Lisa Zimmerman | SUNY: University at Buffalo (original) (raw)

Papers by Lisa Zimmerman

Research paper thumbnail of Analytical performance of a triple quadrupole mass spectrometer compared to a high resolution mass spectrometer for the analysis of polybrominated diphenyl ethers in fish

Analytica Chimica Acta, 2012

h i g h l i g h t s A GC-QQQ-MS/MS method was developed for the analysis of PBDE congeners in fis... more h i g h l i g h t s A GC-QQQ-MS/MS method was developed for the analysis of PBDE congeners in fish. This method was directly compared with a GC-HR-MS analysis of the same samples. Limits of detection were found to be comparable between the two instruments. GC-QQQ-MS/MS results were not statistically different from the GC-HR-MS results. Findings support the suitability of GC-QQQ-MS/MS for analysis of PBDEs in fish.

Research paper thumbnail of Occurrence of Cotton Pesticides in Surface Water of the Mississippi Embayment

Fact Sheet

This fact sheet introduces a study of the nonpoint-source occurrence of pesticides in water of th... more This fact sheet introduces a study of the nonpoint-source occurrence of pesticides in water of the cotton-growing areas of the Southern United States with special emphasis on the Mississippi Embayment (fig. 1). This study is being conducted by the U.S. Geological Survey (USGS) Organic Geochemistry Research Group, which investigates the fate and transport of agricultural chemicals in the environment. The purpose of this fact sheet is to give an overview of the cottongrowing areas of the United States, to provide usage data for cotton pesticides in the United States, to present information on the types of pesticide compounds and concentrations that have been found thus far in the Mississippi Embayment, and to discuss current areas of cotton pesticide research.

Research paper thumbnail of Method of Analysis and Quality-Assurance Practices by the U.S. Geological Survey Organic Geochemistry Research Group-Determination of Four Selected Mosquito Insecticides and a Synergist in Water Using Liquid-Liquid Extraction and Gas Chromatography/Mass Spectrometry

A method of analysis and quality-assurance practices were developed for the determination of four... more A method of analysis and quality-assurance practices were developed for the determination of four mosquito insecticides (malathion, methoprene, phenothrin, and resmethrin) and one synergist (piperonyl butoxide) in water. The analytical method uses liquid-liquid extraction (LLE) and gas chromatography/mass spectrometry (GC/MS). Good precision and accuracy were demonstrated in reagent water, urban surface water, and ground water. The mean accuracies as percentages of the true compound concentrations from water samples spiked at 10 and 50 nanograms per liter ranged from 68 to 171 percent, with standard deviations in concentrations of 27 nanograms per liter or less. The method detection limit for all compounds was 5.9 nanograms per liter or less for 247-milliliter samples. This method is valuable for acquiring information about the fate and transport of these mosquito insecticides and one synergist in water.

Research paper thumbnail of Heterogeneous carbonaceous matter in sedimentary rock lithocomponents causes significant trichloroethylene (TCE) sorption in a low organic carbon content aquifer/aquitard system

Journal of Contaminant Hydrology, 2014

This study evaluated the effects of heterogeneous thermally altered carbonaceous matter (CM) on t... more This study evaluated the effects of heterogeneous thermally altered carbonaceous matter (CM) on trichloroethylene (TCE) sorption for a low fraction organic carbon content (foc) alluvial sedimentary aquifer and aquitard system (foc=0.046-0.105%). The equilibrium TCE sorption isotherms were highly nonlinear with Freundlich exponents of 0.46-0.58. Kerogen+black carbon was the dominant CM fraction extracted from the sediments and accounted for >60% and 99% of the total in the sands and silt, respectively. Organic petrological examination determined that the kerogen included abundant amorphous organic matter (bituminite), likely of marine origin. The dark calcareous siltstone exhibited the greatest TCE sorption among aquifer lithocomponents and accounted for most sorption in the aquifer. The results suggest that the source of the thermally altered CM, which causes nonlinear sorption, was derived from parent Paleozoic marine carbonate rocks that outcrop throughout much of New York State. A synthetic aquifer-aquitard unit system (10% aquitard) was used to illustrate the effect of the observed nonlinear sorption on mass storage potential at equilibrium. The calculation showed that >80% of TCE mass contained in the aquifer was sorbed on the aquifer sediment at aqueous concentration <1000 μgL(-1). These results show that sorption is likely a significant contributor to the persistence of a TCE groundwater plume in the aquifer studied. It is implied that sorption may similarly contribute to TCE persistence in other glacial alluvial aquifers with similar geologic characteristics, i.e., comprised of sedimentary rock lithocomponents that contain thermally altered CM.

