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Ronald L. Malcolm

Publications and source records attributed to Ronald L. Malcolm.

33 records · Page 2Linked to original sources
USGS1987

Presence and potential significance of aromatic-ketone groups in aquatic humic substances

Aquatic humic- and fulvic-acid standards of the International Humic Substances Society were characterized, with emphasis on carbonyl-group nature and content, by carbon-13 nuclear-magnetic-resonance spectroscopy, proton nuclear-magnetic-resonance spectroscopy, and infrared spectroscopy. After comparing spectral results of underivatized humic and fulvic acids with spectral results of chemically modified derivatives, that allow improved observation of the carbonyl group, the data clearly indicated that aromatic ketone groups comprised the majority of the carbonyl-group content. About one ketone group per monocyclic aromatic ring was determined for both humic and fulvic acids. Aromatic-ketone groups were hypothesized to form by photolytic rearrangements and oxidation of phenolic ester and hydrocarbon precursors; these groups have potential significance regarding haloform formation in water, reactivity resulting from active hydrogen of the methyl and methylene adjacent to the ketone groups, and formation of hemiketal and lactol structures. Aromatic-ketone groups also may be the point of attachment between aliphatic and aromatic moieties of aquatic humic-substance structure.

Georgia↗
USGS1985

Pyrolysis-mass spectrometry/pattern recognition on a well-characterized suite of humic samples

A suite of well-characterized humic and fulvic acids of freshwater, soil and plant origin was subjected to pyrolysis-mass spectrometry and the resulting data were analyzed by pattern recognition and factor analysis. A factor analysis plot of the data shows that the humic acids and fulvic acids can be segregated into two distinct classes. Carbohydrate and phenolic components are more pronounced in the pyrolysis products of the fulvic acids, and saturated and unsaturated hydrocarbons contribute more to the humic acid pyrolysis products. A second factor analysis plot shows a separation which appears to be based primarily on whether the samples are of aquatic or soil origin.

Geochimica et Cosmochimica Acta↗
USGS1983

The contribution of humic substances to the acidity of colored natural waters

An operationally defined carboxyl content of humic substances extracted from rivers, streams, lakes, wetlands, and groundwaters throughout the United States and Canada is reported. Despite the diversity of the samples, only small variations were observed in this humic carboxyl content. The dissociation behavior of two combined fulvic/humic acid extracts was studied and it was found that the dissociation of the humics varied in a predictable manner with pH. Using a carboxyl content of 10 μeq/ mg humic organic carbon, and mass action quotient calculated from sample pH, the ionic balances of three highly colored Nova Scotia rivers were estimated.

Geochimica et Cosmochimica Acta↗
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

Preliminary data from a series of artificial recharge experiments at Stanton, Texas

A series of artificial recharge experiments was conducted by the U.S. Geological Survey at an experimental site located in Stanton, Texas. Five tests were performed from March 1977 through December 1978 to: (1) Evaluate the hydraulic properties of the aquifer; (2) test sampling and monitoring equipment; (3) compare tracers for future use in hydrologic investigations; and (4) determine the radial and vertical distribution of hydraulic properties at the site. Suites of inorganic, and both volatile and nonvolatile organic tracers were used in the tests, and comparative data were obtained from sampling points at several radial distances and depths from the injection well. Hydraulic data from aquifer tests and geologic data from core material also were obtained during the investigation.

Texas↗
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↗
USGS1979

Concentration and fractionation of hydrophobic organic acid constituents from natural waters by liquid chromatography

A scheme is presented which used adsorption chromatography with pH gradient elution and size-exclusion chromatography to concentrate and separate hydrophobic organic acids from water. A review of chromatographic processes involved in the flow scheme is also presented. Organic analytes which appear in each aqueous fraction are quantified by dissolved organic carbon analysis. Hydrophobic organic acids in a water sample are concentrated on a porous acrylic resin. These acids usually constitute approximately 30-50 percent of the dissolved organic carbon in an unpolluted water sample and are eluted with an aqueous eluent (dilute base). The concentrate is then passed through a column of polyacryloylmorpholine gel, which separates the acids into high- and low-molecular-weight fractions. The high- and low-molecular-weight eluates are reconcentrated by adsorption chromatography, then are eluted with a pH gradient into strong acids (predominately carboxylic acids) and weak acids (predominately phenolic compounds). For standard compounds and samples of unpolluted waters, the scheme fractionates humic substances into strong and weak acid fractions that are separated from the low molecular weight acids. A new method utilizing conductivity is also presented to estimate the acidic components in the methanol fraction.

