (S Parental HA), indicating minimal interference of ash components with carboxyl and phenolic (and/or enolic) groups. Fractionation of HA, combined with theoretical analysis of H-binding, can distinguish the supramolecular vs. macromolecular nature of fractions within the same parental HA.

Environmental Science and Pollution Research↗

USGS2009

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

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

Georgia↗

USGS2009

Systematic approaches to comprehensive analyses of natural organic matter

The more that is learned of the chemistry of aquatic natural organic matter (NOM) the greater is the scientific appreciation of the vast complexity of this subject. This complexity is due not only to a multiplicity of precursor molecules in any environment but to their associations with each other and with other components of local environments such as clays, mineral acids and dissolved metals. In addition, this complex system is subject to constant change owing to environmental variables and microbial action. Thus, there is a good argument that no two NOM samples are exactly the same even from the same source at nearly the same time. When ubiquity of occurrence, reaction with water treatment chemicals, and subsequent human exposure are added to the list of NOM issues, one can understand the appeal that this subject holds for a wide variety of environmental scientists.

Annals of Environmental Science↗

USGS2008

Co-precipitation of dissolved organic matter by calcium carbonate in Pyramid Lake, Nevada

Our previous research has demonstrated that dissolved organic matter (DOM) influences calcium carbonate mineral formation in surface and ground water. To better understand DOM mediation of carbonate precipitation and DOM co-precipitation and/or incorporation with carbonate minerals, we characterized the content and speciation of DOM in carbonate minerals and in the lake water of Pyramid Lake, Nevada, USA. A 400-gram block of precipitated calcium carbonate from the Pyramid Lake shore was dissolved in 8 liters of 10% acetic acid. Particulate matter not dissolved by acetic acid was removed by centrifugation. DOM from the carbonate rock was fractionated into nine portions using evaporation, dialysis, resin adsorption, and selective precipitations to remove acetic acid and inorganic constituents. The calcium carbonate rock contained 0.23% DOM by weight. This DOM was enriched in polycarboxylic proteinaceous acids and hydroxy-acids in comparison with the present lake water. DOM in lake water was composed of aliphatic, alicyclic polycarboxylic acids. These compound classes were found in previous studies to inhibit calcium carbonate precipitation. DOM fractions from the carbonate rock were 14 C-age dated at about 3,100 to 3,500 years before present. The mechanism of DOM co-precipitation and/or physical incorporation in the calcium carbonate is believed to be due to formation of insoluble calcium complexes with polycarboxylic proteinaceous acids and hydroxy-acids that have moderately large stability constants at the alkaline pH of the lake. DOM co-precipitation with calcium carbonate and incorporation in precipitated carbonate minerals removes proteinaceous DOM, but nearly equivalent concentrations of neutral and acidic forms of organic nitrogen in DOM remain in solution. Calcium carbonate precipitation during lime softening pretreatment of drinking water may have practical applications for removal of proteinaceous disinfection by-product precursors.

Nevada↗

USGS2007

Discovery of cyanuric acid during an assessment of natural organic matter in stormflow water of the Santa Ana River, southern California, 2003-2004

A stormflow study of natural organic matter and organic contaminants in the Santa Ana River, the Mill Creek tributary, and an urban drain tributary discovered cyanuric acid in variable concentrations up to 510 g/L. Cyanuric acid was isolated with a hydrophilic natural organic matter (NOM) fraction, and its identity was confirmed by a combination of infrared spectrometry, 13C-nuclear magnetic resonance (13C-NMR) spectrometry, and electrospray ionization/mass spectrometry. Cyanuric acid concentrations, based upon 13C-NMR spectral quantitation, increased during the peak and recessional flows of the storm hydrographs during three storms at three sites. The greatest fluxes of cyanuric acid were observed in the Santa Ana River during the third storm. The most likely source of cyanuric acid is as a metabolite of triazine herbicides, based on hydrographs, land uses of the drainage basins, and the yearly application rates of triazine herbicides. The daily flux of cyanuric acid in Santa Ana River stormflow during the third storm was calculated to be about 1 percent of the yearly application rate for triazine herbicides. Cyanuric acid was not detected in ground water at wells adjacent to the Santa Ana River.

California↗

USGS2005

Characterization of dissolved and particulate natural organic matter (NOM) in Neversink Reservoir, New York

Natural organic matter (NOM) was isolated from the water of the Neversink Reservoir, part of the New York City water supply, located in the Catskill Mountains of New York. The NOM was fractionated into the following nine different fractions by the isolation procedure: (1) coarse particulates, (2) fine-particulate organics, (3) solvent-extractable organics, (4) hydrophobic neutrals (HPON fraction), (5) dissolved colloids, (6) bases, (7) hydrophobic acids (HPOA), (8) transphilic acids + neutrals (TPI-A+N), and (9) hydrophilic acids + neutrals (HPI-A+N). Each of these fractions, with exception of the first and the third which were too small for the complete series of analyses, was characterized by elemental, carbohydrate, and amino acid analyses, and by nuclear magnetic resonance and infrared spectrometry. The data obtained from these analyses indicate (1) that the fine-particulate organics and colloids are mainly composed of peptidoglycans, and lipopolysaccharides derived from algal, bacterial, and fungal cell walls, (2) that the HPO-N fraction most likely consists of a mixture of alicyclic terpenes and carbohydrates, (3) that the HPOA fraction consists mainly of lignin components conjugated to carbohydrates, (4) that the TPI-A+N and the HPI-A+N fractions most likely represent complex mixtures of relatively low molecular weight carboxylic acids derived from terpenes, carbohydrates, and peptides, and (5) that the base fraction is composed of free amino acids, browning reaction products, and peptide fragments.