Research paper thumbnail of Detection of persistent organic pollutants in the Mississippi Delta using semipermeable membrane devices

Science of The Total Environment, 2000

From semipermeable membrane devices (SPMDs) placed in five Mississippi Delta streams in 1996 and ... more From semipermeable membrane devices (SPMDs) placed in five Mississippi Delta streams in 1996 and 1997, the persistent organic pollutants (POPs) aldrin, chlordane, DCPA, DDT, dieldrin, endrin, heptachlor, mirex, nonachlor, and toxaphene were detected. In addition, the insecticides chlorpyriphos, endosulfan, and hexachlorocyclohexanes were detected. Two low-solubility herbicides not detected commonly in surface water, pendimethalin and trifluralin, were also detected.

Research paper thumbnail of Analysis of selected herbicide metabolites in surface and ground water of the United States

Science of The Total Environment, 2000

Ž. One of the primary goals of the US Geological Survey USGS Laboratory in Lawrence, Kansas, is t... more Ž. One of the primary goals of the US Geological Survey USGS Laboratory in Lawrence, Kansas, is to develop analytical methods for the analysis of herbicide metabolites in surface and ground water that are vital to the study of herbicide fate and degradation pathways in the environment. Methods to measure metabolite concentrations from three major classes of herbicides ᎏ triazine, chloroacetanilide and phenyl-urea ᎏ have been developed. Methods for triazine metabolite detection cover nine compounds: six compounds are detected by gas chromatographyrmass spectrometry; one is detected by high-performance liquid chromatography with diode-array detection; and eight are detected by liquid chromatographyrmass spectrometry. Two metabolites of the chloroacetanilide herbicides ᎏ ethane sulfonic acid and oxanilic acid ᎏ are detected by high-performance liquid chromatography with diode-array detection and liquid chromatographyrmass spectrometry. Alachlor ethane sulfonic acid also has been detected by solid-phase extraction and enzyme-linked immunosorbent assay. Six phenylurea metabolites are all detected by liquid chromatographyrmass spectrometry; four of the six metabolites also are detected by gas chromatographyrmass spectrometry. Additionally, surveys of herbicides and their metabolites in surface water, ground water, lakes, reservoirs, and rainfall have been conducted through the USGS laboratory in Lawrence. These surveys have been useful in determining herbicide and metabolite occurrence and temporal distribution and have shown that metabolites may be useful in evaluation of non-point-source contamination.

Research paper thumbnail of Statewide Survey of Hormones and Antibiotics in Surface Waters of Delaware

JAWRA Journal of the American Water Resources Association, 2013

ABSTRACT Water-quality surveys have confirmed the presence of hormones and antibiotics in surface... more ABSTRACT Water-quality surveys have confirmed the presence of hormones and antibiotics in surface waters of the United States, which may be of concern to aquatic life. We investigated the concentrations of hormones and antibiotics in surface waters of the state of Delaware to determine – how they compared against environmental thresholds, how they varied across the state, and if they were correlated with land use type. Fifty surface water locations were sampled during early spring and late summer. Water samples were initially screened with ELISA followed by analysis with LC/MS/MS. The measured ranges of hormone concentrations were: 0-3.71 ng/l for estrone, 0-4.65 ng/l for estrone-3-sulfate, and 0-6.27 ng/l for 17β-estradiol. The measured ranges of antibiotics were: 0-3.30 ng/l for sulfamerazine, 0-10.74 ng/l for sulfamethoxazole, and 0-2.29 ng/l for tetracycline. The predicted no-effect concentration (PNEC) for estrone was exceeded for three samples and the PNEC for 17β-estradiol was exceeded for 11 samples. In general, concentrations and detection frequencies were lower in the summer than the spring. The highest concentrations of hormones and antibiotics were spatially distributed in agricultural and urban areas; however, the correlations between land use type and the concentrations were weak. This study was the first statewide survey of hormones and antibiotics for Delaware and provided important baseline data on these emerging contaminants.