Water Supply Paper↗
USGS1977

Geochemistry of the Mattole River in Northern California

The chemical composition of streams can vary greatly with changing discharge during storm runoff. These chemical changes are related to the pathways of various water parcels from the time they fall as rain until they enter the stream, and to the interactions between water and sediment during transport downstream. In order to understand better the chemical variations during storms, an extensive investigation was made of the Mattole River, a chemically clean coastal stream in Mendocino County, California. The Mattole drains a topographically mature basin of 620 sw km which has relief of about 1200 m, a long summer dry season, and mean annual rainfall of about 2300 mm. The stream flow is composed of seasonally varying proportions of four flow components, namely, surface runoff, quick-return flow (rainfall having brief and intimate contact with the soil before entering the surface drainage), delayed-return flow, and base runoff. Each component is identified by its characteristic chemistry and by the time delay between rainfall and entrance into the stream. Information is also presented on rain chemistry, adsorption reactions of suspended sediments in the fresh and brackish environments, and compositional variation of river sediments with particle size. (Woodard-USGS)

Open-File Report↗
USGS1976

Physical, chemical, and biological aspects of subsurface organic waste injection near Wilmington, North Carolina

From May 1968 to December 1972, an industrial organic waste was injected at rates of 100 to 200 gallons per minute (6.3 to 12.6 litres per second) into a sand, gravel, and limestone aquifer of Late Cretaceous age by Hercules Inc. located near Wilmington, North Carolina. This report presents both field and laboratory data pertaining to the physical, chemical, and biological effects of waste injection into the subsurface at this particular site, a case history of the operation, predictions of the reactions between certain organic wastes and the aquifer components, and descriptions of the effects of these reactions on the subsurface movement of the wastes. The case history documents a situation in which subsurface waste injection could not be considered a successful means of waste disposal. The first injection well was used only for 1 year due to excessive wellhead pressure build-up above the specified pressure limit of 150 pounds per square inch (10.3 bars). A second injection well drilled as a replacement operated for only 5 months before it too began to have problems with plugging. Upward leakage of waste into shallower aquifers was also detected at several wells in the injection-observation well system. The multiple problems of plugging, high pressures, and waste leakage suggested that the reactive nature of the waste with the aquifer into which it was injected was the primary reason for the difficulties experienced with waste injection. A site study was initiated in June 1971 to investigate waste-aquifer interactions. The first stage of the study determined the hydrogeologic conditions at the site, and characterized the industrial waste and the native ground water found in the injection zone and other aquifers. The injection zone consisted of multiple permeable zones ranging in depth from about 850 to 1,000 feet (259 to 305 metres) below land surface. In addition to the injection zone, aquifers were found near depths of 60, 300, 500, and 700 feet (18, 91, 152, and 213 metres) below land surface. The aquifers from 300 feet (91 metres) down to the injection zone were flowing artesian with the natural pressure of the injection zone being 65 feet (20 metres) above land surface at the site. The dissolved solids concentration in the native ground water increased with depth to an average value of 20,800 mg/l (milligram per litre) (two-thirds that of seawater) in the water from the injection zone. Sodium chloride was the major dissolved solid, and all of the ground water below 300-feet (91-metres) depth was slightly alkaline. Dissolved organic carbon of the industrial waste averaged 7,100 mg/l and 95 percent of the organic carbon was identified and quantified. The major organic waste constituents in order of decreasing abundance were acetic acid, formic acid, p-toluic acid, formaldehyde, methanol, terephthalic acid, phthalic acid, and benzoic acid. Prior to injection, the waste was neutralized with lime to pH 4 so that the major inorganic waste constituent was calcium at a concentration of 1,300 mg/l. The second stage of the site study involved the observation of waste-aquifer interactions at various wells as the waste arrived and passed by the wells. Water samples obtained from three observation wells located 1,500 to 2,000 feet (457 to 607 metres) from the original injection well gave evidence for biochemical waste transformations at low waste concentrations. Gas that effervesced from these water samples contained up to 54 percent methane by volume. Ferrous iron concentrations as high as 35 mg/l, hydrogen sulfide gas, and sulfide precipitates were additional indicators of biochemical reductive processes in the subsurface environment. Approximately 3,000 organisms per millilitre were found in uncontaminated ground water from the injection zone whereas in waste-contaminated wells, the number increased to levels as high as 1,000,000 organisms per millilitre. High concentrations of waste were found to be toxic to microo

Professional Paper↗
USGS1976

Organic carbon and nitrogen concentrations and annual organic carbon load of six selected rivers of the United States

