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Sample records for acetochlor alachlor butachlor

  1. Biodegradation of acetanilide herbicides acetochlor and butachlor in soil.

    PubMed

    Ye, Chang-ming; Wang, Xing-jun; Zheng, He-hui

    2002-10-01

    The biodegradation of two acetanilide herbicides, acetochlor and butachlor in soil after other environmental organic matter addition were measured during 35 days laboratory incubations. The herbicides were applied to soil alone, soil-SDBS (sodium dodecylbenzene sulfonate) mixtures and soil-HA (humic acid) mixtures. Herbicide biodegradation kinetics were compared in the different treatment. Biodegradation products of herbicides in soil alone samples were identified by GC/MS at the end of incubation. Addition of SDBS and HA to soil decreased acetochlor biodegradation, but increased butachlor biodegradation. The biodegradation half-life of acetochlor and butachlor in soil alone, soil-SDBS mixtures and soil-HA mixtures were 4.6 d, 6.1 d and 5.4 d and 5.3 d, 4.9 d and 5.3 d respectively. The biodegradation products were hydroxyacetochlor and 2-methyl-6-ethylaniline for acetochlor, and hydroxybutachlor and 2,6-diethylaniline for butachlor. PMID:12491727

  2. Derived Reference Doses (RfDs) for the environmental degradates of the herbicides alachlor and acetochlor: results of an independent expert panel deliberation.

    PubMed

    Gadagbui, Bernard; Maier, Andrew; Dourson, Michael; Parker, Ann; Willis, Alison; Christopher, John P; Hicks, Lebelle; Ramasamy, Santhini; Roberts, Stephen M

    2010-01-01

    An independent peer expert panel was convened under the auspices of the Alliance for Risk Assessment (ARA) to review toxicology data and derive oral Reference Doses (RfDs) for four environmental degradates of the acetanilide herbicides, alachlor and acetochlor. The degradates included in this evaluation were (1) alachlor tertiary-ethanesulfonic acid (ESA), (2) alachlor tertiary-oxanilic acid (OXA), (3) acetochlor ESA, and (4) acetochlor OXA. Each degradate was judged to have sufficient data for developing low to medium confidence RfD, with use of an additional uncertainty factor (UF) to cover data gaps. Body weight decreases were identified as the most sensitive treatment-related adverse effect for RfD development. A composite UF of 1000 (10 for human variability in sensitivity, 10 for interspecies differences in sensitivity, and 10 for subchronic to chronic and database deficiency combined; i.e., 10(A)x10(H)x10(S&D)) for each degradate was considered reasonable, while noting that an argument could be made for an UF of 3000 (10(A)x10(H)x30(S&D)). Based on the available data, an oral RfD of 0.2 mg/kg-day is recommended for both acetochlor ESA and acetochlor OXA and an oral RfD of 0.8 mg/kg-day is recommended for both alachlor ESA and alachlor OXA. PMID:20206657

  3. Accurate mass analysis of ethanesulfonic acid degradates of acetochlor and alachlor using high-performance liquid chromatography and time-of-flight mass spectrometry

    USGS Publications Warehouse

    Thurman, E.M.; Ferrer, I.; Parry, R.

    2002-01-01

    Degradates of acetochlor and alachlor (ethanesulfonic acids, ESAs) were analyzed in both standards and in a groundwater sample using high-performance liquid chromatography-time-of-flight mass spectrometry with electrospray ionization. The negative pseudomolecular ion of the secondary amide of acetochlor ESA and alachlor ESA gave average masses of 256.0750??0.0049 amu and 270.0786??0.0064 amu respectively. Acetochlor and alachlor ESA gave similar masses of 314.1098??0.0061 amu and 314.1153??0.0048 amu; however, they could not be distinguished by accurate mass because they have the same empirical formula. On the other hand, they may be distinguished using positive-ion electrospray because of different fragmentation spectra, which did not occur using negative-ion electrospray.

  4. Characterization of a Novel Butachlor Biodegradation Pathway and Cloning of the Debutoxylase (Dbo) Gene Responsible for Debutoxylation of Butachlor in Bacillus sp. hys-1.

    PubMed

    Gao, Yang; Jin, Lei; Shi, Hui; Chu, Zhangjie

    2015-09-30

    Bacillus sp. strain hys-1, which was isolated from active sludge, could degrade >90% butachlor at a concentration of 100 mg/L within 7 days. The present work revealed that strain hys-1 could mineralize butachlor via the following pathway: butachlor was initially metabolized to 2-chloro-N-(2,6-diethylphenyl)-N-methylacetamide by debutoxylation and then transformed to form 2-chloro-N-(2,6-diethylphenyl)acetamide by N-demethylation. Subsequently, it was converted to 2,6-diethylaniline and further mineralized into CO2 and H2O. In addition, the catalytic efficiency of crude cell extracts descended as follows: alachlor > acetochlor > butachlor. Furthermore, a novel 744 bp gene responsible for transforming butachlor into 2-chloro-N-(2,6-diethylphenyl)-N-methylacetamide was cloned from strain hys-1 and the encoding debutoxylase was designated Dbo. Then Dbo was expressed in Escherichia coli BL21 (DE3) and purified using Ni-nitrilotriacetic acid affinity chromatography. Dbo displayed the highest activity against butachlor at pH 6.5 and 30 °C. Metal ions played an important role in Dbo activity. To the best of the authors' knowledge, this is the first report that strain hys-1 can mineralize butachlor by a novel metabolic mechanism and the first identification of a gene encoding butachlor debutoxylase. PMID:26368393

  5. Alachlor

    Integrated Risk Information System (IRIS)

    Alachlor ; CASRN 15972 - 60 - 8 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effect

  6. Acetochlor

    Integrated Risk Information System (IRIS)

    Acetochlor ; CASRN 34256 - 82 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effe

  7. Occurrence of alachlor and its sulfonated metabolite in rivers and reservoirs of the midwestern United States: The importance of sulfonation in the transport of chloroacetanilide herbicides

    USGS Publications Warehouse

    Thurman, E.M.; Goolsby, D.A.; Aga, D.S.; Pomes, M.L.; Meyer, M.T.

    1996-01-01

    Alachlor and its metabolite, 2-[(2',6'-diethylphenyl)- (methoxymethyl)amino]-2-oxoethanesulfonate (ESA), were identified in 76 reservoirs in the midwestern United States using immunoassay, liquid chromatography, and gas chromatography/mass spectrometry. The median concentration of ESA (0.48 ??g/L) exceeded the median concentration of alachlor (<0.05 ??g/L), with highest values in the upper Midwest. ESA also was detected in the Mississippi River from the mouth to the headwaters at concentrations of 0.2-1.5 ??g/L, exceeding the concentration of alachlor. In a field runoff study, alachlor rapidly formed ESA. It is hypothesized that a glutathione conjugate forms, which later oxidizes in soil to ESA. The removal of the chlorine atom lessens the toxicity of the parent compound and increases runoff potential. It is hypothesized further that sulfonic acid metabolites of other chloroacetanilides, including acetochlor, butachlor, metolachlor, and propachlor, also occur in surface water.

  8. METHOD DEVELOPMENT FOR ALACHLOR ESA AND OTHER ACENTANILIDE HERBICIDE DEGRADATION PRODUCTS

    EPA Science Inventory

    Introduction: Acetanilide herbicides are frequently applied in the U.S. on crops (corn, soybeans, popcorn, etc.) to control broadleaf and annual weeds. The acetanilide and acetamide herbicides currently registered for use in the U.S. are alachlor, acetochlor, metolachlor, propa...

  9. ANALYTICAL METHOD DEVELOPMENT FOR ALACHLOR ESA AND OTHER ACETANILIDE PESTICIDE TRANSFORMATION PRODUCTS

    EPA Science Inventory

    Acetanilide herbicides are frequently applied in the U.S. on crops (corn, soybeans, popcorn, etc.) to control broadleaf and annual weeds. The acetanilide herbicides currently registered for use in the U.S. are: alachlor, acetochlor, metolachlor, propachlor, dimethenamid and fluf...

  10. Metolachlor and alachlor breakdown product formation patterns in aquatic field mesocosms

    USGS Publications Warehouse

    Graham, W.H.; Graham, D.W.; DeNoyelles, F., Jr.; Smith, V.H.; Larive, C.K.; Thurman, E.M.

    1999-01-01

    The transformation of metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)- N-(2-methoxy-1-methyl)ethyl)acetamide] and alachlor [2-chloro-N-(2,6- diethylphenyl)-N-methoxymethyl)acetamide] in aquatic systems was investigated using outdoor tank mesocosms. Metolachlor and alachlor levels and their ethane sulfonic acid (ESA) and oxanillic acid breakdown products were monitored over time under five experimental treatments (each in quadruplicate). Background water conditions were identical in all treatments with each treatment differing based on the level and type(s) of herbicide present. Treatments included a noherbicide control, 10 ??g/L metolachlor, 25 ??g/L metolachlor, 25 ??g/L alachlor, and 25 ??g/L alachlor plus 25 ??g/L metolachlor in combination. The experiment was initiated by adding herbicide(s) to the units to the target concentrations; herbicide and breakdown product levels and other chemical parameters were then monitored for 85 days. In general, metolachlor half-lives were longer than alachlor half-lives under all treatments, although the differences were not statistically significant. Metolachlor half-lives (??95% confidence limits) ranged from 33.0 d (??14.1 d) to 46.2 d (??40.0 d), whereas alachlor half- lives ranged from 18.7 d (??3.5 d) to 21.0 d (??6.5 d) for different treatments. Formation patterns of ESA were similar in all treatments, whereas oxanillic acid formation differed for the two herbicides. Alachlor oxanillic acid was produced in larger quantities than metolachlor oxanillic acid and either ESA under equivalent conditions. Our results suggest that the transformation pathways for alachlor and metolachlor in aquatic systems are similar and resemble the acetochlor pathway in soils proposed by Feng (Pestic. Biochem. Physiol. 1991, 34, 136); however, the oxanillic acid branch of the pathway is favored for alachlor as compared with metolachlor.The transformation of metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N- (2-methoxy-1-methylethy

  11. Comparative proteome analysis of butachlor-degrading bacteria

    NASA Astrophysics Data System (ADS)

    Wang, Jinhua; Lu, Yitong; Chen, Yingying

    2008-01-01

    A Pseudomonas putida strain, named ER1, was isolated from an agricultural soil and found to actively degrade the herbicide butachlor. The enzyme extracted from ER1 could degrade butachlor. Furthermore, incubation of ER1 in a medium containing 50 mg/kg of butachlor after 3 days resulted in the high butachlor-degrading enzyme activity of ER1. Response of ER1 to butachlor might be related to changes in protein composition at both quantitative and qualitative levels. Total proteins were extracted from control strain (incubated in the medium without butachlor) and the treated strain (incubated in the medium with butachlor). The proteins were separated by two-dimensional gel electrophoresis. Of the total number of ER1 protein, 11 spots were significantly changed under butachlor stress. Analysis by matrix-assisted laser desorption/ionization mass spectrometry and tandem mass spectrometry coupled with database searching allowed the function of some proteins which were similar to the hydrolases activity or oxidoreductase activity.