Research paper thumbnail of Analysis and Detection of the Herbicides Dimethenamid and Flufenacet and Their Sulfonic and Oxanilic Acid Degradates in Natural Water

Journal of Agricultural and Food Chemistry, 2002

Dimethenamid [2-chloro-N-(2,4-dimethyl-3-thienyl)-N-(2-methoxy-1-methylethyl)acetamide] and flufe... more Dimethenamid [2-chloro-N-(2,4-dimethyl-3-thienyl)-N-(2-methoxy-1-methylethyl)acetamide] and flufenacet [N-(4-fluorophenyl)-N-(1-methylethyl)-2-(5-(trifluoromethyl)-1,3,4-thiadiazol-2-yl)oxy] were isolated by C-18 solid-phase extraction and separated from their ethanesulfonic acid (ESA) and oxanilic acid (OXA) degradates during their elution using ethyl acetate for the parent compound, followed by methanol for the polar degradates. The parent compounds were detected using gas chromatographymass spectrometry in selected-ion mode. The ESA and OXA degradates were detected using highperformance liquid chromatography-electrospray mass spectrometry (HPLC-ESPMS) in negativeion mode. The method detection limits for a 123-mL sample ranged from 0.01 to 0.07 µg/L. These methods are compatible with existing methods and thus allow for analysis of 17 commonly used herbicides and 18 of their degradation compounds with one extraction. In a study of herbicide transport near the mouth of the Mississippi River during 1999 and 2000, dimethenamid and its ESA and OXA degradates were detected in surface water samples during the annual spring flushes. For flufenacet, the only detections at the study site were for the ESA degradates in samples collected at the peak of the herbicide spring flush in 2000. The low frequency of detections in surface water likely is due to dimethenamid and flufenacet being relatively new herbicides. In addition, detectable amounts of the stable degradates have not been detected in ground water.

Research paper thumbnail of Regional Water-Quality Analysis of 2,4-D and Dicamba in River Water Using Gas Chromatography-Isotope Dilution Mass Spectrometry

International Journal of Environmental Analytical Chemistry, 2001

... Because SPE-ELISA did not provide reliable results for the analysis of low con-centrations of... more ... Because SPE-ELISA did not provide reliable results for the analysis of low con-centrations of 2,4-D in surface-water samples ... References [I] LP Gianessi and JE Anderson, Pesticide Use in US Crop Production: National Data Report, National Center for Food and Agricultural ...

Research paper thumbnail of Identification of a New Sulfonic Acid Metabolite of Metolachlor in Soil

Environmental Science & Technology, 1996

... 9) Aga, DS; Thurman, EM; Pomes, ML Anal. Chem.1994, 66, 1495−1499. ... Oxanilic Acid Degradat... more ... 9) Aga, DS; Thurman, EM; Pomes, ML Anal. Chem.1994, 66, 1495−1499. ... Oxanilic Acid Degradates. Sung-Ben Huang, Thomas J. Mayer and Robert A. Yokley. Journal of Agricultural and Food Chemistry 2008 56 (8), 2595-2602. ...

Research paper thumbnail of Relation of Usage to the Occurrence of Cotton and Rice Herbicides in Three Streams of the Mississippi Delta

Environmental Science & Technology, 1998

... 3) Goolsby, DA; Thurman, EM; Pomes, ML; Meyer, M.; Battaglin, WA US Geological Survey Open-Fi... more ... 3) Goolsby, DA; Thurman, EM; Pomes, ML; Meyer, M.; Battaglin, WA US Geological Survey Open-File Report 93-418; 1993; pp 75−89. (4) US EPA. ... 14) Wiese, AF; Savage, KE; Chandler, JM; Liu, LC; Jeffery, LS; Weber, JB; LaFleur, KS J. Environ. Qual. ...

Research paper thumbnail of Formation and Transport of Deethylatrazine and Deisopropylatrazine in Surface Water

Environmental Science & Technology, 1994

Formation and Transport of Deethylatrazine and Deisopropylatrazine in ... E. M. Thurman,' MT... more Formation and Transport of Deethylatrazine and Deisopropylatrazine in ... E. M. Thurman,' MT Meyer, MS Mllls, L, R. Zlmmerman, and CA Perry US. Geological Survey, 4821 Quail Crest Place, Lawrence, Kansas 66049 ... Donald A. Goolsby US. Geological Survey, Denver ...

Research paper thumbnail of Assessing antibiotic sorption in soil: a literature review and new case studies on sulfonamides and macrolides

Chemistry Central Journal, 2014

The increased use of veterinary antibiotics in modern agriculture for therapeutic uses and growth... more The increased use of veterinary antibiotics in modern agriculture for therapeutic uses and growth promotion has raised concern regarding the environmental impacts of antibiotic residues in soil and water. The mobility and transport of antibiotics in the environment depends on their sorption behavior, which is typically predicted by extrapolating from an experimentally determined soil-water distribution coefficient (Kd). Accurate determination of Kd values is important in order to better predict the environmental fate of antibiotics. In this paper, we examine different analytical approaches in assessing Kd of two major classes of veterinary antibiotics (sulfonamides and macrolides) and compare the existing literature data with experimental data obtained in our laboratory. While environmental parameters such as soil pH and organic matter content are the most significant factors that affect the sorption of antibiotics in soil, it is important to consider the concentrations used, the an...

