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At least 19 recordsLinked to original sources
USGS2009

Herbicide metabolites in surface water and groundwater: Introduction and overview

Several future research topics for herbicide metabolites in surface and ground water are outlined in this chapter. They are herbicide usage, chemical analysis of metabolites, and fate and transport of metabolites in surface and ground water. These three ideas follow the themes in this book, which are the summary of a symposium of the American Chemical Society on herbicide metabolites in surface and ground water. First, geographic information systems allow the spatial distribution of herbicide-use data to be combined with geochemical information on fate and transport of herbicides. Next these two types of information are useful in predicting the kinds of metabolites present and their probable distribution in surface and ground water. Finally, methods development efforts may be focused on these specific target analytes. This chapter discusses these three concepts and provides an introduction to this book on the analysis, chemistry, and fate and transport of herbicide metabolites in surface and ground water.

ACS Symposium Series↗
USGS2009

A high-performance liquid chromatography-based screening method for the analysis of atrazine, alachlor, and ten of their transformation products

A high-performance liquid chromatography (HPLC) method is presented for the for the fast, quantitative analysis of the target analytes in water and in low organic-carbon, sandy soils that are known to be contaminated with the parent herbicides. Speed and ease of sample preparation was prioritized above minimizing detection limits. Soil samples were extracted using 80:20 methanol:water (volume:volume). Water samples (50 µL) were injected directly into the HPLC without prior preparation. Method quantification limits for soil samples (10 g dry weight) and water samples ranged from 20 to 110 ng/g and from 20 to 110 µg/L for atrazine and its transformation products and from 80 to 320 ng/g and from 80 to 320 µg/L for alachlor and its transformation products, respectively.

ACS Symposium Series↗
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

Relation of landscape position and irrigation to concentrations of alachlor, atrazine, and selected degradates in regolith in northeastern Nebraska

Concentrations of alachlor, its ethanesulfonic acid degradate, atrazine and its degradates, deethylatrazine and deisopropylatrazine, in the upper regolith and associated shallow aquifers were determined in relation to landscape position (floodplains, terraces, and uplands) and irrigation (nonirrigated and irrigated corn cropland) in 1992. Irrigated and nonirrigated sites were located on each landscape position. Samples were collected from three depths. Canonical discriminant and multivariate analyses were used to interpret data. Herbicides and their degradation products tended to be present in soils with high percent organic matter, low pH, and low sand content. Atrazine was present more frequently on the floodplain at all depths than the other compounds. Atrazine (maximum 17.5 µg/kg) and ethanesulfonic acid (maximum 10 µg/kg) were associated with landscape position, but not with irrigation. Alachlor (maximum 24 µg/kg), deethylatrazine (maximum 1.5 µg/kg), and deisopropylatrazine (maximum 3.5 µg/kg) were not significantly associated with either landscape position or irrigation. Ground-water analytical results suggested that concentrations of these herbicides and degradates in ground water did not differ among landscape position or between irrigated and nonirrigated corn cropland.

ACS Symposium Series↗
USGS2009

Cyanazine, atrazine, and their metabolites as geochemical indicators of contaminant transport in the Mississippi River

The geochemical transport of cyanazine and its metabolite cyanazine amide (CAM) was compared to atrazine and its metabolite deethylatrazine (DEA) at three sites in the Mississippi River basin during 1992 and six sites during 1993. The floods of 1993 caused an uninterrupted exponential decline in herbicide concentrations; whereas, in 1992 herbicide concentrations varied mostly in response to two discrete discharge pulses in the spring and midsummer and were stable during an extended period of summer low-flow. Concentration half-lives calculated from the 1993 data for atrazine were approximately twice those of cyanazine at all sites. The half-life for atrazine and cyanazine was shortest, 22 and 14 days, respectively at the Mississippi River at Clinton, Ill. -- the farthest upstream site -- and longest, 42 and 22 days, respectively, at the Baton Rouge, La. site -- the farthest downstream site. The concentration of CAM exceeded the concentration of DEA through September at all sites where the mean ratio of atrazine-to-cyanazine (ACR) was less than 4.0. The ratio of CAM-to-cyanazine (CAMCR) increased from 0.2 to more than 1.0 and the ratio of DEA-to-atrazine (DAR) increased from less than 0.1 to 0.3 from application in May through early to mid- July. Temporal changes in the CAMCR were used to identify pre- and post-application "slugs" of water transported along the reaches of the Mississippi River.