The organic carbon load during 1969-70 of each of the six rivers in this study is substantial. The 3.4-billion-kilogram (3.7-million-ton) and 47-million-kilogram (52-thousandton) annual organic carbon loads of the Mississippi River and the Brazos River (Tex.), respectively, were approximately equally distributed between dissolved and suspended phases, whereas the 725-million-kilogram (79.8-million-ton) organic load of the Missouri River was primarily in the suspended phase. The major portion of the 6.4-million-kilogram (7.3 thousand-ton) and the 19-million-kilogram (21-thousand-ton) organic carbon loads of the Sopchoppy River (Fla.) and the Neuse River (N.C.), respectively, was in the dissolved phase. DOC (dissolved organic carbon) concentrations in most rivers were usually less than 8 milligrams per litre. SOC (suspended organic carbon) concentrations fluctuated markedly with discharge, ranging between 1 and 14 percent, by weight, in sediment of most rivers. DOC concentrations were found to be independent of discharge, whereas SOC and SIC (suspended inorganic carbon) concentrations were positively correlated with discharge. Seasonal fluctuations in DOC and SOC were exhibited by the Missouri, Neuse, Ohio, and Brazos Rivers, but both SOC and DOC concentrations were relatively constant throughout the year in the Mississippi and Sopchoppy Rivers. The carbon-nitrogen ratio in the sediment phase of all river waters averaged less than 8 1 as compared with 12:1 or greater for most soils. This high nitrogen content shows a nitrogen enrichment of the stream sediment over that in adjacent soils, which suggests that different decomposition and humification processes are operating in streams than in the soils. The abundance of organic material in the dissolved and suspended phase of all river waters in this study indicate a large capacity factor for various types of organic reactivity within all streams and the quantitative importance of organic constituents in relation to the water quality of rivers and streams.

Water Supply Paper↗
USGS1976

Method and importance of obtaining humic and fulvic acids of high purity

A detailed procedure incorporating centrifugation, pressure filtration, dialysis, resin exchange, and freeze drying is given for the extraction and purification of fulvic and humic acids from soils and sediments. By use of the procedure humic acids have been prepared which have less than 0.22 percent ash. The isolation of relatively ash-free natural organic matter preparations is an essential prerequisite to the characterization of organic reactivity in natural systems. Inorganic impurities of amorphous and crystalline clay minerals and various inorganic metal ions often lead to numerous complications and errors during experimentation with organic matter because the inorganic substances associated with the organic phase cause variable reactivity of the organic substances.

Journal of Research of the U.S. Geological Survey↗
USGS1974

Occurrence of dissolved organic carbon in selected ground-water samples in the United States

A study of nonvolatile DOC (dissolved organic carbon) in ground water was conducted to establish base levels of naturally occurring dissolved organic materials. Samples of ground water were obtained at 100 sites in 27 States. Samples were pressure filtered at the time of collection and immediately frozen on dry ice. DOC concentrations were determined by wet oxidation of organic carbon to carbon dioxide which was measured by an infrared analyzer. The DOC concentrations ranged from less than the 0.1 mg/l limit of detection to 15 mg/l. Concentrations of DOC were directly correlated with specific conductance and alkalinity, but did not correlate with pH. The DOC mean concentration was 1.2 mg/l; however, the DOC median value was lower at 0.7 mg/l. Differences in DOC concentration for various types of consolidated rock aquifers were slight; for example, median DOC values for sandstone, limestone, and crystalline rock aquifer types ranged from 0.5 to 0.7 mg/l. No difference was found in the median DOC concentration between shallow (<200 ft; 61 m) and deep (>200 ft) sand and gravel aquifers.

Journal of Research of the U.S. Geological Survey↗
USGS1973

Preparative free-flow electrophoresis as a method of fractionation of natural organic materials

Preparative free-flow electrophoresis was found to be an efficient method of conducting large-scale fractionations of the natural organic polyelectrolytes occurring in many surface waters and soils. The method of free-flow electrophoresis obviates, the problem of adsorption upon a supporting medium and permits the use of high potential gradients and currents because of an efficient cooling system. Separations were monitored by determining organic carbon concentration with a dissolved carbon analyzer, and color was measured by absorbance at 400 nanometers. Organic materials from waters and soils were purified by filtration, hydrogen exchange, and dialysis and were concentrated by freeze drying or freeze concentration. In electrophoretic fractionations of natural organic materials typically found in surface waters and soils, color was found to increase with the charge of the fraction.

Water Supply Paper↗
USGS1973

Fractionation and characterization of natural organic matter from certain rivers and soils by free-flow electrophoresis

Soluble river organic matter and soil fulvic acids from a variety of environments were compared by examining the free-flow electrophoretic fractionation curves of organic carbon, color, and polysaccharides. Significant amounts of virtually colorless organic material were found in both the soil and the river preparations. Polysaccharides comprised 20-75 percent of the colorless material in the soil fulvic acids but only 3.2-7.0 percent of the colorless material in the river preparations. A significant amount of polysaccharides was complexed with organic materials having negative charges. Amounts of polysaccharides were greater in the Fairbanks soil from Alaska than in the soils from North Carolina or Iowa, and they were greater in the Tahquamenon River in Michigan than in the two rivers in Florida; this suggests that polysaccharide degradation is slower in cooler environments. For all of the organic preparations which were fractionated, the intensity of the yellow color increased as the charge on the organic anion increased. Highly colored, negatively charged organic material was found to be present in greater amounts in the subsurface spodic soil horizon of the Lakewood and Fairbanks soils than in the surface mollic horizon of the Macksburg soil. Infrared spectroscopy and elemental analysis of four pooled fractions of the Fairbanks fulvic acid indicated increasing aromatic character with increasing negative charge. An increase in the carboxyl content with negative charge suggests the carboxyl group as the primary source of the negative charge.

Water Supply Paper↗