  12. REMOVAL OF ALACHLOR FROM DRINKING WATER

    EPA Science Inventory

    Alachlor (Lasso) is a pre-emergent herbicide used in the production of corn and soybeans. U.S. EPA has studied control of alachlor in drinking water treatment processes to define treatability before setting maximum contaminant levels and to assist water utilities in selecting con...

  13. In vivo percutaneous absorption of acetochlor in the rhesus monkey: dose-response and exposure risk assessment.

    PubMed

    Wester, R C; Melendres, J L; Maibach, H I

    1996-10-01

    Percutaneous absorption of three topical dose levels of [14C]acetochlor in the rhesus monkey were determined for exposure risk assessment. The topical doses were 30.7, 0.43 and 0.03 mg acetochlor in 40 microliters commercial formulation and aqueous dilutions thereof, spread over 10 cm3 skin surface area (lower abdominal). The dosing area was not covered. The skin application time was 24 hr. The dosed skin surface area was washed with 50% soap (Ivory Liquid) and water at the end of the 24-hr dosing period. An intravenous dose of 0.43 mg was also administered to determine the excretory kinetics of acetochlor in the rhesus monkey. The same four monkeys were used for all dose administrations. Bioavailability was determined by radioactivity disposition in blood, urine and faeces. Percutaneous absorption was 23.1 +/- 8.7, 17.3 +/- 5.9 and 4.9 +/- 1.4% for 0.03, 0.43 and 30.7 mg doses, respectively. Assuming a constant state of absorption, the hourly exposure flux (microgram/cm2/hr) was 0.03 +/- 0.01 for the 0.03 mg dose (3 micrograms/cm2). Increasing the dose approximately 15-fold to 0.43 mg (43 micrograms/cm2) resulted in a 10-fold increase in flux to 0.3 microgram/cm2/hr. Increasing the dose a further 70-fold to 30.7 mg (3070 micrograms/cm2) resulted in only another 21-fold increase in flux (6.3 +/- 1.8 micrograms/cm2/hr). Thus, the efficiency of absorption (%) decreased with increased topical dose, but the amount (mass/flux) of acetochlor absorbed always increased with increased dose. Plasma levels of topical acetochlor at the high dose were detectable at 1 hr and continued at a relatively steady level through the 24-hr dosing period. After the skin surface wash (24 hr) plasma levels decreased but were still detectable at the last 168-hr sampling period. Acetochlor, recently EPA approved as an herbicide for corn crops, is carcinogenic; however, farmers will use half as much acetochlor/acre as other herbicides. The percutaneous absorption of acetochlor is equal to that

  14. Biodegradation of alachlor by soil streptomycetes.

    PubMed

    Durães Sette, L; Mendonça Alves Da Costa, L A; Marsaioli, A J; Manfio, G P

    2004-06-01

    Streptomycetes resistant to the herbicide alachlor [2-chloro-2',6'-diethyl- N-(methoxymethyl) acetanilide] were used in degradation assays to characterize the products of alachlor biodegradation. Of six strains tested, Streptomyces sp. LS166, LS177, and LS182 were able to grow at an alachlor concentration of 144 mg l(-1) and degraded approximately 60-75% of the alachlor in 14 days, as evaluated by high performance liquid chromatography. The alachlor biodegradation products were identified by gas chromatography-mass spectrometry based on mass spectral data and fragmentation patterns. All compounds detected in these assays were similar for all streptomycetes strains tested, and involved dechlorination with subsequent N-dealkylation and cyclization of the remaining N-substituent with one of the ethyl groups to produce indole and quinoline derivatives. The enzymatic pathway used by Streptomyces sp. LS182 did not generate DEA (2',6'-diethylaniline), a carcinogenic derivative of alachlor reported in other studies. Given the high degradation rates observed here, the Streptomyces strains tested may be useful in the degradation/detoxification processes of alachlor. PMID:14727088

  15. Herbicide transport trends in Goodwater Creek experimental watershed II: acetochlor, alachlor, metolachlor, and metribuzin

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Farmers in the Midwestern United States continue to be reliant on soil-applied herbicides for weed control in row crop production, and herbicide contamination of surface waters. Runoff-prone watersheds remain an environmental problem. The primary objective of this study was to analyze trends in conc...

  16. Biodegradation and mineralization of metolachlor and alachlor by Candida xestobii.

    PubMed

    Munoz, Ana; Koskinen, William C; Cox, Lucía; Sadowsky, Michael J

    2011-01-26

    Metolachlor (2-chloro-6'-ethyl-N-(2-methoxy-1-methylethyl)aceto-o-toluidide) is a pre-emergent chloroacetanilide herbicide used to control broadleaf and annual grassy weeds in a variety of crops. The S enantiomer, S-metolachlor, is the most effective form for weed control. Although the degradation of metolachlor in soils is thought to occur primarily by microbial activity, little is known about the microorganisms that carry out this process and the mechanisms by which this occurs. This study examined a silty-clay soil (a Luvisol) from Spain, with 10 and 2 year histories of metolachlor and S-metolachlor applications, respectively, for microorganisms that had the ability to degrade this herbicide. Tis paper reports the isolation and characterization of pure cultures of Candida xestobii and Bacillus simplex that have the ability to use metolachlor as a sole source of carbon for growth. Species assignment was confirmed by morphological and biochemical criteria and by sequence analysis of 18S and 16S rRNA, respectively. High-performance liquid chromatography (HPLC) and liquid chromatography-mass spectrometry (LC-MS) analyses indicated that C. xestobii degraded 60% of the added metolachlor after 4 days of growth and converted up to 25% of the compound into CO(2) after 10 days. In contrast, B. simplex biodegraded 30% of metolachlor following 5 days of growth in minimal medium. In contrast, moreover, the yeast degraded other acetanilide compounds and 80% of acetochlor (2-chloro-N-ethoxymethyl-6'-ethylaceto-o-toluidide) and alachlor (2-chloro-2',6'-diethyl-N-methoxymethylacetanilide) were degraded after 15 and 41 h of growth, respectively. The results of these studies indicate that microorganisms comprising two main branches of the tree of life have acquired the ability to degrade the same novel chlorinated herbicide that has been recently added to the biosphere. PMID:21190381

  17. DNA adduct formation by alachlor metabolites

    SciTech Connect

    Brown, M.A.; Kimmel, E.C.; Casida, J.E.

    1988-01-01

    The extent of DNA adduct formation by alachlor (ArN(CH/sub 2/OCH/sub 3/)C(O)CH/sub 2/Cl wherein Ar is 2,6-diethylphenyl) and its metabolites is used as a guide to deduce the causal agent(s) in the carcinogenicity of this major herbicide. (/sup 14/C-phenyl)Alachlor is compared to its two metabolic cleavage products, (/sup 14/C-phenyl) 2-chloro-N-(2,6-diethylphenyl)acetamide (CDEPA) (ArNHC(O)CH/sub 2/Cl) and (/sup 14/C-phenyl)2,6-diethylaniline (DEA) (ArNH/sub 2/), and to (/sup 14/C-methoxy)alachlor in various in vitro and in vivo systems. Horseradish peroxidase and hydrogen peroxide activate DEA, but not CEDPA or alachlor, for formation of adducts with calf thymus DNA, which probably involves 2,6-diethylnitrosobenzene (ArNO) as an intermediate. Mouse liver microsomes and NADPH are both required to enhance the binding from each labeled preparation to calf thymus DNA; 4-fold higher labeling is observed from (/sup 14/C-methoxy)- than from (/sup 14/C-phenyl)alachlor. This 4-fold preferential DNA labeling from the /sup 14/C-methoxy compound is likewise found in the liver of mice treated intraperitoneally. Mouse liver protein and hemoglobin are also labeled, in vivo, with (/sup 14/C-phenyl)alachlor, -CDEPA and -DEA, and, as with the DNA, the labeling of these proteins is 1.5- to 2-fold higher with (/sup 14/C-methoxy)alachlor.

  18. [Determination of acetochlor and oxyfluorfen by capillary gas chromatography].