Research paper thumbnail of Linker-Assisted Immunoassay and Liquid Chromatography/Mass Spectrometry for the Analysis of Glyphosate

Analytical Chemistry, 2002

A novel, sensitive, linker-assisted enzyme-linked immunosorbent assay (L'ELISA) was compa... more A novel, sensitive, linker-assisted enzyme-linked immunosorbent assay (L'ELISA) was compared to on-line solid-phase extraction (SPE) with high-performance liquid chromatography/mass spectrometry (HPLC/MS) for the analysis of glyphosate in surface water and groundwater samples. The L'ELISA used succinic anhydride to derivatize glyphosate, which mimics the epitotic attachment of glyphosate to horseradish peroxidase hapten. Thus, L'ELISA recognized the derivatized glyphosate more effectively (detection limit of 0.1 microg/L) and with increased sensitivity (10-100 times) over conventional ELISA and showed the potential for other applications. The precision and accuracy of L'ELISA then was compared with on-line SPE/HPLC/MS, which detected glyphosate and its degradate derivatized with 9-fluorenylmethyl chloroformate using negative-ion electrospray (detection limit 0.1 microg/ L, relative standard deviation +/- 15%). Derivatization efficiency and matrix effects were minimized by adding an isotope-labeled glyphosate (2-13C15N). The accuracy of L'EUSA gave a false positive rate of 18% between 0.1 and 1.0 microg/L and a false positive rate of only 1% above 1.0 microg/L The relative standard deviation was +/- 20%. The correlation of L'ELISA and HPLC/MS for 66 surface water and groundwater samples was 0.97 with a slope of 1.28, with many detections of glyphosate and its degradate in surface water but not in groundwater.

Research paper thumbnail of Spatial pattern of hormone and antibiotic concentrations in surface waters in Delaware

ABSTRACT Water quality surveys of the U.S. have confirmed the presence of hormones and antibiotic... more ABSTRACT Water quality surveys of the U.S. have confirmed the presence of hormones and antibiotics in some surface waters. Although the reported concentrations of these substances are extremely low, there is substantial concern about their effect on aquatic species. For example, chronic exposure to estradiol (E2β) concentrations as low as 40 ng/L have been shown to cause endocrine disruption in fish. Furthermore, there is potential for contaminants to enter our drinking supply. Significant sources of hormones and antibiotics include discharge from concentrated animal feeding operations (CAFOs) and wastewater treatment plants as well as runoff from agricultural land receiving application of animal manure. Since Sussex County, Delaware is one of the leading poultry producing counties in the nation, and many farmers in the state use poultry litter as fertilizer for their crops, it is critical to study the concentrations of contaminants in surface waters. Fifty surface water (streams, lakes, and ponds) sampling locations throughout the state of Delaware were chosen based on DNREC (Delaware Department of Natural Resources and Environmental Control) data. Locations with the highest nitrogen and phosphorus levels were assumed to be associated with agriculture and wastewater sources and therefore were likely to be contaminated with hormones and antibiotics. The first set of sampling occurred in April representing high-flow conditions, and the second set will occur in September representing low-flow conditions. Water samples will be screened through the cost-effective enzyme-linked immunosorbent assay (ELISA) method followed by more rigorous analyses of selected samples using liquid chromatography-mass spectrometry (LC/MS/MS). ELISA screening includes estradiol (E2β), sulfamethazine and triclosan, while LC/MS/MS will quantify both free and conjugated forms of estrone (E1), estradiol (E2β), estriol (E3), as well as selected sulfa and tetracycline antibiotics. Initial ELISA results indicate a range of 0-40 ng/L for E2β, 0-18 μg/L for sulfamethazine, and 0-3 μg/L for triclosan; however, previous studies have shown that the ELISA method tends to overestimate due to cross-reactivity and matrix effects, and therefore we expect lower concentrations from LC/MS/MS. All LC/MS/MS results are expected by December 2011. Results will be compared to the predicted no-effect concentrations to determine whether these contaminants pose a threat to aquatic species and wildlife. ArcGIS was used to plot the measured concentrations on the Delaware state map to provide a spatial representation of the potential contamination. Watersheds were delineated for each of the sampling locations, and land use, physical characteristics of the land, and potential sources of contaminants within the watersheds have been analyzed to explore any relationships with measured contaminant concentrations.

