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J.R. Garbarino

Publications and source records attributed to J.R. Garbarino.

16 recordsLinked to original sources
USGS2006

Anaerobic biotransformation of organoarsenical pesticides monomethylarsonic acid and dimethylarsinic acid

Monomethylarsonic acid (MMAV) and dimethylarsinic acid (DMAV) are extensively utilized as pesticides, introducing large quantities of arsenic into the environment. Once released into the environment, these organoarsenicals are subject to microbial reactions. Aerobic biodegradation of MMAV and DMAV has been evaluated, but little is known about their fate in anaerobic environments. The objective of this study was to evaluate the biotransformation of MMAV and DMAV in anaerobic sludge. Biologically mediated conversion occurred under methanogenic or sulfate-reducing conditions but not in the presence of nitrate. Monomethylarsonous acid (MMAIII) was consistently observed as an important metabolite of MMAV degradation, and it was recovered in molar yields ranging from 5 to 47%. The main biotransformation product identified from DMAV metabolism was MMAV, which was recovered in molar yields ranging from 8 to 65%. The metabolites indicate that reduction and demethylation are important steps in the anaerobic bioconversion of MMAV and DMAV, respectively. ?? 2006 American Chemical Society.

Journal of Agricultural and Food Chemistry↗
USGS2006

Anaerobic biotransformation of roxarsone and related N-substituted phenylarsonic acids

Large quantities of arsenic are introduced into the environment through land application of poultry litter containing the organoarsenical feed additive roxarsone (3-nitro-4-hydroxyphenylarsonic acid). The objective of this study was to evaluate the bioconversion of roxarsone and related N-substituted phenylarsonic acid derivatives under anaerobic conditions. The results demonstrate that roxarsone is rapidly transformed in the absence of oxygen to the corresponding aromatic amine, 4-hydroxy-3-aminophenylarsonic acid (HAPA). The formation of HAPA is attributable to the facile reduction of the nitro group. Electron-donating substrates, such as hydrogen gas, glucose, and lactate, stimulated the rate of nitro group reduction, indicating a microbial role. During long-term incubations, HAPA and the closely related 4-aminophenylarsonic acid (4-APA) were slowly biologically eliminated by up to 99% under methanogenic and sulfate-reducing conditions, whereas little or no removal occurred in heat-killed inoculum controls. Arsenite and, to a lesser extent, arsenate were observed as products of the degradation. Freely soluble forms of the inorganic arsenical species accounted for 19-28% of the amino-substituted phenylarsonic acids removed. This constitutes the first report of a biologically catalyzed rupture of the phenylarsonic group under anaerobic conditions. ?? 2006 American Chemical Society.

Environmental Science & Technology↗
USGS2005

Factors controlling tungsten concentrations in ground water, Carson Desert, Nevada

n investigation of a childhood leukemia cluster by US Centers for Disease Control and Prevention revealed that residents of the Carson Desert, Nevada, are exposed to high levels of W and this prompted an investigation of W in aquifers used as drinking water sources. Tungsten concentrations in 100 ground water samples from all aquifers used as drinking water sources in the area ranged from 0.27 to 742 μg/l. Ground water in which W concentrations exceed 50 μg/l principally occurs SE of Fallon in a geothermal area. The principal sources of W in ground water are natural and include erosion of W-bearing mineral deposits in the Carson River watershed upstream of Fallon, and, possibly, upwelling geothermal waters. Ground water in the Fallon area is strongly reducing and reductive dissolution of Fe and Mn oxyhydroxides may be releasing W; however, direct evidence that the metal oxides contain W is not available. Although W and Cl concentrations in the Carson River, a lake, and water from many wells, appear to be controlled by evaporative concentration, evaporation alone cannot explain the elevated W concentrations found in water from some of the wells. Concentrations of W exceeding 50 μg/l are exclusively associated with Na &#x2013; HCO 3 "> Na–HCO3 and Na–Cl water types and pH > 8.0; in these waters, geochemical modeling indicates that W exhibits <10% adsorption. Tungsten concentrations are strongly and positively correlated with As, B, F, and P, indicating either common sources or common processes controlling their concentrations. Geochemical modeling indicates W concentrations are consistent with pH-controlled adsorption of W. The geochemical model PHREEQC was used to calculate IAP values, which were compared with published Ksp values for primary W minerals. FeWO 4 , MnWO 4 , Na 2 WO 4 , and MgWO 4 were undersaturated and CaWO 4 and SrWO 4 were approaching saturation. These conclusions are tentative because of uncertainty in the thermodynamic data. The similar behavior of As and W observed in this study suggests ground water in areas where elevated As concentrations are present also may contain elevated W concentrations, particularly if there is a mineral or geothermal source of W and reducing conditions develop in the aquifer.