    PubMed

    Xiang, Wen-Sheng; Wang, Xiang-Jing; Wang, Jing; Wang, Qing

    2002-09-01

    A method is described for the determination of acetochlor and oxyfluorfen by capillary gas chromatography with FID and an SE-30 capillary column (60 m x 0.53 mm i. d., 1.5 microm), using dibutyl phthalate as the internal standard. The standard deviations for acetochlor and oxyfluorfen concentration(mass fraction) were 0.44% and 0.47% respectively. The relative standard deviations for acetochlor and oxyfluorfen were 0.79% and 0.88% and the average recoveries for acetochlor and oxyfluorfen were 99.3% and 101.1% respectively. The method is simple, rapid and accurate. PMID:16358708

  19. 40 CFR 180.470 - Acetochlor; tolerances for residues.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 24 2011-07-01 2011-07-01 false Acetochlor; tolerances for residues. 180.470 Section 180.470 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD Specific Tolerances § 180.470 Acetochlor; tolerances for residues....

  20. Comprehensive spectroscopic probing the interaction and conformation impairment of bovine serum albumin (BSA) by herbicide butachlor.

    PubMed

    Liu, Xiaoyi; Ling, Zhaoxing; Zhou, Xing; Ahmad, Farooq; Zhou, Ying

    2016-09-01

    Butachlor is an effective herbicide to deal with undesired weeds selectively and is used at high levels in Asian countries. However, its interaction and impairment effect on BSA was still not clear. In this study, we investigated the interaction between butachlor and bovine serum albumin (BSA) by multi-spectroscopic methods including UV absorption, circular dichroism (CD) spectra, Fourier transform infrared (FTIR) spectra and fluorescence spectra under physiological conditions (pH=7.4). The results revealed that there was a static quenching of BSA induced by butachlor stemmed from the formation of complex. Based on thermodynamic data, the interaction of butachlor with BSA was due to happen, and van der Waals force as well as hydrogen bond were the major forces contributed to the interaction. The binding constant Kb and number of binding site of butachlor with BSA were 5.158×10(5) and 1.372 at 303K, respectively. The distance r between donor (BSA) and acceptor (butachlor) was 0.113nm, obtained according to the Förster theory. The results revealed that butachlor induced conformational changes in BSA but the secondary structure of BSA was still retained. In addition, the microenvironment around chromophore residues of BSA, for example, tryptophan, changed as well, resulting from the formation of more hydrogen bonds. PMID:27419617

  1. The toxic mechanism of high lethality of herbicide butachlor in marine flatfish flounder, Paralichthys olivaceus

    NASA Astrophysics Data System (ADS)

    Guo, Huarong; Yin, Licheng; Zhang, Shicui; Feng, Wenrong

    2010-09-01

    The toxic mechanism of herbicide butachlor to induce extremely high lethality in marine flatfish flounder, Paralichthys Olivaceus, was analyzed by histopathological examination, antioxidant enzymes activities and ATP content assay. Histopathological examination of gill, liver and kidney of exposed fishes showed that gill was a target organ of butachlor. The butachlor seriously impaired the respiration of gills by a series of lesions such as edema, lifting and detachment of lamellar epithelium, breakdown of pillar cells, and blood congestion. The dysfunction of gill respiration caused suffocation to the exposed flounder with extremely high acute lethality. Antioxidant enzyme activity assay of the in vitro cultured flounder gill (FG) cells exposed to butachlor indicated that butachlor markedly inhibited the antioxidant enzyme activities of Superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GPX). Furthermore, along with the decline of antioxidant enzyme activities, ATP content in the exposed FG cells decreased, too. This infers that the oxidative stress induced by butachlor can inhibit the production of cellular ATP. Similar decrease of ATP content was also observed in the exposed flounder gill tissues. Taken together, as in FG cells, butachlor possibly induced a short supply of ATP in pillar cells by inhibiting the antioxidant enzyme activities and then affecting the contractibility of the pillar cells, which in turn resulted in the blood congestion and suffocation of exposed flounder.

  2. Exposure to butachlor causes thyroid endocrine disruption and promotion of metamorphosis in Xenopus laevis.

    PubMed

    Li, Shuying; Li, Meng; Wang, Qiangwei; Gui, Wenjun; Zhu, Guonian

    2016-06-01

    Butachlor is extensively applied in rice paddy ecosystem in china, and has been widespread contaminant in the aquatic environment. Here, Xenopus laevis was used for the evaluation of teratogenesis developmental toxicity, and disruption of thyroid system when exposure to different concentrations of butachlor by window phase exposure. Acute toxicity investigation shown that 96 h-LC50 value of butachlor was 1.424 mg L(-1) and 0.962 mg L(-1) for tadpoles (starting from stages 46/47) and embryos (starting from stages 8/9), respectively. Exposure to butachlor caused malformation, including abnormal eye, pericardial edema, enlarged proctodaeum and bent tail. Window phase exposure test indicated that butachlor significantly promote the contents of whole-body thyroid hormones (THs, T3 and T4) at higher levels, indicating thyroid endocrine disruption. At 7 days, exposure to butachlor up-regulated the mRNA expression of genes involved in THs synthesis and metabolism (tshα, tg, tpo and dio1) and THs receptors (trα and trβ). At 14 days, up-regulation of the mRNA expression of genes related to THs synthesis and metabolism (tshα, tshβ, tg, tpo, dio1, dio2 and ttr) and THs receptors (trβ) were also observed after the exposure to butachlor. At 21 days, butachlor up-regulated the mRNA expression of tshα, tg, tpo genes and down-regulated the mRNA expression of tshβ, tg, dio1, ttr and trα genes. These results showed that butachlor could change the mRNA expression of genes involved in the HPT axis and increase whole-body thyroid hormones levels of X. laevis tadpoles in a dose- and time-dependent manner, causing thyroid endocrine disruption and developmental toxicity. PMID:26971167

  3. Thyroid endocrine disruption of acetochlor on zebrafish (Danio rerio) larvae.

    PubMed

    Yang, Mei; Hu, Jingjin; Li, Shuying; Ma, Youning; Gui, Wenjun; Zhu, Guonian

    2016-06-01

    The herbicide acetochlor is widely used and detected in the environment and biota, and has been suspected to disrupt the thyroid endocrine system, but underlying mechanisms have not yet been clarified. In the present study, zebrafish larvae (7 days post-fertilization) were exposed to a series concentration of acetochlor (0, 1, 3, 10, 30, 100 and 300 µg l(-1) ) within a 14-day window until 21 days post-fertilization. Thyroid hormones and mRNA expression profiles of genes involved in the hypothalamic-pituitary-thyroid (HPT) axis were analyzed. Exposure to the positive control, 3,5,3'-triiodothyronine (T3 ), altered the mRNA expression, suggesting that the HPT axis in the critical window of zebrafish responded to chemical exposure and could be used to evaluate the effects of chemicals on the thyroid endocrine system. The mRNA expressions of genes involved in thyroid hormone synthesis (tshβ, slc5a5 and tpo) were upregulated significantly with acetochlor treatment, which might be responsible for the increased thyroxine concentrations. The downregulation of genes related to thyroid hormone metabolism (dio1 and ugt1ab) and transport (ttr) in zebrafish larvae exposed to acetochlor might further explain the increased thyroxine levels and decreased T3 levels. The mRNA expression of the thyroid hormone receptor (trα) was also upregulated upon acetochlor exposure. Results suggested that acetochlor altered mRNA expression of the HPT axis-related genes and changed the whole body thyroid hormone levels in zebrafish larvae. It demonstrated that acetochlor could cause endocrine disruption of the thyroid system by simulating the biological activity of T3 . Copyright © 2015 John Wiley & Sons, Ltd. PMID:26397822

  4. Nuclear Magnetic Resonance Identification of New Sulfonic Acid Metabolites of Chloroacetanilide Herbicides

    USGS Publications Warehouse

    Morton, M.D.; Walters, F.H.; Aga, D.S.; Thurman, E.M.; Larive, C.K.

    1997-01-01

    The detection of the sulfonic acid metabolites of the chloroacetanilide herbicides acetochlor, alachlor, butachlor, propachlor, and, more recently, metolachlor in surface and ground water suggests that a common mechanism for dechlorination exists via the glutathione conjugation pathway. The identification of these herbicides and their metabolites is important due to growing public awareness and concern about pesticide levels in drinking water. Although these herbicides are regulated, little is known about the fate of their metabolites in soil. The sulfonic acid metabolites were synthesized by reaction of the parent compounds with an excess of sodium sulfite. Acetochlor, alachlor, butachlor, metolachlor, and propachlor and their sulfonic acid metabolites were studied by nuclear magnetic resonance spectroscopy and fast atom bombardment mass spectrometry. This paper provides a direct method for the preparation and characterization of these compounds that will be useful in the analysis and study of chloracetanilide herbicides and their metabolites.

  5. Combined effects of cadmium and butachlor on soil enzyme activities and microbial community structure

    NASA Astrophysics Data System (ADS)

    Wang, Jinhua; Lu, Yitong; Shen, Guoqing

    2007-02-01

    The combined effects of cadmium (Cd, 10 mg/kg of soil) and butachlor (5, 10 and 50 mg/kg of soil) on enzyme activities and microbial community structure were assessed in phaeozem soil. The result showed that phosphatase activities were decreased in soils with Cd (10 mg/kg of soil) alone whereas urease acitivities were unaffected by Cd. Urease and phosphatase activities were significantly reduced by high butachlor concentration (50 mg/kg of soil). When Cd and butachlor concentrations in soils were added at milligram ratio of 2:1 or 1:2, urease and phosphatase activities were decreased, while enzyme activities were greatly improved at the ratio of 1:5. This study indicates that the combined effects of Cd and butachlor on soil urease and phosphatase activities depend largely on the addition concentration ratios to soils. The random amplified polymorphic DNA (RAPD) analysis showed that the changes occurring in RAPD profiles of different treated samples included variation in loss of normal bands and appearance of new bands compared with the control soil. The RAPD fingerprints showed substantial differences between the control and treated soil samples, with apparent changes in the number and size of amplified DNA fragments. The results showed that the addition of high concentration butachlor and the combined applied Cd and butachlor significantly affected the diversity of microbial community. The present results suggest that RAPD analysis in conjunction with other biomarkers such as soil enzyme parameter etc. would prove a powerful ecotoxicological tool.