Research paper thumbnail of Analytical performance of a triple quadrupole mass spectrometer compared to a high resolution mass spectrometer for the analysis of polybrominated diphenyl ethers in fish

Analytica Chimica Acta, 2012

h i g h l i g h t s A GC-QQQ-MS/MS method was developed for the analysis of PBDE congeners in fis... more h i g h l i g h t s A GC-QQQ-MS/MS method was developed for the analysis of PBDE congeners in fish. This method was directly compared with a GC-HR-MS analysis of the same samples. Limits of detection were found to be comparable between the two instruments. GC-QQQ-MS/MS results were not statistically different from the GC-HR-MS results. Findings support the suitability of GC-QQQ-MS/MS for analysis of PBDEs in fish.

Research paper thumbnail of Occurrence of Cotton Pesticides in Surface Water of the Mississippi Embayment

Fact Sheet

This fact sheet introduces a study of the nonpoint-source occurrence of pesticides in water of th... more This fact sheet introduces a study of the nonpoint-source occurrence of pesticides in water of the cotton-growing areas of the Southern United States with special emphasis on the Mississippi Embayment (fig. 1). This study is being conducted by the U.S. Geological Survey (USGS) Organic Geochemistry Research Group, which investigates the fate and transport of agricultural chemicals in the environment. The purpose of this fact sheet is to give an overview of the cottongrowing areas of the United States, to provide usage data for cotton pesticides in the United States, to present information on the types of pesticide compounds and concentrations that have been found thus far in the Mississippi Embayment, and to discuss current areas of cotton pesticide research.

Research paper thumbnail of Method of Analysis and Quality-Assurance Practices by the U.S. Geological Survey Organic Geochemistry Research Group-Determination of Four Selected Mosquito Insecticides and a Synergist in Water Using Liquid-Liquid Extraction and Gas Chromatography/Mass Spectrometry

A method of analysis and quality-assurance practices were developed for the determination of four... more A method of analysis and quality-assurance practices were developed for the determination of four mosquito insecticides (malathion, methoprene, phenothrin, and resmethrin) and one synergist (piperonyl butoxide) in water. The analytical method uses liquid-liquid extraction (LLE) and gas chromatography/mass spectrometry (GC/MS). Good precision and accuracy were demonstrated in reagent water, urban surface water, and ground water. The mean accuracies as percentages of the true compound concentrations from water samples spiked at 10 and 50 nanograms per liter ranged from 68 to 171 percent, with standard deviations in concentrations of 27 nanograms per liter or less. The method detection limit for all compounds was 5.9 nanograms per liter or less for 247-milliliter samples. This method is valuable for acquiring information about the fate and transport of these mosquito insecticides and one synergist in water.

Research paper thumbnail of Heterogeneous carbonaceous matter in sedimentary rock lithocomponents causes significant trichloroethylene (TCE) sorption in a low organic carbon content aquifer/aquitard system

Journal of Contaminant Hydrology, 2014

This study evaluated the effects of heterogeneous thermally altered carbonaceous matter (CM) on t... more This study evaluated the effects of heterogeneous thermally altered carbonaceous matter (CM) on trichloroethylene (TCE) sorption for a low fraction organic carbon content (foc) alluvial sedimentary aquifer and aquitard system (foc=0.046-0.105%). The equilibrium TCE sorption isotherms were highly nonlinear with Freundlich exponents of 0.46-0.58. Kerogen+black carbon was the dominant CM fraction extracted from the sediments and accounted for >60% and 99% of the total in the sands and silt, respectively. Organic petrological examination determined that the kerogen included abundant amorphous organic matter (bituminite), likely of marine origin. The dark calcareous siltstone exhibited the greatest TCE sorption among aquifer lithocomponents and accounted for most sorption in the aquifer. The results suggest that the source of the thermally altered CM, which causes nonlinear sorption, was derived from parent Paleozoic marine carbonate rocks that outcrop throughout much of New York State. A synthetic aquifer-aquitard unit system (10% aquitard) was used to illustrate the effect of the observed nonlinear sorption on mass storage potential at equilibrium. The calculation showed that >80% of TCE mass contained in the aquifer was sorbed on the aquifer sediment at aqueous concentration <1000 μgL(-1). These results show that sorption is likely a significant contributor to the persistence of a TCE groundwater plume in the aquifer studied. It is implied that sorption may similarly contribute to TCE persistence in other glacial alluvial aquifers with similar geologic characteristics, i.e., comprised of sedimentary rock lithocomponents that contain thermally altered CM.

