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Atrazine and its metabolites as indicators of stream-aquifer interaction in Kansas, USA

A survey of atrazine and its metabolites in Kansas ground water indicated that ground-water quality was impacted by stream-aquifer interaction between rivers in the Kansas River basin and their adjacent alluvial aquifers. Atrazine was detected in 19 of the 78 samples. The most common metabolite, deethylatrazine, was detected in 25 samples, 18 of which also had atrazine. The deethylatrazine/atrazine ratio (DAR) of < 1.0 indicates rapid movement of agricultural chemicals to ground water. In this study, 12 of 18 samples had DAR values < 1.0, suggesting rapid recharge to the aquifers. Hydroxyatrazine is seldom detected in ground water. In this study hydroxyatrazine was detected primarily in wells sited in alluvium of rivers. These rivers contain atrazine in varying concentrations. Results of the study suggest that stream-aquifer interaction is a process contributing to the presence of both atrazine and its metabolites in ground water in these areas.A survey of atrazine and its metabolites in Kansas ground water indicated that ground water quality was impacted by stream-aquifer interaction between rivers in the Kansas River basin and their adjacent alluvial aquifers. Atrazine was detected in 19 of the 78 samples. The most common metabolite, deethylatrazine, was detected in 25 samples, 18 of which also had atrazine. The deethylatrazine/attrazine ratio (DAR) of < 1.0 indicates rapid movement of agricultural chemicals to ground water. In this study, 12 of 18 samples had DAR values < 1.0, suggesting rapid recharge to the aquifers. Hydroxyatrazine is seldom detected in ground water. In this study hydroxyatrazine was detected primarily in wells sited in alluvium of rivers. These rivers contain atrazine in varying concentration. Results of the study suggest that stream-aquifer interaction is a process contributing to the presence of both attrazine and its metabolites in ground water in these areas.

Kansas

Use of field-applied quality control samples to monitor performance of a Goulden large-sample extractor/GC-MS method for pesticides in water

Since 1985, the Goulden large-sample extractor (GLSE) has been used to isolate a broad array of trace-organic contaminants from large volumes of water. In this study, field-applied quality control measures, including matrix and surrogate spikes and blanks, were used to monitor method performance from GLSE extraction through GC-MS analysis. The method was applied to the determination of multiple classes of pesticides isolated from 4- to 112-L filtered surface-water samples. Average recoveries of six surrogate compounds ranged from 84 ?? 18% for [2H10]diazinon to 15 ?? 13% for 4,4'-[2H8]DDT, the low recoveries for which were largely a result of unmonitored breakdown of this surrogate by the GC injection system. Field-matrix-spike samples were prepared by fortifying 10-L, 35-L, and 110-L filtered surface-water samples with 68 pesticides to amended concentrations of 11- to 50-ng/L each. Recoveries ranged from not detected to greater than 100%. Variability in pesticide recoveries from triplicate 10-L water samples collected at one site averaged 5.7% relative standard deviation and did not exceed 19%.Since 1985, the Goulden large-sample extractor (GLSE) has been used to isolate a broad array of trace-organic contaminants from large volumes of water. In this study, field-applied quality control measures, including matrix and surrogate spikes and blanks, were used to monitor method performance from GLSE extraction through GC-MS analysis. The method was applied to the determination of multiple classes of pesticides isolated from 4- to 112-L filtered surface-water samples. Average recoveries of six surrogate compounds ranged from 84 ?? 18% for [2H10]diazinon to 15 ?? 13% for 4,4???-[2H8]DDT, the low recoveries for which were largely a result of unmonitored breakdown of this surrogate by the GC injection system. Field-matrix-spike samples were prepared by fortifying 10-L, 35-L, and 110-L filtered surface-water samples with 68 pesticides to amended concentrations of 11- to 50-ng/L each. Recoveries ranged from not detected to greater than 100%. Variability in pesticide recoveries from triplicate 10-L water samples collected at one site averaged 5.7% relative standard deviation and did not exceed 19%.