  6. Adsorption-desorption behavior of acetochlor to soils in the presence of some environmental substances.

    PubMed

    Ye, Chang-ming; Lei, Zhi-fang

    2002-04-01

    The behavior of herbicide acetochlor adsorption-desorption to soil in the presence of humic acid (HA), anionic surfactant sodium dodecylbenzene sulfonate (SDBS), cationic surfactant hexadecyltrimethyl-ammonium bromide (HDAB) and NH4NO3 as a chemical fertilizer was studied. Observed acetochlor adsorption isotherm were well described using Freundlich isotherm equation, from which the desorption isotherm equation has been deduced. The deduced equation can more directly describe acetochlor desorption process. The results showed that the enhance of acetochlor adsorption capacity by solid HA was greater than by soluble HA. The presence of NH4 NO3 can slightly enhance acetochlor adsorption to soil by comparison with that measured in NH4 NO3-free solution. In soil-water system, surfactant-acetochlor interaction is very complex, and the surfactant adsorptions as well as acetochlor adsorption need to be considered. When acetochlor-soil suspensions contained lower concentration SDBS or HDAB (40 mg/L), Kf for acetochlor adsorption was decreased in comparison to that measured in SDBS- or HDAB-free solution. When acetochlor-soil suspensions contained higher concentration SDBS or HDAB (corresponding 1400 mg/L or 200 mg/L), Kf for acetochlor adsorption was increased in comparison to that measured in SDBS- or HDAB-free solution. PMID:12046299

  7. Isolation and characterization of a pseudomonas oleovorans degrading the chloroacetamide herbicide acetochlor.

    PubMed

    Xu, Jun; Qiu, Xinghui; Dai, Jiayin; Cao, Hong; Yang, Min; Zhang, Jing; Xu, Muqi

    2006-06-01

    To date, no pure bacterial cultures that could degrade acetochlor have been described. In this study, one strain of microorganism capable of degrading acetochlor, designated as LCa2, was isolated from acetochlor-contaminated soil. The strain LCa2 is Pseudomonas oleovorans according to the criteria of Bergey's manual of determinative bacteriology and sequence analysis of the partial 16S rRNA gene. Optimum growth temperature and pH were 35 degrees C and 8.0, respectively. The strain could degrade 98.03% of acetochlor treated at a concentration of 7.6 mg l(-1) after 7 days of incubation and could tolerate 200 mg l(-1) of acetochlor. When the acetochlor concentration became higher, the degradation cycle became longer. The acetochlor biodegradation products were identified by GC-MS based on mass spectral data and fragmentation patterns. The main plausible degradative pathways involved dechlorination, hydroxylation, N-dealkylation, C-dealkylation and dehydrogenation. PMID:16715401

  8. Clastogenicity of pentachlorophenol, 2,4-D and butachlor evaluated by Allium root tip test.

    PubMed

    Ateeq, Bushra; Abul Farah, M; Niamat Ali, M; Ahmad, Waseem

    2002-02-15

    The meristematic mitotic cells of Allium cepa is an efficient cytogenetic material for chromosome aberration assay on environmental pollutants. For assessing genotoxicity of pentachlorophenol (PCP), 2,4-dichlorophenoxyacetic acid (2,4-D) and 2-chloro-2,6-diethyl-N-(butoxymethyl) acetanilide (butachlor), 50% effective concentration (EC(50)), c-mitosis, stickiness, chromosome breaks and mitotic index (MI) were used as endpoints of genotoxicity. EC(50) values for PCP and butachlor are 0.73 and 5.13 ppm, respectively. 2,4-D evidently induced morphological changes at higher concentrations. Some changes like crochet hooks, c-tumours and broken roots were unique to 2,4-D at 5-20 ppm. No such abnormalities were found in PCP and butachlor treated groups, however, root deteriorated and degenerated at higher concentrations (<3 ppm) in PCP. MI in 2,4-D showed a low average of 14.32% followed by PCP (19.53%), while in butachlor it was recorded 71.6%, which is near to the control value. All chemicals induced chromosome aberrations at statistically significant level. The highest chromosome aberration frequency (11.90%) was recorded in PCP at 3 ppm. Large number of c-mitotic anaphases indicated that butachlor acts as potent spindle inhibitor, whereas, breaks, bridges, stickiness and laggards were most frequently found in PCP showing that it is a potent clastogen. PMID:11815249

  9. Acetochlor in the hydrologic system in the midwestern United States, 1994

    USGS Publications Warehouse

    Kolpin, D.W.; Nations, B.K.; Goolsby, D.A.; Thurman, E.M.

    1996-01-01

    The herbicide acetochlor [2-chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)acetamide] was given conditional registration in the United States by the U.S. Environmental Protection Agency in March 1994. This registration provided a rare opportunity to investigate the occurrence of a pesticide during its first season of extensive use in the midwestern United States. Water samples collected and analyzed by the U.S. Geological Survey during 1994 documented the distribution of acetochlor in the hydrologic system; it was detected in 29% of the rain samples from four sites in Iowa, 17% of the stream samples from 51 sites across nine states, and 0% of the groundwater samples from 38 wells across eight states. Acetochlor exhibited concentration increases in rain and streams following its application to corn in the midwestern United States, with 75% of the rainwater and 35% of the stream samples having acetochlor detected during this time period. Acetochlor concentrations in rain decreased as the growing season progressed. Based on the limited data collected for this study, it is anticipated that acetochlor concentrations will have a seasonal pattern in rain and streams similar to those of other acetanilide herbicides examined. Possible explanations for the absence of acetochlor in groundwater for this study include the rapid degradation of acetochlor in the soil zone, insufficient time for this first extensive use of acetochlor to have reached the aquifers sampled, and the possible lack of acetochlor use in the recharge areas for the wells examined.

  10. 40 CFR 180.249 - Alachlor; tolerances for residues.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., calculated as alachlor in or on the following raw agricultural commodities. Commodity Parts per million Beans, dry 0.1 Beans, succulent lima 0.1 Cattle, fat 0.02 Cattle, meat byproducts 0.02 Cattle, meat 0.02...

  11. 40 CFR 180.249 - Alachlor; tolerances for residues.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., calculated as alachlor in or on the following raw agricultural commodities. Commodity Parts per million Beans, dry 0.1 Beans, succulent lima 0.1 Cattle, fat 0.02 Cattle, meat byproducts 0.02 Cattle, meat 0.02...

  12. 40 CFR 180.249 - Alachlor; tolerances for residues.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., calculated as alachlor in or on the following raw agricultural commodities. Commodity Parts per million Beans, dry 0.1 Beans, succulent lima 0.1 Cattle, fat 0.02 Cattle, meat byproducts 0.02 Cattle, meat 0.02...

  13. 40 CFR 180.249 - Alachlor; tolerances for residues.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., calculated as alachlor in or on the following raw agricultural commodities. Commodity Parts per million Beans, dry 0.1 Beans, succulent lima 0.1 Cattle, fat 0.02 Cattle, meat byproducts 0.02 Cattle, meat 0.02...

  14. Evaluation of mortality and cancer incidence among alachlor manufacturing workers.

    PubMed Central

    Acquavella, J F; Riordan, S G; Anne, M; Lynch, C F; Collins, J J; Ireland, B K; Heydens, W F

    1996-01-01

    Alachlor is the active ingredient in a family of preemergence herbicides. We assessed mortality rates from 1968 to 1993 and cancer incidence rates from 1969 to 1993 for manufacturing workers with potential alachlor exposure. For workers judged to have high alachlor exposure, mortality from all causes combined was lower than expected [23 observed, standardized mortality ratio (SMR) = 0.7, 95% CI, 0.4-1.0], cancer mortality was similar to expected (6 observed, SMR = 0.7, 95% CI, 0.3-1.6), and there were no cancer deaths among workers with 5 or more years high exposure and 15 or more years since first exposure (2.3 expected, SMR = 0, 95% CI, 0-1.6). Cancer incidence for workers with high exposure potential was similar to the state rate [18 observed, standardized incidence ratio (SIR) = 1.2, 95% CI, 0.7-2.0], especially for workers exposed for 5 or more years and with at least 15 years since first exposure (4 observed, SIR = 1.0, 95% CI, 0.3-2.7). The most common cancer for these latter workers was colorectal cancer (2 observed, SIR 3.9, 95% CI, 0.5-14.2 among workers). Despite the limitations of this study with respect to small size and exposure estimating, the findings are useful for evaluating potential alachlor-related health risks because past manufacturing exposures greatly exceeded those characteristic of agricultural operations. These findings suggest no appreciable effect of alachlor exposure on worker mortality or cancer incidence rates during the study period. PMID:8841758