Research paper thumbnail of Detection of persistent organic pollutants in the Mississippi Delta using semipermeable membrane devices

Science of The Total Environment, 2000

From semipermeable membrane devices (SPMDs) placed in five Mississippi Delta streams in 1996 and ... more From semipermeable membrane devices (SPMDs) placed in five Mississippi Delta streams in 1996 and 1997, the persistent organic pollutants (POPs) aldrin, chlordane, DCPA, DDT, dieldrin, endrin, heptachlor, mirex, nonachlor, and toxaphene were detected. In addition, the insecticides chlorpyriphos, endosulfan, and hexachlorocyclohexanes were detected. Two low-solubility herbicides not detected commonly in surface water, pendimethalin and trifluralin, were also detected.

Research paper thumbnail of Analysis of selected herbicide metabolites in surface and ground water of the United States

Science of The Total Environment, 2000

Ž. One of the primary goals of the US Geological Survey USGS Laboratory in Lawrence, Kansas, is t... more Ž. One of the primary goals of the US Geological Survey USGS Laboratory in Lawrence, Kansas, is to develop analytical methods for the analysis of herbicide metabolites in surface and ground water that are vital to the study of herbicide fate and degradation pathways in the environment. Methods to measure metabolite concentrations from three major classes of herbicides ᎏ triazine, chloroacetanilide and phenyl-urea ᎏ have been developed. Methods for triazine metabolite detection cover nine compounds: six compounds are detected by gas chromatographyrmass spectrometry; one is detected by high-performance liquid chromatography with diode-array detection; and eight are detected by liquid chromatographyrmass spectrometry. Two metabolites of the chloroacetanilide herbicides ᎏ ethane sulfonic acid and oxanilic acid ᎏ are detected by high-performance liquid chromatography with diode-array detection and liquid chromatographyrmass spectrometry. Alachlor ethane sulfonic acid also has been detected by solid-phase extraction and enzyme-linked immunosorbent assay. Six phenylurea metabolites are all detected by liquid chromatographyrmass spectrometry; four of the six metabolites also are detected by gas chromatographyrmass spectrometry. Additionally, surveys of herbicides and their metabolites in surface water, ground water, lakes, reservoirs, and rainfall have been conducted through the USGS laboratory in Lawrence. These surveys have been useful in determining herbicide and metabolite occurrence and temporal distribution and have shown that metabolites may be useful in evaluation of non-point-source contamination.

Research paper thumbnail of Statewide Survey of Hormones and Antibiotics in Surface Waters of Delaware

JAWRA Journal of the American Water Resources Association, 2013

ABSTRACT Water-quality surveys have confirmed the presence of hormones and antibiotics in surface... more ABSTRACT Water-quality surveys have confirmed the presence of hormones and antibiotics in surface waters of the United States, which may be of concern to aquatic life. We investigated the concentrations of hormones and antibiotics in surface waters of the state of Delaware to determine – how they compared against environmental thresholds, how they varied across the state, and if they were correlated with land use type. Fifty surface water locations were sampled during early spring and late summer. Water samples were initially screened with ELISA followed by analysis with LC/MS/MS. The measured ranges of hormone concentrations were: 0-3.71 ng/l for estrone, 0-4.65 ng/l for estrone-3-sulfate, and 0-6.27 ng/l for 17β-estradiol. The measured ranges of antibiotics were: 0-3.30 ng/l for sulfamerazine, 0-10.74 ng/l for sulfamethoxazole, and 0-2.29 ng/l for tetracycline. The predicted no-effect concentration (PNEC) for estrone was exceeded for three samples and the PNEC for 17β-estradiol was exceeded for 11 samples. In general, concentrations and detection frequencies were lower in the summer than the spring. The highest concentrations of hormones and antibiotics were spatially distributed in agricultural and urban areas; however, the correlations between land use type and the concentrations were weak. This study was the first statewide survey of hormones and antibiotics for Delaware and provided important baseline data on these emerging contaminants.