International Journal of Environmental Analytical

Regional water-quality analysis of 2,4-D and dicamba in river water using gas chromatography-isotope dilution mass spectrometry

Gas chromatography with isotope dilution mass spectrometry (GC-MS) and enzyme-linked immunosorbent assay (ELISA) were used in regional National Water Quality Assessment studies of the herbicides, 2,4-D and dicamba, in river water across the United States. The GC-MS method involved solid-phase extraction, derivatized with deuterated 2,4-D, and analysis by selected ion monitoring. The ELISA method was applied after preconcentration with solid-phase extraction. The ELISA method was unreliable because of interference from humic substances that were also isolated by solid-phase extraction. Therefore, GC-MS was used to analyzed 80 samples from river water from 14 basins. The frequency of detection of dicamba (28%) was higher than that for 2,4-D (16%). Concentrations were higher for dicamba than for 2,4-D, ranging from less than the detection limit (7lt; 0.05 μg/L) to 3.77μg/L, in spite of 5 times more annual use of 2,4-D as compared to dicamba. These results suggest that 2,4-D degrades more rapidly in the environment than dicamba.

International Journal of Environmental Analytical

Occurrence of antibiotics in water from 13 fish hatcheries, 2001-2003

A 2-year study of extensive and intensive fish hatcheries was conducted to assess the general temporal occurrence of antibiotics in aquaculture. Antibiotics were detected in 15% of the water samples collected during the 2001-2002 collection period and in 31% of the samples during the 2003 collection period. Antibiotics were detected more frequently in samples from the intensive hatcheries (17 and 39%) than in samples from the extensive hatcheries (14 and 4%) during the 2001-2002 and 2003 collection periods, respectively. The maximum ormetoprim, oxytetracycline, and sulphadimethoxine concentrations were higher in samples from the intensive hatcheries (12, 10, and 36 &micro;g L-1), respectively, than in samples from the extensive hatcheries (<0.05, 0.31, and 1.2 &micro;g L-1), respectively. Sulphadimethoxine persisted for a longer period of time (up to 48 days) than ormetoprim (up to 28 days) and oxytetracycline (less than 20 days).

International Journal of Environmental Analytical

Input, flux, and persistence of six select pesticides in San Francisco Bay

Temporal patterns of pesticide inputs to San Francisco Bay were identified and correlated with timing of application and transport mechanism. Fluxes were calculated from measured concentrations and estimated flow. Persistence of the pesticides under typical riverine or estuarine conditions were estimated from laboratory experiments. Simazine was detected most frequently and had the highest flux into the Bay, which could be explained by its continuous use and long half-life. In comparison, diazinon was detected at lower concentrations and had a lower flux which corresponded to its lower use and shorter half-life. The order-of-magnitude lower fluxes of carbofuran and methidathion corresponded to their lower use and expected hydrolysis. Molinate was detected at the highest concentration but its flux was lower than expected, considering its very high use and persistence in the laboratory experiments. Additional loss of molinate is likely to occur from volatilization and photodegradation on the rice fields. Although thiobencarb had the second highest use, it had the lowest flux of the six pesticides, which can be attributed to its loss via hydrolysis, photodegradation, volatilization, and sorption to sediments. Fluxes into San Francisco Bay were equal to or greater than those reported for other estuaries, except for the Gulf of Mexico.

California

Use of a watershed model to characterize the fate and transport of fluometuron, a soil-applied cotton herbicide, in surface water

The Soil and Water Assessment Tool (SWAT) was used to characterize the fate and transport of fluometuron (a herbicide used on cotton) in the Bogue Phalia Basin in northwestern Mississippi, USA. SWAT is a basin-scale watershed model, able to simulate hydrological, chemical, and sediment transport processes. After adjustments to a few parameters (specifically the SURLAG variable, the runoff curve number, Manning's N for overland flow, soil available water capacity, and the base-flow alpha factor) the SWAT model fit the observed streamflow well (the Coefficient of Efficiency and R2 were greater than 60). The results from comparing observed fluometuron concentrations with simulated concentrations were reasonable. The simulated concentrations (which were daily averages) followed the pattern of observed concentrations (instantaneous values) closely, but could be off in magnitude at times. Further calibration might have improved the fit, but given the uncertainties in the input data, it was not clear that any improvement would be due to a better understanding of the input variables. ?? 2007 Taylor & Francis.