Nevada↗
USGS2005

Effects of iron on arsenic speciation and redox chemistry in acid mine water

Concern about arsenic is increasing throughout the world, including areas of the United States. Elevated levels of arsenic above current drinking-water regulations in ground and surface water can be the result of purely natural phenomena, but often are due to anthropogenic activities, such as mining and agriculture. The current study correlates arsenic speciation in acid mine drainage and mining-influenced water with the important water-chemistry properties Eh, pH, and iron(III) concentration. The results show that arsenic speciation is generally in equilibrium with iron chemistry in low pH AMD, which is often not the case in other natural-water matrices. High pH mine waters and groundwater do not always hold to the redox predictions as well as low pH AMD samples. The oxidation and precipitation of oxyhydroxides deplete iron from some systems, and also affect arsenite and arsenate concentrations through sorption processes. ?? 2004 Elsevier B.V. All rights reserved.

Journal of Geochemical Exploration↗
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

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

Presence of organoarsenicals used in cotton production in agricultural water and soil of the Southern United States

Arsenicals have been used extensively in agriculture in the United States as insecticides and herbicides. Mono- and disodium methylarsonate and dimethylarsinic acid are organoarsenicals used to control weeds in cotton fields and as defoliation agents applied prior to cotton harvesting. Because the toxicity of most organoarsenicals is less than that of inorganic arsenic species, the introduction of these compounds into the environment might seem benign. However, biotic and abiotic degradation reactions can produce more problematic inorganic forms of arsenic, such as arsenite [As(III)] and arsenate [As(V)]. This study investigates the occurrences of these compounds in samples of soil and associated surface and groundwaters. Preliminary results show that surface water samples from cotton-producing areas have elevated concentrations of methylarsenic species (>10 ??g of As/L) compared to background areas (<1 ??g of As/L). Species transformations also occur between surface waters and adjacent soils and groundwaters, which also contain elevated arsenic. The data indicate that point sources of arsenic related to agriculture might be responsible for increased arsenic concentrations in local irrigation wells, although the elevated concentrations did not exceed the new (2002) arsenic maximum contaminant level of 10 ??g/L in any of the wells sampled thus far.

Journal of Agricultural and Food Chemistry↗
USGS2002

Preserving the distribution of inorganic arsenic species in groundwater and acid mine drainage samples

The distribution of inorganic arsenic species must be preserved in the field to eliminate changes caused by metal oxyhydroxide precipitation, photochemical oxidation, and redox reactions. Arsenic species sorb to iron and manganese oxyhydroxide precipitates, and arsenite can be oxidized to arsenate by photolytically produced free radicals in many sample matrices. Several preservatives were evaluated to minimize metal oxyhydroxide precipitation, such as inorganic acids and ethylenediaminetetraacetic acid (EDTA). EDTA was found to work best for all sample matrices tested. Storing samples in opaque polyethylene bottles eliminated the effects of photochemical reactions. The preservation technique was tested on 71 groundwater and six acid mine drainage samples. Concentrations in groundwater samples reached 720 ??g-As/L for arsenite and 1080 ??g-As/L for arsenate, and acid mine drainage samples reached 13 000 ??g-As/L for arsenite and 3700 ??g-As/L for arsenate. The arsenic species distribution in the samples ranged from 0 to 90% arsenite. The stability of the preservation technique was established by comparing laboratory arsenic speciation results for samples preserved in the field to results for subsamples speciated onsite. Statistical analyses indicated that the difference between arsenite and arsenate concentrations for samples preserved with EDTA in opaque bottles and field speciation results were analytically insignificant. The percentage change in arsenite:arsenate ratios for a preserved acid mine drainage sample and groundwater sample during a 3-month period was -5 and +3%, respectively.