Scientific Investigations Report↗

USGS2004

Factors that affect molecular weight distribution of Suwannee river fulvic acid as determined by electrospray ionization/mass spectrometry

Effects of methylation, molar response, multiple charging, solvents, and positive and negative ionization on molecular weight distributions of aquatic fulvic acid were investigated by electrospray ionization/mass spectrometry. After preliminary analysis by positive and negative modes, samples and mixtures of standards were derivatized by methylation to minimize ionization sites and reanalyzed. Positive ionization was less effective and produced more complex spectra than negative ionization. Ionization in methanol/water produced greater response than in acetonitrile/water. Molar response varied widely for the selected free acid standards when analyzed individually and in a mixture, but after methylation this range decreased. After methylation, the number average molecular weight of the Suwannee River fulvic acid remained the same while the weight average molecular weight decreased. These differences are probably indicative of disaggregation of large aggregated ions during methylation. Since the weight average molecular weight decreased, it is likely that aggregate formation in the fulvic acid was present prior to derivatization, rather than multiple charging in the mass spectra.

Georgia↗

USGS2004

Fractionation and characterization of organic matter in wastewater from a swine waste-retention basin

Organic matter in wastewater sampled from a swine waste-retention basin in Iowa was fractionated into 14 fractions on the basis of size (particulate, colloid, and dissolved); volatility; polarity (hydrophobic, transphilic, hydrophilic); acid, base, neutral characteristics; and precipitate or flocculates (floc) formation upon acidification. The compound-class composition of each of these fractions was determined by infrared and 13C-NMR spectral analyses. Volatile acids were the largest fraction with acetic acid being the major component of this fraction. The second most abundant fraction was fine particulate organic matter that consisted of bacterial cells that were subfractionated into extractable lipids consisting of straight chain fatty acids, peptidoglycans components of bacterial cell walls, and protein globulin components of cellular plasma. The large lipid content of the particulate fraction indicates that non-polar contaminants, such as certain pharmaceuticals added to swine feed, likely associate with the particulate fraction through partitioning interactions. Hydrocinnamic acid is a major component of the hydrophobic acid fraction, and its presence is an indication of anaerobic degradation of lignin originally present in swine feed. This is the first study to combine particulate organic matter with dissolved organic matter fractionation into a total organic matter fractionation and characterization.

Scientific Investigations Report↗

USGS2004

Tannins and terpenoids as major precursors of Suwannee River fulvic acid

Suwannee River fulvic acid (SRFA) was fractionated into 7 fractions by normal-phase chromatography on silica gel followed by reverse-phase fractionation on XAD-8 resin that produced 18 subfractions. Selected major subfractions were characterized by 13C-nuclear magnetic resonance (NMR), infrared spectrometry, and elemental analyses. 13C-NMR spectra of the subfractions were more indicative of precursor structures than unfractionated SRFA, and gave spectral profiles that indicated SRFA mass was about equally split between tannin precursors and terpenoid precursors. Lignin precursors were minor components. Synthesis of 13C-NMR data with elemental data for subfractions derived from both tannin and terpenoid precursors revealed high ring contents and low numbers of carbon per rings which is indicative of fused ring structures that are extensively substituted with carboxyl and methyl groups. These results ruled out extended chain structures for SRFA. This information is useful for determining sources and properties of fulvic acid in drinking water supplies as tannins are more reactive with chlorine to produce undesirable disinfection by-products than are terpenoids.

Scientific Investigations Report↗

USGS2003

Peer reviewed: Characterizing aquatic dissolved organic matter

Whether it causes aesthetic concerns such as color, taste, and odor; leads to the binding and transport of organic and inorganic contaminants; produces undesirable disinfection byproducts; provides sources and sinks for carbon; or mediates photochemical processes, the nature and properties of dissolved organic matter (DOM) in water are topics of significant environmental interest. DOM is also a major reactant in and product of biogeochemical processes in which the material serves as a carbon and energy source for biota and controls levels of dissolved oxygen, nitrogen, phosphorus, sulfur, numerous trace metals, and acidity.

