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10 recordsLinked to original sources
USGS2009

Estimation of the potential for atrazine transport in a silt loam soil

The transport potential of the herbicide atrazine (2-chloro-4-ethyl-6-isopropyl- s -triazine) through a 1-meter-thick root zone of corn ( Zea mays L.) in a silty-loam soil in Kansas was estimated for a 22-year period (1972-93) using the one-dimensional water-flow and solute-transport model LEACHM. Results demonstrate that, for this soil, atrazine transport is directly related to the amount and timing of rain that follows spring applications of atrazine. Two other critical transport factors were important in wet years — [1] variability in atrazine application rate, and [2] atrazine degradation rates below the root zone. Results demonstrate that the coincidence of heavy rain soon after atrazine application can cause herbicide to move below the rooting zone into depths at which biodegradation rates are assumed to be low but are often unknown. Atrazine that reaches below the rooting zone and persists in the underlying soil can subsequently be transported into ground water as soil water drains, typically after the growing season. A frequency analysis of atrazine concentrations in subsurface drainage, combined with field data, demonstrates the relative importance of critical transport factors and confirms a need for definitive estimates of atrazine-degradation rates below the root zone. The analysis indicates that periodic leaching of atrazine can be expected for this soil when rainfall that exceeds 20 cm/mo coincides with atrazine presence in soil.

ACS Symposium Series↗
USGS2009

Organic geochemistry and sources of natural aquatic foams

Aquatic foams and stream-water samples were collected from two pristine sites for humic substances isolation and characterization. Biomarker compounds identified in foam and stream humic substances included phospholipid fatty acids, steroids, and lignin. Results showed that foams had a 10 to 20 fold greater DOC concentration and were enriched in humic substances (90% by weight of DOC) that showed increased hydrophobicity, aliphatic character, and compositional complexity compared to host stream humic substances (55 to 81% by weight of DOC). Foam humic substances also were enriched in humic acid (36 to 83% by weight) compared to host stream humic substances (10 to 14% by weight). Biomarkers, which contributed less than 5% by weight to the DOC pool, indicated higher plants, bacteria, algae, fungi, and diatoms as DOC sources. It is proposed that aquatic foams may be important media for the concentration and transport of organic substances in the aquatic environment.

ACS Symposium Series↗
USGS2009

Error evaluation of methyl bromide aerodynamic flux measurements

Methyl bromide volatilization fluxes were calculated for a tarped and a nontarped field using 2 and 4 hour sampling periods. These field measurements were averaged in 8, 12, and 24 hour increments to simulate longer sampling periods. The daily flux profiles were progressively smoothed and the cumulative volatility losses increased by 20 to 30% with each longer sampling period. Error associated with the original flux measurements was determined from linear regressions of measured wind speed and air concentration as a function of height, and averaged approximately 50%. The high errors resulted from long application times, which resulted in a nonuniform source strength; and variable tarp permeability, which is influenced by temperature, moisture, and thickness. The increase in cumulative volatilization losses that resulted from longer sampling periods were within the experimental error of the flux determination method.

ACS Symposium Series↗
USGS2009

Anthropogenic molecular markers: Tools to identify the sources and transport pathways of pollutants

The activities of modern civilization have released to the oceans a wide variety of both mobilized natural compounds and synthetic compounds not found prior to modern times. Many of these compounds provide a means of identifying sources of inputs and pathways of movement of chemicals through oceanic ecosystems and serve as molecular markers of human activities. A coastal ocean (Tokyo Bay) and a deep ocean (Deep Water Dump Site 106 in the Western North Atlantic Ocean) example are presented. In the deep ocean study, the correlation between potential sewage marker, i.e. linear alkylbenzenes (LABs), and polychlorinated biphenyls (PCBs) concentrations indicates a contribution of sewage sludge PCBs to the dump site sediments.

ACS Symposium Series↗
USGS2009

Polychlorinated biphenyls as probes of biogeochemical processes in rivers

A field study was conducted to investigate the use of PCB (polychlorinated biphenyl) congener and homolog assemblages as tracers of biogeochemical processes in the Milwaukee and Manitowoc Rivers in southeastern Wisconsin from 1993 to 1995. PCB congeners in the dissolved and suspended particle phases, along with various algal indicators (algal carbon and pigments), were quantitated in the water seasonally. In addition, PCB congener assemblages were determined seasonally in surficial bed sediments. Biogeochemical processes investigated included: determination of the source of suspended particles and bottom sediments by comparison with known Aroclor mixtures, water-solid partitioning, and algal uptake of PCBs. Seasonal differences among the PCB assemblages were observed mainly in the dissolved phase, somewhat less in the suspended particulate phase, and not at all in the bed sediments.