Environmental Science & Technology↗
USGS2002

Contaminants in arctic snow collected over northwest Alaskan sea ice

Snow cores were collected over sea ice from four northwest Alaskan Arctic estuaries that represented the annual snowfall from the 1995-1996 season. Dissolved trace metals, major cations and anions, total mercury, and organochlorine compounds were determined and compared to concentrations in previous arctic studies. Traces (<4 nanograms per liter, ng L-1) of cis- and trans-chlordane, dimethyl 2,3,5,6-tetrachloroterephthalate, dieldrin, endosulfan II, and PCBs were detected in some samples, with endosulfan I consistently present. High chlorpyrifos concentrations (70-80 ng L-1) also were estimated at three sites. The snow was highly enriched in sulfates (69- 394 mg L-1), with high proportions of nonsea salt sulfates at three of five sites (9 of 15 samples), thus indicating possible contamination through long-distance transport and deposition of sulfate-rich atmospheric aerosols. Mercury, cadmium, chromium, molybdenum, and uranium were typically higher in the marine snow (n = 15) in relation to snow from arctic terrestrial studies, whereas cations associated with terrigenous sources, such as aluminum, frequently were lower over the sea ice. One Kasegaluk Lagoon site (Chukchi Sea) had especially high concentrations of total mercury (mean = 214 ng L-1, standard deviation = 5 ng L-1), but no methyl mercury was detected above the method detection limit (0.036 ng L-1) at any of the sites. Elevated concentrations of sulfate, mercury, and certain heavy metals might indicate mechanisms of contaminant loss from the arctic atmosphere over marine water not previously reported over land areas. Scavenging by snow, fog, or riming processes and the high content of deposited halides might facilitate the loss of such contaminants from the atmosphere. Both the mercury and chlorpyrifos concentrations merit further investigation in view of their toxicity to aquatic organisms at low concentrations.

Water, Air, & Soil Pollution↗
USGS1996

The effect of membrane filtration on dissolved trace element concentrations

The almost universally accepted operational definition for dissolved constituents is based on processing The almost universally accepted operational definition for dissolved constituents is based on processing whole-water samples through a 0.45-μm membrane filter. Results from field and laboratory experiments indicate that a number of factors associated with filtration, other than just pore size (e.g., diameter, manufacturer, volume of sample processed, amount of suspended sediment in the sample), can produce substantial variations in the ‘disolved’ concentrations of such elements as Fe, Al, Cu, Zn, Pb, Co, and Ni. These variations result from the inclusion/exclusion of colloidally-associated trace elements. Thus, 'dissolved' concentrations quantitated by analyzing filtrates generated by processing whole-water through similar pore-sized membrane filters may not be equal/comparable. As such, simple filtration through a 0.45-μm membrane filter may no longer represent an acceptable operational definition for dissolved chemical constituents. This conclusion may have important implications for environmental studies and regulatory agencies.