  15. Comparative metabolism of chloroacetamide herbicides and selected metabolites in human and rat liver microsomes.

    PubMed Central

    Coleman, S; Linderman, R; Hodgson, E; Rose, R L

    2000-01-01

    Acetochlor [2-chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methyl-phenyl)-acetamide], alachlor [N-(methoxymethyl)-2-chloro-N-(2, 6-diethyl-phenyl)acetamide], butachlor [N-(butoxymethyl)-2-chloro-N-(2,6-diethyl-phenyl)acetamide], and metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide] are pre-emergent herbicides used in the production of agricultural crops. These herbicides are carcinogenic in rats: acetochlor and alachlor cause tumors in the nasal turbinates, butachlor causes stomach tumors, and metolachlor causes liver tumors. It has been suggested that the carcinogenicity of these compounds involves a complex metabolic activation pathway leading to a DNA-reactive dialkylbenzoquinone imine. Important intermediates in this pathway are 2-chloro-N-(2,6-diethylphenyl)acetamide (CDEPA) produced from alachlor and butachlor and 2-chloro-N-(2-methyl-6-ethylphenyl)acetamide (CMEPA) produced from acetochlor and metolachlor. Subsequent metabolism of CDEPA and CMEPA produces 2,6-diethylaniline (DEA) and 2-methyl-6-ethylaniline (MEA), which are bioactivated through para-hydroxylation and subsequent oxidation to the proposed carcinogenic product dialkylbenzoquinone imine. The current study extends our earlier studies with alachlor and demonstrates that rat liver microsomes metabolize acetochlor and metolachlor to CMEPA (0.065 nmol/min/mg and 0.0133 nmol/min/mg, respectively), whereas human liver microsomes can metabolize only acetochlor to CMEPA (0.023 nmol/min/mg). Butachlor is metabolized to CDEPA to a much greater extent by rat liver microsomes (0.045 nmol/min/mg) than by human liver microsomes (< 0.001 nmol/min/mg). We have determined that both rat and human livers metabolize both CMEPA to MEA (0.308 nmol/min/mg and 0.541 nmol/min/mg, respectively) and CDEPA to DEA (0.350 nmol/min/mg and 0.841 nmol/min/mg, respectively). We have shown that both rat and human liver microsomes metabolize MEA (0.035 nmol/min/mg and 0.069 nmol/min/mg, respectively

  16. Impacts of the herbicide butachlor on the larvae of a paddy field breeding frog (Fejervarya limnocharis) in subtropical Taiwan

    USGS Publications Warehouse

    Liu, Wan-Yi; Wang, Ching-Yuh; Wang, Tsu-Shing; Fellers, Gary M.; Lai, Bo-Chi; Kam, Yeong-Choy

    2011-01-01

    Butachlor is the most commonly used herbicide on paddy fields in Taiwan and throughout Southeast Asia. Since paddy fields provide habitat for pond breeding amphibians, we examined growth, development, time to metamorphosis, and survival of alpine cricket frog tadpoles (Fejervarya limnocharis) exposed to environmentally realistic concentrations of butachlor. We documented negative impacts of butachlor on survival, development, and time to metamorphosis, but not on tadpole growth. The 96 h LC50 for tadpoles was 0.87 mg/l, much lower than the 4.8 mg/l recommended dosage for application to paddy fields. Even given the rapid breakdown of butachlor, tadpoles would be exposed to concentrations in excess of their 96 h LC50 for an estimated 126 h. We also documented DNA damage (genotoxicity) in tadpoles exposed to butachlor at concentrations an order of magnitude less than the 4.8 mg/l recommended application rate. We did not find that butachlor depressed cholinesterase activity of tadpoles, unlike most organophosphorus insecticides. We conclude that butachlor is likely to have widespread negative impacts on amphibians occupying paddy fields with traditional herbicide application.

  17. Joint acute toxicity of the herbicide butachlor and three insecticides to the terrestrial earthworm, Eisenia fetida.

    PubMed

    Wang, Yanhua; Cang, Tao; Yu, Ruixian; Wu, Shenggan; Liu, Xinju; Chen, Chen; Wang, Qiang; Cai, Leiming

    2016-06-01

    The herbicide butachlor and three insecticides phoxim, chlorpyrifos, and lambda-cyhalotrhin are widely used pesticides with different modes of action. As most previous laboratory bioassays for these pesticides have been conducted solely based on acute tests with a single compound, only limited information is available on the possible combined toxicity of these common chemicals to soil organisms. In this study, we evaluated their mixture toxicity on the terrestrial earthworm, Eisenia fetida, with binary, ternary, and quaternary mixtures. Two different types of bioassays were employed in our work, including a contact filter paper toxicity test and a soil toxicity test. Mixture toxicity effects were assessed using the additive index method. For all of the tested binary mixtures (butachlor-phoxim, butachlor-chlorpyrifos, and butachlor-lambda-cyhalothrin), significant synergistic interactions were observed after 14 days in the soil toxicity assay. However, greater additive toxicity was found after 48 h in the contact toxicity bioassay. Most of the ternary and quaternary mixtures exhibited significant synergistic effects on the worms in both bioassay systems. Our findings would be helpful in assessing the ecological risk of these pesticide mixtures to soil invertebrates. The observed synergistic interactions underline the necessity to review soil quality guidelines, which are likely underestimating the adverse combined effects of these compounds. PMID:26946506

  18. KINETICS OF ALACHLOR TRANSFORMATION AND IDENTIFICATION OF METABOLITES UNDER ANAEROBIC CONDITIONS. (R825549C037)

    EPA Science Inventory

    Alachlor is one of the two most commonly used herbicides in the United States. In the environment, little mineralization of this compound has been found to occur, and metabolites of alachlor may be formed and could accumulate. The objectives of this study were to determine the...

  19. Boule gene expression underpins the meiotic arrest in spermatogenesis in male rainbow trout (Oncorhynchus mykiss) exposed to DEHP and butachlor.

    PubMed

    Ahmadivand, Sohrab; Farahmand, Hamid; Teimoori-Toolabi, Ladan; Mirvaghefi, Alireza; Eagderi, Soheil; Geerinckx, Tom; Shokrpoor, Sara; Rahmati-Holasoo, Hooman

    2016-01-01

    Boule, the ancestor of the DAZ (Deleted in AZoospermia) gene family, in most organisms is mainly involved in male meiosis. The present study investigates the effects of the plasticizer DEHP (50mg/kg body weight) and herbicide butachlor (0.39mg/L) on male rainbow trout (Oncorhynchus mykiss) for a 10-day period in two independent experiments. The results showed that plasma testosterone (T) concentrations were significantly lower in fish exposed to either DEHP or butachlor compared to the control fish (P<0.05). Fish showed a significantly elevated hepatosomatic index (HSI) in the butachlor treatment (P<0.05). However, no significant difference was observed in HSI values in the DEHP treatment (P>0.05). In addition, no significant differences were found in the gonadosomatic index (GSI) in both DEHP and butachlor treatments (P>0.05). Histologically, testes of male trout in the control groups were well differentiated and filled with large numbers of cystic structures containing spermatozoa. In contrast, the testes of male trout contained mostly spermatocytes with few spermatozoa in both treated group, suggesting that DEHP and butachlor may inhibit the progression of meiosis. Also, boule gene expression was significantly lower in the testes of male trout affected by DEHP and butachlor in comparison with their control groups (P<0.05), which confirmed the meiotic arrest in affected trout. Based on the results, the present study demonstrated that DEHP and butachlor can inhibit the progression of spermatogenesis in male trout, potentially by causing an arrest of meiosis, maybe due to down-regulation of boule gene expression through T and/or IGF1 via ERK1/2 signaling in T-independent pathways. In addition, these results confirmed that boule can be considered as a predictive marker to assess meiotic efficiency. PMID:26027538

  20. Effect of Butachlor on Antioxidant Enzyme Status and Lipid Peroxidation in Fresh Water African Catfish, (Clarias gariepinus)

    PubMed Central

    Farombi, E. O.; Ajimoko, Y. R.; Adelowo, O. A.

    2008-01-01

    The present study was undertaken to evaluate the influence of butachlor, a widely used herbicide, on antioxidant enzyme system and lipid peroxidation formation in African cat fish (Clarias gariepinus). Fish were exposed to sub-lethal concentrations of butachlor 1, 2, 2.5 ppm and sacrificed 24hrs after treatment. A significant increase in malondialdehyde formation was observed in the liver, kidney, gills and heart of the fish following exposure to different concentrations of butachlor. Superoxide dismutase and catalase activities increased in the liver and kidney but decreased in the gills and heart in a concentration-dependent pattern. Glutathione level and glutathione-S-transferase activities increased (P<0.05) in the liver but decreased in the kidneys, gills and heart when fishes were exposed to the three concentrations of butachlor. The results suggest that butachlor induced oxidative stress in the various tissues of the fish particularly in the kidney and as such the organ may be subjected to severe oxidative toxicity due to depressed glutathione detoxification system. PMID:19151438

  1. Mechanism study of alachlor biodegradation by Paecilomyces marquandii with proteomic and metabolomic methods.

    PubMed

    Szewczyk, Rafał; Soboń, Adrian; Słaba, Mirosława; Długoński, Jerzy

    2015-06-30

    Alachlor is an herbicide that is widely used worldwide to protect plant crops against broadleaf weeds and annual grasses. However, due to its endocrine-disrupting activity, its application had been banned in the European Union. As described in our earlier work, Paecilomyces marquandii is a microscopic fungus capable of alachlor removal by N-acetyl oxidation. Our current work uses proteomics and metabolomics to gain a better understanding of alachlor biodegradation by the microscopic fungus P. marquandii. The data revealed that the addition of alachlor reduced the culture growth and glucose consumption rates. Moreover, the rates of glycolysis and the tricarboxylic acids (TCA) cycle increased during the initial stage of growth, and there was a shift toward the formation of supplementary materials (UDP-glucose/galactose) and reactive oxygen species (ROS) scavengers (ascorbate). Proteomic analysis revealed that the presence of xenobiotics resulted in a strong upregulation of enzymes related to energy, sugar metabolism and ROS production. However, the unique overexpression of cyanide hydratase in alachlor-containing cultures may implicate this enzyme as the key protein involved in the alachlor biodegradation pathway. The characterization of P. marquandii-mediated alachlor removal in terms of cell structure and function provides a deeper insight into the strategies of microorganisms toward xenobiotic biodegradation. PMID:25765177

  2. ANALYTICAL METHOD DEVELOPMENT FOR ALACHLOR ESA AND OTHER ACETANILIDE HERBICIDE DEGRADATION PRODUCTS

    EPA Science Inventory

    In 1998, USEPA published a Drinking Water Contaminant Candidate List (CCL) of 50 chemicals and 10 microorganisms. "Alachlor ESA and other acetanilide herbicide degradation products" is listed on the the 1998 CCL. Acetanilide degradation products are generally more water soluble...