Wisconsin↗
USGS2009

Source and transport of desethylatrazine and desisopropylatrazine to groundwater of the midwestern United States

Based on usage of the parent compounds and studies of their dissipation in corn fields, atrazine (6-chloro-N-ethyl-N'-(1-methylethyl-1,3,5-triazine-2,4-diamine)), cyanazine (2-[[4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl]amino]-2-methylpropionitrile), and simazine (6-chloro-N,N'diethyl-1,3,5-triazine-2,4-diamine) are thought to be the important contributors of desethylatrazine (6-chloro-N-(1-methylethyl)-1,3,5-triazine-2,4-diamine) or DEA and desisopropylatrazine(6-chloro-N-ethyl)-1,3,5-triazine-2,4-diamine) or DIA to ground water. Atrazine degrades to both DEA and DIA by dealkylation. DEA is transported through the unsaturated zone more readily than DIA because of the more rapid degradation of DIA in the shallow unsaturated zone. Both cyanazine and simazine degrade to DIA by dealkylation, and DIA may be an indicator of leaching and subsequent degradation from both parent compounds. Because cyanazine has an acid intermediate that is mobile in the unsaturated zone, it may be an important source for DIA transport to ground water. Based on a regional survey of ground water of the Midwest during the Spring and Summer of 1991, DEA occurs most frequently with detections of DEA (15.4%) > atrazine (14.7%) > DIA (4%) > simazine (0.7%) > cyanazine (0.3%) > propazine (no detections). The DEA to atrazine ratio (DAR) is an indicator of atrazine source and transport, with the lowest ratios indicating most rapid transport.

ACS Symposium Series↗
USGS2009

Chitin: 'Forgotten' source of nitrogen: From modern chitin to thermally mature kerogen: Lessons from nitrogen isotope ratios

Chitinous biomass represents a major pool of organic nitrogen in living biota and is likely to have contributed some of the fossil organic nitrogen in kerogen. We review the nitrogen isotope biogeochemistry of chitin and present preliminary results suggesting interaction between kerogen and ammonium during thermal maturation. Modern arthropod chitin may shift its nitrogen isotope ratio by a few per mil depending on the chemical method of chitin preparation, mostly because N-containing non-amino-sugar components in chemically complex chitin cannot be removed quantitatively. Acid hydrolysis of chemically complex chitin and subsequent ion-chromatographic purification of the "deacetylated chitin-monomer" D-glucosamine (in hydrochloride form) provides a chemically well-defined, pure amino-sugar substrate for reproducible, high-precision determination of δ 15 N values in chitin. δ 15 N values of chitin exhibited a variability of about one per mil within an individual's exoskeleton. The nitrogen isotope ratio differed between old and new exoskeletons by up to 4 per mil. A strong dietary influence on the δ 15 N value of chitin is indicated by the observation of increasing δ 15 N values of chitin from marine crustaceans with increasing trophic level. Partial biodegradation of exoskeletons does not significantly influence δ 15 N values of remaining, chemically preserved amino sugar in chitin. Diagenesis and increasing thermal maturity of sedimentary organic matter, including chitin-derived nitrogen-rich moieties, result in humic compounds much different from chitin and may significantly change bulk δ 15 N values. Hydrous pyrolysis of immature source rocks at 330°C in contact with 15 N-enriched NH 4 Cl, under conditions of artificial oil generation, demonstrates the abiogenic incorporation of inorganic nitrogen into carbon-bound nitrogen in kerogen. Not all organic nitrogen in natural, thermally mature kerogen is therefore necessarily derived from original organic matter, but may partly result from reaction with ammonium-containing pore waters.

ACS Symposium Series↗
USGS2009

Methyl tert-butyl ether in ground and surface water of the United States: National-scale relations between MTBE occurrence in surface and ground water and MTBE use in gasoline

The detection frequency of methyl tert -butyl ether (MTBE) in ground and surface water of the United States is positively related to the content of MTBE in gasoline in various metropolitan areas of the U.S. The frequency of detection of MTBE is generally higher in areas that use larger amounts of MTBE in gasoline. Sampling of surface and ground water by the U.S. Geological Survey's National Water-Quality Assessment (NAWQA) Program between 1993 and 1998 revealed a frequent detection of low concentrations of MTBE. In this analysis, data from several national-scale gasoline surveys are examined and data from one survey that is most extensive in geographic and temporal coverage is used to relate the detection of MTBE in ground and surface water to the volumetric content of MTBE in gasoline.

ACS Symposium Series↗
USGS2011

Redox chemistry and natural organic matter (NOM): Geochemists' dream, analytical chemists' nightmare

Natural organic matter (NOM) is an inherently complex mixture of polyfunctional organic molecules. Because of their universality and chemical reversibility, oxidation/reductions (redox) reactions of NOM have an especially interesting and important role in geochemistry. Variabilities in NOM composition and chemistry make studies of its redox chemistry particularly challenging, and details of NOM-mediated redox reactions are only partially understood. This is in large part due to the analytical difficulties associated with NOM characterization and the wide range of reagents and experimental systems used to study NOM redox reactions. This chapter provides a summary of the ongoing efforts to provide a coherent comprehension of aqueous redox chemistry involving NOM and of techniques for chemical characterization of NOM. It also describes some attempts to confirm the roles of different structural moieties in redox reactions. In addition, we discuss some of the operational parameters used to describe NOM redox capacities and redox states, and describe nomenclature of NOM redox chemistry. Several relatively facile experimental methods applicable to predictions of the NOM redox activity and redox states of NOM samples are discussed, with special attention to the proposed use of fluorescence spectroscopy to predict relevant redox characteristics of NOM samples.

ACS Symposium Series↗