Water, Air, & Soil Pollution↗
USGS1996

The effect of using different 0.45 μm filter membranes on 'dissolved' element concentrations in natural waters

The effect of 4 different 0.45 μm pore size filter membrane systems on the ‘dissolved’ concentration of 28 elements in 5 natural water samples of varying matrix is reported. In 3 of the 5 waters, consistently higher concentrations of most elements (minor and trace) are obtained using Nucleopore 47 mm filter and the cellulose acetate/nitrate 47 mm filter than those measured using the 142 mm cellulose nitrate MFS filter or the Gelman capsule 47 mm filter. These distinct and coherent patterns in elemental behaviour disappear for the other 2 samples, an organic-rich peat water of high suspended load and a mineralised sample high in Si and Ca. Thus the nature and degree of filtration artifacts is matrix-dependent. These trends are evident in both data sets produced by 2 independent laboratories using different instrumentation, techniques and calibrating procedures. The average relative standard deviation in elemental concentration across the 4 filter types is in the range 9–21%. The presence of such filtration artifacts must be considered in projects where, for example, seasonal variability of water composition is under examination, data from various sources are being merged or hydrogeochemical surveys are being conducted.

Applied Geochemistry↗
USGS1996

Inductively coupled plasma-mass spectrometric method for the determination of dissolved trace elements in natural water

An inductively coupled plasma-mass spectrometry method was developed for the determination of dissolved Al, As, B, Ba, Be, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Sr, Tl, U, V, and Zn in natural waters. Detection limits are generally in the 50-100 picogram per milliliter (pg/mL) range, with the exception of As which is in the 1 microgram per liter (ug/L) range. Interferences associated with spectral overlap from concomitant isotopes or molecular ions and sample matrix composition have been identified. Procedures for interference correction and reduction related to isotope selection, instrumental operating conditions, and mathematical data processing techniques are described. Internal standards are used to minimize instrumental drift. The average analytical precision attainable for 5 times the detection limit is about 16 percent. The accuracy of the method was tested using a series of U.S. Geological Survey Standard Reference Water Standards (SWRS), National Research Council Canada Riverine Water Standard, and National Institute of Standards and Technology (NIST) Trace Elements in Water Standards. Average accuracies range from 90 to 110 percent of the published mean values.

Open-File Report↗
USGS1985

Statistical evaluation of an inductively coupled plasma atomic emission spectrometric method for routine water quality testing

In an interlaboratory test, inductively coupled plasma atomic emission spectrometry (ICP-AES) was compared with flame atomic absorption spectrometry and molecular absorption spectrophotometry for the determination of 17 major and trace elements in 100 filtered natural water samples. No unacceptable biases were detected. The analysis precision of ICP-AES was found to be equal to or better than alternative methods. Known-addition recovery experiments demonstrated that the ICP-AES determinations are accurate to between plus or minus 2 and plus or minus 10 percent; four-fifths of the tests yielded average recoveries of 95-105 percent, with an average relative standard deviation of about 5 percent.

Applied Spectroscopy↗
USGS1983

Ground-water contamination by organic bases derived from coal-tar wastes

A fluid sample from a shallow aquifer contaminated by coal-tar wastes was analyzed for organic bases. The sample consisted of a mixture of aqueous and oily-tar phases. The phases were separated by centrifugation and filtration. Organic bases were isolated from each phase by pH adjustment and solvent extraction. Organic bases in the oily-tar phase were further purified by neutral-alumina, micro-column adsorption chromatography. Separation and identification of the organic bases in each phase were achieved by using capillary gas chromatography-mass spectrometry-computer (GC-MS-COM) and probe distillation-high resolution mass spectrometry (PD-HRMS) techniques. Organic bases present in the aqueous phase included primary aromatic amines (such as aniline, alkylated anilines, and naphthylamines) as well as azaarenes (such as alkylated pyridines, quinolines, acridine, and benzoquinolines). The oily-tar phase contained acridine, benzacridines, dibenzacridines, and numerous other azaarenes, the elemental compositions of which were determined by PD-HRMS. Azaarenes in the oily-tar phase, varying in size from 6 to 12 rings, are reported for the first time. The origin and environmental significance of these compounds are discussed.

Environmental Toxicology and Chemistry↗