International Journal of Environmental Analytical

Development and evaluation of a gas chromatographic method for the determination of triazine herbicides in natural water samples

A multi-residue method is described for the determination o triazine herbicides in natural water samples. The technique uses solvent extraction followed by gas chromatographic separation and detection employing nitrogen-selective devices. Seven compounds can be determined simultaneously at a nominal detection limit of 0.1 μg/L in a 1-litre sample. Three different natural water samples were used for error analysis via evaluation of recovery efficiencies and estimation of overall method precision. As an alternative to liquid-liquid partition (solvent extraction) for removal of compounds of interest from water, solid-phase extraction (SPE) techniques employing chromatographic grade silicas with chemically modified surfaces have been examined. SPE is found to provide rapid and efficient concentration with quantitative recovery of some triazine herbicides from natural water samples. Concentration factors of 500 to 1000 times are obtained readily by the SPE technique.

International Journal of Environmental Analytical

A laboratory and field evaluation of a portable immunoassay test for triazine herbicides in environmental water samples

The usefulness and sensitivity, of a portable immunoassay test for the semiquantitative field screening of water samples was evaluated by means of laboratory and field studies. Laboratory results indicated that the tests were useful for the determination of atrazine concentrations of 0.1 to 1.5 &mu;g/L. At a concentration of 1 &mu;g/L, the relative standard deviation in the difference between the regression line and the actual result was about 40 percent. The immunoassay was less sensitive and produced similar errors for other triazine herbicides. After standardization, the test results were relatively insensitive to ionic content and variations in pH (range, 4 to 10), mildly sensitive to temperature changes, and quite sensitive to the timing of the final incubation step, variances in timing can be a significant source of error. Almost all of the immunoassays predicted a higher atrazine concentration in water samples when compared to results of gas chromatography. If these tests are used as a semiquantitative screening tool, this tendency for overprediction does not diminish the tests' usefulness. Generally, the tests seem to be a valuable method for screening water samples for triazine herbicides.

International Journal of Environmental Analytical

The deethylatrazine/atrazine ratio as an indicator of the onset of the spring flush of herbicides into surface water of the Midwestern United States

The ratio of deethylatrazine to atrazine (DAR) may be used to record the first major runoff of herbicides from non-point-source corn fields to surface water in the Midwestern United States. The DAR dramatically decreases from ∼0.5 to < 0.1 upon application of herbicide and the first major runoff event of a basin. The DAR then gradually increases to values of approximately 0.4–0.6 during the harvest season. Furthermore, the DAR may be used in studies of surface water movement to give a temporal indicator of water moving into reservoirs for possible storage of herbicides. It is hypothesized that deethylatrazine, which accounts for only 6% of the degradation of atrazine, becomes a significant metabolite in surface water (∼ 50% of parent compound) because of its selective removal from soil. This removal process may be an important concept for consideration in studies of herbicide contamination of rivers and reservoirs.