  3. COMETABOLISM OF LOW CONCENTRATIONS OF PROPACHLOR, ALACHLOR, AND CYCLOATE IN SEWAGE AND LAKE WATER

    EPA Science Inventory

    Low concentrations of propachlor (2-chloro-N-isopropylacetanilide) and alachlor (2-chlor-2', 6'-diethyl-N-(methoxymethyl)acetanilide) were not mineralized, cycloate (S-ethyl-N-ethylthiocyclohexanecarbamate) was slowly or not mineralized, and aniline and cyclohexylamine were readi...

  4. Degradation of alachlor using an enhanced sono-Fenton process with efficient Fenton's reagent dosages.

    PubMed

    Wang, Chikang; Liu, Zonghan

    2015-01-01

    In this study, an enhanced sono-Fenton process for the degradation of alachlor is presented. At high ultrasonic power, low pH, and in the presence of adequate Fenton's reagent dosages, alachlor degradation can reach nearly 100%. The toxicity of treated alachlor wastewater, which was measured by changes in cell viability, slightly decreased after the Fenton or ultrasound/H2O2 process and significantly decreased after the enhanced sono-Fenton process. A satisfactory relationship was observed between the total organic carbon removal and cell viability increment, indicating that alachlor mineralization is a key step in reducing the toxicity of the solution. The formation of alachlor degradation byproducts was observed during the oxidation process, in which the first step was the substitution of a chloride by a hydroxyl group. In conclusion, the enhanced sono-Fenton process was effective in the degradation and detoxification of alachlor within a short reaction time. Thus, the treated wastewater can then be passed through a biological treatment unit for further treatment. PMID:25996814

  5. Protocatechuic Acid Promoted Alachlor Degradation in Fe(III)/H2O2 Fenton System.

    PubMed

    Qin, Yaxin; Song, Fahui; Ai, Zhihui; Zhang, Pingping; Zhang, Lizhi

    2015-07-01

    In this study, we demonstrate that protocatechuic acid (PCA) can significantly promote the alachlor degradation in the Fe(III)/H2O2 Fenton oxidation system. It was found that the addition of protocatechuic acid could increase the alachlor degradation rate by 10 000 times in this Fenton oxidation system at pH = 3.6. This dramatic enhancement of alachlor degradation was attributed to the complexing and reduction abilities of protocatechuic ligand, which could form stable complexes with ferric ions to prevent their precipitation and also accelerate the Fe(III)/Fe(II) cycle to enhance the ·OH generation. Meanwhile, the Fe(III)/PCA/H2O2 system could also work well at near natural pH even in the case of PCA concentration as low as 0.1 mmol/L. More importantly, both alachlor and PCA could be effectively mineralized in this Fenton system, suggesting the environmental benignity of PCA/Fe(III)/H2O2 Fenton system. We employed gas chromatography-mass spectrometry to identify the degradation intermediates of alachlor and then proposed a possible alachlor degradation mechanism in this novel Fenton oxidation system. This study provides an efficient way to remove chloroacetanilide herbicides, and also shed new insight into the possible roles of widely existed phenolic acids in the conversion and the mineralization of organic contaminants in natural aquatic environment. PMID:26066010

  6. Formation and transport of the sulfonic acid metabolites of alachlor and metolachlor in soil

    USGS Publications Warehouse

    Aga, D.S.; Thurman, E.M.

    2001-01-01

    Alachlor and metolachlor are dechlorinated and transformed into their corresponding ethane sulfonic acid (ESA) metabolites in soil. In a field-disappearance study, it was shown that alachlor ESA was formed at a faster rate and at concentrations 2-4 times higher than metolachlor ESA, conforming with the observed longer disappearance half-life of metolachlor (15.5 d) in the field as compared to alachlor (8 d). Runoff data also showed higher concentrations of alachlor ESA as compared to metolachlor ESA, even though they were applied at the same levels. Data from soil cores showed transport of the ESA compounds in soil to as far down as 75-90 cm below the surface, at concentrations ranging from less than 0.5 ??g/L to about 50 ??g/L. In contrast, no parent herbicide was detected at these depths. This observation correlates with the higher log KOC values for alachlor (3.33) and metolachlor (3.01) relative to their corresponding ESA metabolites, alachlor ESA (2.26), and metolachlor ESA (2.29).

  7. Influence of rhizosphere microbial ecophysiological parameters from different plant species on butachlor degradation in a riparian soil.

    PubMed

    Yang, Changming; Wang, Mengmeng; Li, Jianhua

    2012-01-01

    Biogeochemical processes in riparian zones regulate contaminant movement to receiving waters and often mitigate the impact of upland sources of contaminants on water quality. However, little research has been reported on the microbial process and degradation potential of herbicide in a riparian soil. Field sampling and incubation experiments were conducted to investigate differences in microbial parameters and butachlor degradation in the riparian soil from four plant communities in Chongming Island, China. The results suggested that the rhizosphere soil had significantly higher total organic C and water-soluble organic C relative to the nonrhizosphere soil. Differences in rhizosphere microbial community size and physiological parameters among vegetation types were significant. The rhizosphere soil from the mixed community of Phragmites australis and Acorus calamus had the highest microbial biomass and biochemical activity, followed by A. calamus, P. australis and Zizania aquatica. Microbial ATP, dehydrogenase activity (DHA), and basal soil respiration (BSR) in the rhizosphere of the mixed community of P. australis and A. calamus were 58, 72, and 62% higher, respectively, than in the pure P. australis community. Compared with the rhizosphere soil of the pure plant communities, the mixed community of P. australis and A. calamus displayed a significantly greater degradation rate of butachlor in the rhizosphere soil. Residual butachlor concentrations in rhizosphere soil of the mixed community of P. australis and A. calamus and were 48, 63, and 68% lower than three pure plant communities, respectively. Butachlor degradation rates were positively correlated to microbial ATP, DHA, and BSR, indicating that these microbial parameters may be useful in assessing butachlor degradation potential in the riparian soil. PMID:22565253

  8. Field-scale mobility and persistence of commercial and stargh-encapusulated atrazine and alachlor

    SciTech Connect

    Gish, T.J.; Shirmohammadi, A.; Wienhold, B.J.

    1994-03-01

    Recent laboratory studies have shown that starch-encapsulation (SE) may reduce leachate losses of certain pesticides. This study compares field-scale mobility and persistence of SE-atrazine [2-chloro-4-ethylamino-6-isopropylamino-s-triazine] and alachlor [2-chloro-N(2,6 diethylphenyl)-N-(methoxymethyl)acetamide] to that of a commerciall formulation (CF) of atrazine and alachlor. The research site consisted of four (0.25 ha) fields. Two fields were under no-tillage management (NT) and two were under conventional tillage (CT). One field in each tillage system received SE-formulated atritzine and alachlor, while the others received CF-atrazine and alachlor. Chemical movement and persistence was determined by analysis of surface samples ({approximately}3 cm) taken immediately after application and 1.1-m soil cores collected seven times over 2 yr. No significant difference in herbicide residue levels was observed between NT and CT, but there was a herbicide formulation effect. Soil residue analysis suggests that SE-atrazine was more persistent and less mobile than CF-atrazine. Starch- encapsulated-alachlor was slightly more persistent than CF-alachlor, but no differences in mobility between formulations was observed. The differential field behavior between SE-herbicides is attributed to the faster release of alachlor from the starch granules. Increased atrazine persistence was attributed to the reduction of leachate losses. The reduction in atrazine leaching is likely due to the slow release from the starch granules and subsequent diffusion into the son matrix where it is less subject to preferential flow processes. 20 refs., 6 figs., 1 tab.

  9. Atrazine, alachlor, and cyanazine in a large agricultural river system

    USGS Publications Warehouse

    Schottler, S.P.; Eisenreich, Steven J.; Capel, P.D.

    1994-01-01

    Atrazine, alachlor, and cyanazine exhibited maximum concentrations of about 1000-6000 ng/L in the Minnesota River in 1990 and 1991, resulting from precipitation and runoff following the application period. Transport of these herbicides to the river occurs via overland flow or by infiltration to tile drainage networks. Suspended sediment, SO42-, and Cl- concentrations were used as indicators of transport mechanisms. The atrazine metabolite, DEA, was present in the river throughout the year. The ratio of DEA to atrazine concentration was used to calculate an apparent first-order soil conversion rate of atrazine to DEA. Half lives of 21-58 d were calculated for 1990 and 1991, respectively. The longer conversion rate in 1991 results from rapid flushing from the soil and minimum exposure to soil microorganisms. Total flux of herbicide to the river was 1-6.5 t, with over 60% of this loading occurring during the month of June. Loading to the river accounts for less than 1.5% of applied herbicide. ?? 1994 American Chemical Society.