Research paper thumbnail of Analysis and Detection of the Herbicides Dimethenamid and Flufenacet and Their Sulfonic and Oxanilic Acid Degradates in Natural Water

Journal of Agricultural and Food Chemistry, 2002

Dimethenamid [2-chloro-N-(2,4-dimethyl-3-thienyl)-N-(2-methoxy-1-methylethyl)acetamide] and flufe... more Dimethenamid [2-chloro-N-(2,4-dimethyl-3-thienyl)-N-(2-methoxy-1-methylethyl)acetamide] and flufenacet [N-(4-fluorophenyl)-N-(1-methylethyl)-2-(5-(trifluoromethyl)-1,3,4-thiadiazol-2-yl)oxy] were isolated by C-18 solid-phase extraction and separated from their ethanesulfonic acid (ESA) and oxanilic acid (OXA) degradates during their elution using ethyl acetate for the parent compound, followed by methanol for the polar degradates. The parent compounds were detected using gas chromatographymass spectrometry in selected-ion mode. The ESA and OXA degradates were detected using highperformance liquid chromatography-electrospray mass spectrometry (HPLC-ESPMS) in negativeion mode. The method detection limits for a 123-mL sample ranged from 0.01 to 0.07 µg/L. These methods are compatible with existing methods and thus allow for analysis of 17 commonly used herbicides and 18 of their degradation compounds with one extraction. In a study of herbicide transport near the mouth of the Mississippi River during 1999 and 2000, dimethenamid and its ESA and OXA degradates were detected in surface water samples during the annual spring flushes. For flufenacet, the only detections at the study site were for the ESA degradates in samples collected at the peak of the herbicide spring flush in 2000. The low frequency of detections in surface water likely is due to dimethenamid and flufenacet being relatively new herbicides. In addition, detectable amounts of the stable degradates have not been detected in ground water.

Research paper thumbnail of Regional Water-Quality Analysis of 2,4-D and Dicamba in River Water Using Gas Chromatography-Isotope Dilution Mass Spectrometry

International Journal of Environmental Analytical Chemistry, 2001

... Because SPE-ELISA did not provide reliable results for the analysis of low con-centrations of... more ... Because SPE-ELISA did not provide reliable results for the analysis of low con-centrations of 2,4-D in surface-water samples ... References [I] LP Gianessi and JE Anderson, Pesticide Use in US Crop Production: National Data Report, National Center for Food and Agricultural ...

Research paper thumbnail of Identification of a New Sulfonic Acid Metabolite of Metolachlor in Soil

Environmental Science & Technology, 1996

... 9) Aga, DS; Thurman, EM; Pomes, ML Anal. Chem.1994, 66, 1495−1499. ... Oxanilic Acid Degradat... more ... 9) Aga, DS; Thurman, EM; Pomes, ML Anal. Chem.1994, 66, 1495−1499. ... Oxanilic Acid Degradates. Sung-Ben Huang, Thomas J. Mayer and Robert A. Yokley. Journal of Agricultural and Food Chemistry 2008 56 (8), 2595-2602. ...

Research paper thumbnail of Relation of Usage to the Occurrence of Cotton and Rice Herbicides in Three Streams of the Mississippi Delta

Environmental Science & Technology, 1998

... 3) Goolsby, DA; Thurman, EM; Pomes, ML; Meyer, M.; Battaglin, WA US Geological Survey Open-Fi... more ... 3) Goolsby, DA; Thurman, EM; Pomes, ML; Meyer, M.; Battaglin, WA US Geological Survey Open-File Report 93-418; 1993; pp 75−89. (4) US EPA. ... 14) Wiese, AF; Savage, KE; Chandler, JM; Liu, LC; Jeffery, LS; Weber, JB; LaFleur, KS J. Environ. Qual. ...

Research paper thumbnail of Formation and Transport of Deethylatrazine and Deisopropylatrazine in Surface Water

Environmental Science & Technology, 1994

Formation and Transport of Deethylatrazine and Deisopropylatrazine in ... E. M. Thurman,' MT... more Formation and Transport of Deethylatrazine and Deisopropylatrazine in ... E. M. Thurman,' MT Meyer, MS Mllls, L, R. Zlmmerman, and CA Perry US. Geological Survey, 4821 Quail Crest Place, Lawrence, Kansas 66049 ... Donald A. Goolsby US. Geological Survey, Denver ...

Research paper thumbnail of Assessing antibiotic sorption in soil: a literature review and new case studies on sulfonamides and macrolides

Chemistry Central Journal, 2014

The increased use of veterinary antibiotics in modern agriculture for therapeutic uses and growth... more The increased use of veterinary antibiotics in modern agriculture for therapeutic uses and growth promotion has raised concern regarding the environmental impacts of antibiotic residues in soil and water. The mobility and transport of antibiotics in the environment depends on their sorption behavior, which is typically predicted by extrapolating from an experimentally determined soil-water distribution coefficient (Kd). Accurate determination of Kd values is important in order to better predict the environmental fate of antibiotics. In this paper, we examine different analytical approaches in assessing Kd of two major classes of veterinary antibiotics (sulfonamides and macrolides) and compare the existing literature data with experimental data obtained in our laboratory. While environmental parameters such as soil pH and organic matter content are the most significant factors that affect the sorption of antibiotics in soil, it is important to consider the concentrations used, the an...