International Journal of Environmental Analytical

Environmental presence and persistence of pharmaceuticals: An overview

Emerging contaminants (ECs) in the environment &ndash; that is, chemicals with domestic, municipal, industrial, or agricultural sources that are not commonly monitored but may have the potential for adverse environmental effects &ndash; is a rapidly growing field of research. The use of &ldquo;emerging&rdquo; is not intended to infer that the presence of these compounds in the environment is new. These chemicals have been released into the environment as long as they have been in production or, in the case of hormones and other endogenous compounds, since the rise of animal life. What is emerging is the interest by the scientific and lay communities in the presence of these chemicals in the environment, the analytical capabilities required for detection, and the subtle effects that very small concentrations of these chemicals appear to have on aquatic biota. In December 2006, Environmental Science & Technology devoted an entire special issue (volume 40, number 23) to the topic of ECs, illustrating the increased interest in the subject. Within the EGs, one particular class that has seen a substantial increase in research over the past 10 years is pharmaceuticals and personal-care products (PPCPs). This increased research interest can be demonstrated by several means, including requests for proposals from funding agencies, but the clearest indication of a focused effort to understand the introduction, transformation, and potential health and environmental effects of PPCPs and ECs, in general, is the number of published reports. This increase can be shown by examining six environmental journals that regularly publish PPCP-related papers &ndash; Chemosphere , Environmental Science & Technology , Environmental Toxicology and Chemistry , Science of the Total Environment , Water Research , and Water Science and Technology . In 1998 there were 22 papers published on pharmaceuticals, antibiotics, or drugs in these 6 journals; by 2006, this number increased sixfold to 132 papers (Figure 1.1). This growth can be attributed to a number of factors. The presence of pharmaceuticals in surface-water samples from Europe and the United States was documented in several sentinel papers. These ground-breaking works encouraged other scientists to examine the rivers, streams, lakes, and reservoirs in their regions for such chemicals. In addition, the intense public attention paid to news reports on the environmental detections of these chemicals and possible effects of aquatic life has made this issue visible to the wastewater-treatment, drinking-water treatment, and regulatory communities. This has driven the funding bodies associated with these communities to fund studies or request proposals that address the presence, fate, and effects of PPCPs in aquatic systems. The release of the first comprehensive reconnaissance of pharmaceuticals and other wastewater contaminants in the United States provides an example of the intense media interest in this topic. Within 6 days on online publication of this study, 72 newspapers across the United States had published articles describing the results, either locally written or based on international media syndicate reports. There also was substantial concurrent coverage by local and national radio and television outlets, including the Cable News Network, ABC World News Tonight , and National Public Radio. A substantial fraction of these news stories may be attributable to press releases and media briefings prior to publication. However, the interest by television and print journalists in reporting the results of a peer-reviewed journal article to the general public was motivated by the recognition that describing the presence of PPCPs in water supplies would be of interest to the public. To better convey the results of the study published by Koplin et al. to the public, a separate general-interest fact sheet was published to summarize the important points of the study. Because PPCPs are commonly and widely used by individuals, there is likely a preexisting, personal identification with these compounds that does not occur for the wide range of other organic and inorganic contaminants whose presence in the environment has previously been described. This greater public &ldquo;name recognition&rdquo; makes itself known through the media to the regulatory and technical community and has prompted interest in sponsoring research that defines the composition and concentrations of PPCPs in potential sources and their fate and effects following relase into the environment. Independent of the drivers that potentially fuel the interest in studies of PPCPs, it is clear that PPCP research has grown beyond surface-water studies to examine issues such as: &bull; Presence in other matrices, such as groundwater, landfill leachates, sediments, and biosolids. &bull; Environmental transport and fate in surface water, groundwater, and soils amended with reclaimed water or biosolids. &bull; PPCP source elucidation, such as wastewater treatment plant (WWTP) effluents, confined animal feeding operations (CAFOs), and aquaculture. &bull; Removal during wastewater and drinking-water treatment. &bull; Effects on aquatic ecosystems, terrestrial ecosystems, and human health. The chapters in this book provide an extensive examination of current environmental pharmaceutical research and are divided into three sections: &ldquo;Occurrence and Analysis of Pharmaceuticals in the Environment,&rdquo; &ldquo;Environment Fate and Transformations of Veterinary Pharmaceuticals,&rdquo; and &ldquo;treatment of Pharmaceuticals in Drinking Water and Wastewater.&rdquo; The purpose of this introductory overview chapter is to outline current (2004-2006) knowledge about the presence and concentration of PPCPs as described in the published literature. Previous reviews should be consulted for discussions on pre-2004 publications. Those reviews will provide the reader with a comprehensive introduction to the topic of PPCPs in the environment. This chapter describes the sources of PPCPs and other organic contaminants often associated with human wastewater into the environment, the range of concentrations present in various environmental compartments, and the potential routes of removal/sequestration. An overview of the sources and fate of veterinary pharmaceuticals will be discussed in Chapter 5, &ldquo;Fate and Transport of Veterinary Medicines in the Soil Environment.&rdquo;

Book chapter