Environmental Science & Technology↗

USGS2003

Biogeochemical processes that produce dissolved organic matter from wheat straw

The chemical reactions that lead to the formation of dissolved organic matter (DOM) in natural waters are poorly understood. Studies on the formation of DOM generally are complicated because almost all DOM isolates have been derived from mixtures of plant species composed of a wide variety of different types of precursor compounds for DOM formation. This report describes a study of DOM derived mainly from bales of wheat straw that had been left in a field for several years. During this period of time, black water from the decomposing wheat straw accumulated in pools in the field. The nuclear magnetic resonance and infrared spectra of the black water DOM indicate that it is composed almost entirely of lignin and carbohydrate polymeric units. Analysis by high-performance size-exclusion chromatography with multi-angle laser-light scattering detection indicates that the number average molecular weight of the DOM is 124,000 daltons. The results presented in this report indicate that the black water DOM is composed of hemicellulose chains cross-linked to lignin oligomers. These types of structures have been shown to exist in the hemicellulose matrix of plant cell walls. The cross-linked lignin-hemicellulose complexes apparently were released from partially degraded wheat-straw cell walls with little alteration. In solution in the black water, these lignin-hemicellulose polymers fold into compact globular particles in which the nonpolar parts of the polymer form the interiors of the particles and the polar groups are on the exterior surfaces of the particles. The tightly folded, compact conformation of these particles probably renders them relatively resistant to microbial degradation. This should be especially the case for the aromatic lignin structures that will be buried in the interiors of the particles.

Water-Resources Investigations Report↗

USGS1992

Identification of persistent anionic surfactant-derived chemicals in sewage effluent and groundwater

Preparative isolation and fractionation procedures coupled with spectrometric analyses were used to identify surfactant-derived contaminants in sewage effluent and sewage-contaminated groundwater from a site located on Cape Cod, Massachusetts. Anionic surfactants and their biodegradation intermediates were isolated from field samples by ion exchange and fractionated by solvent extraction and adsorption chromatography. Fractions were analyzed by 13 C nuclear magnetic resonance spectrometry and gas chromatography-mass spectrometry. Carboxylated residues of alkylphenol polyethoxylate surfactants were detected in sewage effluent and contaminated groundwater. Linear alkylbenzenesulfonates (LAS) were identified in sewage effluent and groundwater. Groundwater LAS composition suggested preferential removal of select isomers and homologs due to processes of biodegradation and partitioning. Tetralin and indane sulfonates (DATS), alicyclic analogs of LAS, were also identified in field samples. Although DATS are a minor portion of LAS formulations, equivalent concentrations of LAS and DATS in groundwater suggested persistence of alicyclic contaminant structures over those of linear structure. Sulfophenyl-carboxylated (SPC) LAS biodegradation intermediates were determined in sewage effluent and groundwater. Homolog distributions suggested that SPC containing 3–10 alkyl-chain carbons persist during infiltration and groundwater transport. Surfactant-derived residues detected in well F 300-50 groundwater have a minimum residence time in the range of 2.7–4.6 yr. LAS detected in groundwater at 500 m from infiltration has been stable over an estimated 50–500 half lives.

Journal of Contaminant Hydrology↗

USGS1982

Organic solutes in ground water at the Idaho National Engineering Laboratory

In August 1980, the U.S. Geological Survey started a reconnaissance survey of organic solutes in drinking water sources, ground-water monitoring wells, perched water table monitoring wells, and in select waste streams at the Idaho National Engineering Laboratory (INEL). The survey was to be a two-phase program. In the first phase, 77 wells and 4 potential point sources were sampled for dissolved organic carbon (DOC). Four wells and several potential point sources of insecticides and herbicides were sampled for insecticides and herbicides. Fourteen wells and four potential organic sources were sampled for volatile and semivolatile organic compounds. The results of the DOC analyses indicate no high level (>20 mg/L DOC) organic contamination of ground water. The only detectable insecticide or herbicide was a DDT concentration of 10 parts per trillion (0.01 microgram per liter) in one observation well. The volatile and semivolatile analyses do not indicate the presence of hazardous organic contaminants in significant amounts (>10 micrograms per liter) in the samples taken. Due to the lack of any significant organic ground-water contamination in this reconnaissance survey, the second phase of the study, which was to follow up the first phase by additional sampling of any contaminated wells, was canceled.

Idaho↗

USGS1979

Analytical method for dissolved-organic carbon fractionation

A standard procedure for analytical-scale dissolved organic carbon fractionation is presented, whereby dissolved organic carbon in water is first fractionated by a nonionic macroreticular resin into acid, base, and neutral hydrophobic organic solute fractions, and next fractionated by ion-exchange resins into acid, base, and neutral hydrophilic solute fractions. The hydrophobic solutes are defined as those sorbed on a nonionic, acrylic-ester macroreticular resin and are differentiated into acid, base, and nautral fractions by sorption/desorption controlled by pH adjustment. The hydrophilic bases are next sorbed on strong-acid ion-exchange resin, followed by sorption of hydrophilic acids on a strong-base ion-exchange resin. Hydrophilic neutrals are not sorbed and remain dissolved in the deionized water at the end of the fractionation procedure. The complete fractionation can be performed on a 200-milliliter filtered water sample, whose dissolved organic carbon content is 5-25 mg/L and whose specific conductance is less than 2,000 μmhos/cm at 25°C. The applications of dissolved organic carbon fractionation analysis range from field studies of changes of organic solute composition with synthetic fossil fuel production, to fundamental studies of the nature of sorption processes.

Water-Resources Investigations Report↗