Research paper thumbnail of Linker-Assisted Immunoassay and Liquid Chromatography/Mass Spectrometry for the Analysis of Glyphosate

Analytical Chemistry, 2002

A novel, sensitive, linker-assisted enzyme-linked immunosorbent assay (L'ELISA) was compa... more A novel, sensitive, linker-assisted enzyme-linked immunosorbent assay (L'ELISA) was compared to on-line solid-phase extraction (SPE) with high-performance liquid chromatography/mass spectrometry (HPLC/MS) for the analysis of glyphosate in surface water and groundwater samples. The L'ELISA used succinic anhydride to derivatize glyphosate, which mimics the epitotic attachment of glyphosate to horseradish peroxidase hapten. Thus, L'ELISA recognized the derivatized glyphosate more effectively (detection limit of 0.1 microg/L) and with increased sensitivity (10-100 times) over conventional ELISA and showed the potential for other applications. The precision and accuracy of L'ELISA then was compared with on-line SPE/HPLC/MS, which detected glyphosate and its degradate derivatized with 9-fluorenylmethyl chloroformate using negative-ion electrospray (detection limit 0.1 microg/ L, relative standard deviation +/- 15%). Derivatization efficiency and matrix effects were minimized by adding an isotope-labeled glyphosate (2-13C15N). The accuracy of L'EUSA gave a false positive rate of 18% between 0.1 and 1.0 microg/L and a false positive rate of only 1% above 1.0 microg/L The relative standard deviation was +/- 20%. The correlation of L'ELISA and HPLC/MS for 66 surface water and groundwater samples was 0.97 with a slope of 1.28, with many detections of glyphosate and its degradate in surface water but not in groundwater.

Research paper thumbnail of Spatial pattern of hormone and antibiotic concentrations in surface waters in Delaware

ABSTRACT Water quality surveys of the U.S. have confirmed the presence of hormones and antibiotic... more ABSTRACT Water quality surveys of the U.S. have confirmed the presence of hormones and antibiotics in some surface waters. Although the reported concentrations of these substances are extremely low, there is substantial concern about their effect on aquatic species. For example, chronic exposure to estradiol (E2β) concentrations as low as 40 ng/L have been shown to cause endocrine disruption in fish. Furthermore, there is potential for contaminants to enter our drinking supply. Significant sources of hormones and antibiotics include discharge from concentrated animal feeding operations (CAFOs) and wastewater treatment plants as well as runoff from agricultural land receiving application of animal manure. Since Sussex County, Delaware is one of the leading poultry producing counties in the nation, and many farmers in the state use poultry litter as fertilizer for their crops, it is critical to study the concentrations of contaminants in surface waters. Fifty surface water (streams, lakes, and ponds) sampling locations throughout the state of Delaware were chosen based on DNREC (Delaware Department of Natural Resources and Environmental Control) data. Locations with the highest nitrogen and phosphorus levels were assumed to be associated with agriculture and wastewater sources and therefore were likely to be contaminated with hormones and antibiotics. The first set of sampling occurred in April representing high-flow conditions, and the second set will occur in September representing low-flow conditions. Water samples will be screened through the cost-effective enzyme-linked immunosorbent assay (ELISA) method followed by more rigorous analyses of selected samples using liquid chromatography-mass spectrometry (LC/MS/MS). ELISA screening includes estradiol (E2β), sulfamethazine and triclosan, while LC/MS/MS will quantify both free and conjugated forms of estrone (E1), estradiol (E2β), estriol (E3), as well as selected sulfa and tetracycline antibiotics. Initial ELISA results indicate a range of 0-40 ng/L for E2β, 0-18 μg/L for sulfamethazine, and 0-3 μg/L for triclosan; however, previous studies have shown that the ELISA method tends to overestimate due to cross-reactivity and matrix effects, and therefore we expect lower concentrations from LC/MS/MS. All LC/MS/MS results are expected by December 2011. Results will be compared to the predicted no-effect concentrations to determine whether these contaminants pose a threat to aquatic species and wildlife. ArcGIS was used to plot the measured concentrations on the Delaware state map to provide a spatial representation of the potential contamination. Watersheds were delineated for each of the sampling locations, and land use, physical characteristics of the land, and potential sources of contaminants within the watersheds have been analyzed to explore any relationships with measured contaminant concentrations.