  10. In vivo percutaneous absorption and skin decontamination of alachlor in rhesus monkey.

    PubMed

    Wester, R C; Melendres, J; Maibach, H I

    1992-05-01

    The objectives of this study were to determine the percutaneous absorption of alachlor relative to formulation dilution with water, and to determine the ability of soap and water, and of water only, to remove alachlor from skin, relative to time. Alachlor is a preemergence herbicide. The in vivo percutaneous absorption of alachlor in rhesus monkeys was 17.3 +/- 3.3, 15.3 +/- 3.9, and 21.4 +/- 14.2% for 24-h skin exposure to Lasso formulation diluted 1:20, 1:40, and 1:80, respectively. In vivo, there was no support for increased alachlor skin absorption with water dilution, as previously reported for in vitro absorption. The average in vivo absorption of 18% applied dose over 24 h (0.75%/h) was similar to the maximum in vitro rate of 0.8%/h using human skin and human plasma as receptor fluid. Dose accountability in vivo was 80.6-95.2%. [14C]Alachlor in Lasso diluted 1:20 with water was placed on rhesus monkeys at concentrations of 23 micrograms/10 microliters/cm2. Skin decontamination at 0 h with soap and water (50% Ivory liquid 1:1 v/v with water) removed 73 +/- 15.8% (n = 4) of the applied dose with the first wash; this increased to a total of 82.3 +/- 14.8% with two additional washes. Decontamination after 1 h removed 87.5 +/- 12.4% with three successive washes. After 3 h decontamination ability decreased, and after 24 h only 51.9 +/- 12.2% could be recovered with three successive washes. Using water only, at 0 h 36.6 +/- 12.3% alachlor was removed with the first wash and the total increased to 56.0 +/- 14.0% with two additional washes. At 24 h the total amount decreased to 28.7 +/- 12.2% for three successive washes. Alachlor as Lasso in field-use rate (11 micrograms/cm2) and undiluted (217 and 300 micrograms/cm2) proportions were left on rhesus monkey skin for 12 h and decontaminated with soap and water (10% Ivory liquid v/v with water). Continual successive washes (6-8 in sequence) recovered 80-90% of the skin-applied alachlor. These results suggest that simple

  11. Removal of alachlor from water by catalyzed ozonation on Cu/Al2O3 honeycomb

    PubMed Central

    2013-01-01

    Background The herbicide alachlor (2-chloro-2′6′-diethyl-N-methoxymethylacetanilide) has been known as a probable human carcinogen, and the MCL (minimum contamination level) for drinking water has been set at 2 μg L-1. Therefore, the advanced methods for effectively removing it from water are a matter of interest. Catalyzed ozonation is a promising method for refractory organics degradation. Cu/Al2O3 catalyzed ozonation for degrading an endocrine disruptor (alachlor) in water was investigated. Results Experimental results showed that the ozonation of alachlor can be effectively catalyzed and enhanced by Cu/Al2O3-honeycomb. The main intermediate products formed (aliphatic carboxylic acids) were mineralized to a large extent in the catalytic process. Conclusions This study has shown that Cu/Al2O3-honeycomb is a feasible and efficient catalyst in the ozonation of alachlor in water. Less intermediate oxidation product was produced in the catalytic process than in the uncatalytic one. Furthermore, the mineralization of alachlor could be enhanced by increasing the pH of the reaction solution. PMID:23977841

  12. METABOLISM OF ALACHLOR AND PROPACHLOR IN SUSPENSIONS OF PRETREATED SOILS AND IN SAMPLES FROM GROUND WATER AQUIFERS

    EPA Science Inventory

    Suspensions of soils treated in the field with alachlor (2-chloro-2',6'diethyl-N-(methoxymethyl)acetanilide) and propachlor (2-chlor-N-isopropylacetanilide) were tested for their ability to metabolize these herbicides. Less than 8% of (14)C ring-labeled alachlor was mineralized i...

  13. Cytogenetic effects of alachlor and/or atrazine in vivo and in vitro

    SciTech Connect

    Meisner, L.F.; Roloff, B.D. ); Belluck, D.A. )

    1992-01-01

    The purpose of this study was to assess the cytogenetic effects of two commonly used herbicides, alachlor and atrazine, which are often found together in groundwater. Chromosome damage was examined in bone marrow cells of mice drinking water containing 20 ppm alachlor and/or 20 ppm atrazine, with an immunosuppressive dose of cyclophosphamide used as a positive control. Chromosome damage was also quantified in human lymphocytes. The in vitro study demonstrated dose related cytogenetic damage not associated with mitotic inhibition or cell death, with damage due to the alachlor-atrazine combination suggesting an additive model. The fact that the elevated mitotic index was associated with immune suppresion in the cyclophosphamide group suggests that death of cells with accumulated chromosomal aberrations resulted in increased bone marrow proliferation, so a higher fraction of cells examined were newer with less damage.

  14. Alachlor transformation patterns in aquatic field mesocosms under variable oxygen and nutrient conditions

    USGS Publications Warehouse

    Graham, D.W.; Miley, M.K.; Denoyelles, F.; Smith, V.H.; Thurman, E.M.; Carter, R.

    2000-01-01

    Alachlor is one of the most commonly used herbicides in both Europe and North America. Because of its toxic properties, its fate and attenuation in natural waters is practically important. This paper assesses factors that affect alachlor decay rate in aquatic systems using field-scale experimental units. In particular, we used field mesocosms (11.3 m3 outdoor fiberglass tanks) to examine the affect of oxygen level and other factors on decay rate in water columns. This is one of the first studies ever performed where diverse water column conditions have been successfully simulated using common mesocosm-scale facilities. Four treatments were assessed, including aerobic systems (aerobic); low nutrient, oxygen-stratified systems (stratified-LN); moderate nutrient, oxygen-stratified systems (stratified-HN); and anaerobic systems (anaerobic). The lowest half-lives were observed in the anaerobic units (9.7 days) followed by the aerobic (21 days), stratified-HN (22 days), and stratified-LN (46 days) units. Our results indicate that alachlor is transformed most rapidly under anaerobic conditions, although the ambient phosphorus level also appears to influence decay rate. In this study, two common alachlor breakdown products, ethane sulfonic acid (ESA) and oxanilic acid, were also monitored. Oxanilic acid was produced in greater quantities than ESA under all treatments with the highest levels being produced in the stratified-HN units. In general, our results suggest that previous laboratory data, which indicated that high rates of alachlor decay can occur under oxygen-free methanogenic conditions, is translatable to field-scale applications. Copyright (C) 2000 Elsevier Science Ltd.Alachlor is one of the most commonly used herbicides in both Europe and North America. Because of its toxic properties, its fate and attenuation in natural waters is practically important. This paper assesses factors that affect alachlor decay rate in aquatic systems using field-scale experimental

  15. Biodegradation of alachlor in liquid and soil cultures under variable carbon and nitrogen sources by bacterial consortium isolated from corn field soil

    PubMed Central

    2013-01-01

    Alachlor, an aniline herbicide widely used in corn production, is frequently detected in water resources. The main objectives of this research were focused on isolating bacterial consortium capable of alachlor biodegradation, assessing the effects of carbon and nitrogen sources on alachlor biodegradation and evaluating the feasibility of using bacterial consortium in soil culture. Kavar corn field soil with a long history of alachlor application in Fars province of Iran has been explored for their potential of alachlor biodegradation. The influence of different carbon compounds (glucose, sodium citrate, sucrose, starch and the combination of these compounds), the effect of nitrogen sources (ammonium nitrate and urea) and different pH (5.5-8.5) on alachlor removal efficiency by the bacterial consortium in liquid culture were investigated. After a multi-step enrichment program 100 days of acclimation, a culture with the high capability of alachlor degradation was obtained (63%). Glucose and sodium citrate had the highest alachlor reduction rate (85%). Alachlor reduction rate increased more rapidly by the addition of ammonium nitrate (94%) compare to urea. Based on the data obtained in the present study, pH of 7.5 is optimal for alachlor biodegradation. After 30 days of incubation, the percent of alachlor reduction were significantly enhanced in the inoculated soils (74%) as compared to uninoculated control soils (17.67%) at the soil moisture content of 25%. In conclusion, bioaugmentation of soil with bacterial consortium may enhance the rate of alachlor degradation in a polluted soil. PMID:23452801

  16. Atrazine and alachlor transport in claypan soils as influenced by differential antecedent soil water content.

    PubMed

    Kazemi, H V; Anderson, S H; Goyne, K W; Gantzer, C J

    2008-01-01

    Increased attention to ground water contamination has encouraged an interest in mechanisms of solute transport through soils. Few studies have investigated the effect of the initial soil water content on the transport and degradation of herbicides for claypan soils. We investigated the effect of claypan soils at initial field capacity vs. permanent wilting level on atrazine and alachlor transport. The soil studied was Mexico silt loam (fine, smectitic, mesic Aeric Vertic Epiaqualf) with a subsoil clay content, primarily montmorillonite, of >40%. Strontium bromide, atrazine, and alachlor were applied to plots; half were at field capacity (Wet treatment), and half were near the permanent wilting point (Dry treatment). Soil cores were removed at selected depths and times, and cores were analyzed for bromide and herbicide concentrations. Bromide, atrazine, and alachlor were detected at the 0.90-m depth in dry plots within 15 d after experiment initiation. Bromide was detected 0.15 m deeper (P < 0.05) in the Dry compared with the Wet treatment at 1, 7, and 60 d after application and >0.30 m deeper (P < 0.01) in the Dry treatment at 15 and 30 d after application; similar treatment results were found for atrazine and alachlor, although on fewer dates with significant differences. The mobility order of the applied chemicals was bromide > atrazine > alachlor. The atrazine apparent half-life was significantly longer in the Dry plots compared with the Wet plots. The retardation factor determined from the relative velocity of each herbicide to that of bromide was higher for alachlor than for atrazine. This study identifies the impact that shrinkage cracks have for different moisture conditions on preferential transport of herbicides in claypan soils. PMID:18574193

  17. Trends in acetochlor concentrations in surface waters of the White River Basin, Indiana, 1994-96

    USGS Publications Warehouse

    Crawford, Charles G.

    1997-01-01

    Corn herbicides are used extensively in the White River Basin and account for about 70 percent of the total agricultural pesticide use in the basin. Acetochlor, a corn herbicide registered for use in 1994, is expected to reduce the total amount of corn herbicides used because of its broad-spectrum weed control and low use rates. Acetochlor is considered to be a probable human carcinogen, and its continued registration is contingent on concentrations in surface and ground water not exceeding target levels. During 1994, acetochlor was detected in only trace concentrations near the mouth of the White River and not at all in a small stream (93-square-mile drainage) in the northern part of the basin. By 1996, peak concentrations were about 2 and 3 micrograms per liter near the mouth of the White River and in the small stream, respectively. The estimated annual average concentration of acetochlor near the mouth of the White River in 1996 was 0.15 micrograms per liter, well below the 2 micrograms per liter criterion for surface-water supplied community-water systems.