Arkansas, Illinois, Kentucky, Louisiana, Mississip↗
USGS2010

A first application of enzyme-linked immunosorbent assay for screening cyclodiene insecticides in ground water

A commercially available enzyme-linked immunosorbent assay (ELISA) plate kit for screening of cyclodiene insecticides (aldrin, chlordane, dieldrin, endosulfan, endrin, and heptachlor) was evaluated for sensitivity, cross reactivity, and overall performance using ground-water samples from a contaminated site. Ground-water contaminants included several pesticide compounds and their manufacturing by-products, as well as many other organic and inorganic compounds. Cross-reactivity studies were carried out for the cyclodiene compounds, and results were compared to those listed by the manufacturer. Data obtained were used to evaluate the sensitivity of the ELISA kit to the cyclodiene compounds in ground water samples with a contaminated matrix. The method quantitation limit for the ELISA kit was 15 μg/L (as chlordane). Of the 56 ground-water samples analyzed using the ELISA plate kits, more than 85% showed cyclodiene insecticide contamination. The ELISA kit showed excellent potential as a screening tool for sites with suspected ground-water contamination by insecticides.

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

Environmental immunoassays: Alternative techniques for soil and water analysis

Analysis of soil and water samples for environmental studies and compliance testing can be formidable, time consuming, and costly. As a consequence, immunochemical techniques have become popular for environmental analysis because they are reliable, rapid, and cost effective. During the past 5 years, the use of immunoassays for environmental monitoring has increased substantially, and their use as an integral analytical tool in many environmental laboratories is now commonplace. This chapter will present the basic concept of immunoassays, recent advances in the development of immunochemical methods, and examples of successful applications of immunoassays in environmental analysis.

ACS Symposium Series↗
USGS2009

Evaluation of immunoassay for the determination of pesticides at a large-scale groundwater contamination site

Pesticide concentrations in ground water at Rocky Mountain Arsenal (RMA) near Denver, Colorado, were determined using solid-phase extraction (SPE) gas chromatography/mass spectrometry (GC/MS) procedures and enzyme-linked immunosorbent assay (ELISA) for cyclodiene insecticides and triazine herbicides. Matrix interferences resulted in inconclusive results for some GC/MS analyses due to baseline disturbances and co-elution, but ELISA analyses consistently gave definitive results in a minimum amount of time. ELISA was used initially as a screening method, and pesticide concentrations and plume extents identified by ELISA were confirmed by SPE-GC/MS. A high degree of correlation was seen between results from GC/MS and ELISA methods for the triazine herbicides (correlation coefficient (R 2 ) = 0.99). All areas with high pesticide concentrations were found to be within the boundaries of RMA.

Colorado↗
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

Transport and degradation of semivolatile hydrocarbons in a petroleum-contaminated aquifer, Bemidji, Minnesota

Polycyclic aromatic hydrocarbons (PAH) were used as probes to identify the processes controlling the transport and fate of aqueous semivolatile hydrocarbons (SVHCs) in a petroleum-contaminated aquifer near Bemidji, Minnesota. PAH and other SVHCs were isolated from ground water by field solid-phase extraction and analyzed using gas chromatography/mass spectrometry. Close to the oil body, aqueous aliphatic hydrocarbon compositions are substantially different from the parent oil, suggesting microbial alteration prior to or during dissolution. Aqueous PAH concentrations are elevated above oil-water equilibrium concentrations directly beneath the oil and decrease dramatically at distances ranging from the 25 to 65 m downgradient from the leading edge of the oil body. Variations in downgradient distributions of naphthalene, fluorene and phenanthrene, coupled with their biodegradation, partitioning and volatility characteristics, suggest that the PAH are useful probes for distinguishing between the biogeochemical processes affecting SVHC transport and persistence in ground water.

Minnesota↗
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

The reduction of aqueous metal species on the surfaces of Fe(II)-containing oxides: The role of surface passivation

The reduction of aqueous transition metal species at the surfaces of Fe(II)- containing oxides has important ramifications in predicting the transport behavior in ground water aquifers. Experimental studies using mineral suspensions and electrodes demonstrate that structural Fe(II) heterogeneously reduces aqueous ferric, cupric, vanadate and chromate ions on magnetite and ilmenite surfaces. The rates of metal reduction on natural oxides is strongly dependent on the extent of surface passivation and redox conditions in the weathering environment. Synchrotron studies show that surface oxidation of Fe(II)-containing oxide minerals decreases their capacity for Cr(VI) reduction at hazardous waste disposal sites.

ACS Symposium Series↗