  18. Cu/Zn-superoxide dismutase and glutathione are involved in response to oxidative stress induced by protein denaturing effect of alachlor in Saccharomyces cerevisiae.

    PubMed

    Rattanawong, Kasidit; Kerdsomboon, Kittikhun; Auesukaree, Choowong

    2015-12-01

    Alachlor is a widely used pre-emergent chloroacetanilide herbicide which has been shown to have many harmful ecological and environmental effects. However, the mechanism of alachlor-induced oxidative stress is poorly understood. We found that, in Saccharomyces cerevisiae, the intracellular levels of reactive oxygen species (ROS) including superoxide anions were increased only after long-term exposure to alachlor, suggesting that alachlor is not a pro-oxidant. It is likely that alachlor-induced oxidative stress may result from protein denaturation because alachlor rapidly induced an increased protein aggregation, leading to upregulation of SSA4 and HSP82 genes encoding heat shock proteins (Hsp) of Hsp70 and Hsp90 family, respectively. Although only SOD1 encoding Cu/Zn-superoxide dismutase (SOD), but not SOD2 encoding Mn-SOD, is essential for alachlor tolerance, both SODs play a crucial role in reducing alachlor-induced ROS. We found that, after alachlor exposure, glutathione production was inhibited while its utilization was increased, suggesting the role of glutathione in protecting cells against alachlor, which becomes more important when lacking Cu/Zn-SOD. Based on our results, it seems that alachlor primarily causes damages to cellular macromolecules such as proteins, leading to an induction of endogenous oxidative stress, of which intracellular antioxidant defense systems are required for elimination. PMID:26518674

  19. RESPIRATION AND OSMOREGULATION OF THE ESTUARINE CRAB RHITHROPANOPEUS HARRISII (GOULD): EFFECTS OF THE HERBICIDE ALACHLOR

    EPA Science Inventory

    The effects of a sudden decrease in salinity and exposure to sublethal concentrations of the herbicide, Alachlor, on osmoregulation and respiration of the crab, Rhithropanopeus harrisii, were studied. 2. Crabs were hyperosmotic regulators at salinities below 24 ppt and became hyp...

  20. Effects of (Anti) Androgenic Endocrine Disruptors (DEHP and Butachlor) on Immunoglobulin M (IgM) and Leukocytes Counts of Male Rainbow Trout (Oncorhynchus mykiss).

    PubMed

    Ahmadivand, Sohrab; Farahmand, Hamid; Mirvaghefi, Alireza; Eagderi, Soheil; Zargar, Ashkan

    2015-06-01

    The effect of two anti-androgenic endocrine disrupting compounds, i.e. the plasticizer di (2-ethylhexyl) phthalate (DEHP) and herbicide butachlor, were evaluated for their effects on immunoglobulin M (IgM) and leukocytes in male rainbow trout. Also, plasma testosterone (T) concentration was measured to confirm their anti-androgenic effects. In the first experiment, trout were treated with 50 mg/kg (body weight) DEHP intraperitoneally, and in the second one, fish were exposed to 0.39 mg/L butachlor for 10 days. The results showed that T concentrations and white blood cells were significantly lower in fish exposed to either DEHP or butachlor compared to control fish (p < 0.05). Fish showed significantly elevated neutrophil levels and decreased lymphocyte levels in the butachlor (p < 0.05); however, no significant difference was observed in lymphocyte and neutrophils values in the DEHP treatment (p > 0.05). In addition, no significant differences were found in IgM, eosinophil and monocyte parameters in either DEHP or butachlor treatments (p > 0.05). These results confirmed that leukocytes counts can be considered as a novel marker of immunotoxicity triggered by (anti) androgenic endocrine disruptors. PMID:25708297

  1. Influence of degradation and sorption processes on the persistence and movement of alachlor and dicamba in soils

    SciTech Connect

    Yen, P.Y.

    1992-01-01

    The impact of herbicide usage in agriculture on ground water quality is controlled by the interaction of herbicide degradation, sorption, and transport processes as the herbicide moves through the soil to ground water. The objectives of this thesis were to determine the influence of degradation and sorption processes on the fate of a non-ionic (alachlor) and a weak acid (dicamba) herbicide in four soils (Kim loam, Port Byron silt loam, Webster silty clay loam, and Estherville sandy loam) as a function of soil depth. Alachlor dissipated rapidly under field conditions in Kim soil. Although laboratory studied underestimated the rate of alachlor degradation compared to field conditions, they showed that microbial degradation rather than leaching below sampling depth was the major dissipation pathway of alachlor in soil. Laboratory studies are showed that soils obtained from lower depths had capacities to degrade alachlor, however, at slower rates than surface soils. Sorption of alachlor to soils was moderate (Freundlich sorption coefficient, K[sub f] = 0.7 to 7.3). Movement of alachlor in Kim soil under field conditions was overestimated by leachability indices calculated based on laboratory degradation and sorption studies. Leachability indices would classify alachlor as a [open quotes]leacher[close quotes] in Kim, Port Byron and Estherville soils. In the case of Webster soil, alachlor would be classified as transitional between a [open quotes]leacher[close quotes] and [open quotes]nonleacher[close quotes]. Field dissipation experiments are currently being conducted to evaluate potential leachability of dicamba in the three Minnesota soils. Laboratory studies showed that degradation of dicamba in the four soils was slow (50% dissipation time, DT[sub 50] > 70 days) due to a long lag phase. Soils below 15 cm depth demonstrated slower dicamba degradation capacities than the surface soils. Sorption of dicamba to these soils was minimal (K[sub f] = 0.004 to 0.50).

  2. Environmental distribution of acetochlor, atrazine, chlorpyrifos, and propisochlor under field conditions.

    PubMed

    Konda, L N; Pásztor, Z

    2001-08-01

    The environmental behavior, movement, distribution, persistence, and runoff by rainfall of the pesticides acetochlor, atrazine, chlorpyrifos, and propisochlor were studied under field conditions during a five-month period at normal weather conditions. The pesticide concentrations in soil depths of 0-5 and 5-20 cm, and in sediment and runoff water samples (collected from an artificial reservoir built in the lower part of the experimental plot) were measured every second week and following every runoff event. The contamination of a stream running across the lowest part of the plot was also monitored. The weather conditions were also recorded at the experimental site. The pesticide residues were quantified by a capillary gas chromatograph equipped with a nitrogen phosphorus selective detector (GC-NPD). There was a consistent decrease in pesticide residues in the 0-5 cm soil layer with time after spaying. At 140 days after treatment only atrazine and chlorpyrifos were present; acetochlor and propisochlor were not detected in this soil layer. Atrazine and chlorpyrifos in the soil at a depth of 5-20 cm were detectable during the whole experimental interval, whereas acetochlor and propisochlor concentrations were below the limit of detection. Pesticide losses by the surface runoff process and the contamination of the stream were closely related to the time of rainfall elapsed after treatment and amount of rain at the experimental plots. Losses were primarily dependent on surface rainfall volume and intensity. The maximum detected residues of atrazine and acetochlor in stream water were 1 order of magnitude higher than the maximum residue limit specified by the European Union (EU) for environmental and drinking water (0.1 microg/L for individual compounds and 0.5 microg/L for total pesticides). Chlorpyrifos and propisochlor were not detected in this matrix. PMID:11513679

  3. Behavior of butachlor and pyrazosulfuron-ethyl in paddy water using micro paddy lysimeters under different temperature conditions in spring and summer.

    PubMed

    Ok, Junghun; Doan, Nguyen Hai; Watanabe, Hirozumi; Thuyet, Dang Quoc; Boulange, Julien

    2012-08-01

    The behavior of butachlor and pyrazosulfuron-ethyl in paddy water was investigated using micro paddy lysimeters with prescribed hydrological conditions under ambient temperature in spring and summer for simulating two rice crop seasons. Although they were not significantly different, the dissipation of both herbicides in paddy water in the summer experiment was faster than in the spring experiment. The half-lives (DT(50)) in paddy water for spring and summer experiments were 3.2 and 2.5 days for butachlor, and 3.1 and 1.6 days for pyrazosulfuron-ethyl, respectively. PMID:22696099

  4. Using mass spectrometry to highlight structures of degradation compounds obtained by photolysis of chloroacetamides: case of acetochlor.

    PubMed

    Souissi, Yasmine; Bourcier, Sophie; Ait-Aissa, Sélim; Maillot-Maréchal, Emmanuelle; Bouchonnet, Stéphane; Genty, Christophe; Sablier, Michel

    2013-10-01

    The photooxidation of acetochlor (a pesticide belonging to the acetamides group) using a polychromatic UV irradiation in ultrapure water was studied. This study reports the efficiency of mass spectrometry for the characterization of photodegradation products of acetochlor. Decompositions of protonated ions MH+are proposed in electrospray (ESI) mode for LC–MS, while electron ionization (EI) and chemical ionization modes (CI) are used for GC–MS. The knowledge of fragmentation and the use of a combination of experiments (MS/MS, high resolution) allow the characterization of photoproducts. Structural elucidation is assisted by the use of photolysed deuterated compounds. Fifteen major degradation products have been characterized, five by LC-QTOF, six photoproducts by GC-ITMS, and four are observed by both techniques. In vitro bioassays based on the quantification of receptor-mediated activity demonstrated that acetochlor photolysis engenders a moderate but significant estrogenic activity. Moreover, a quantitative structure–activity relationship (QSAR) approach was used to assess the potential toxicity effect of acetochlor and its by-products. The predictions were analyzed showing a variety of toxicity profiles of acetochlor photoproducts depending on the toxicological investigated endpoint. PMID:24011417

  5. Cometabolism of low concentrations of propachlor, alachlor, and cycloate in sewage and lake water.

    PubMed

    Novick, N J; Alexander, M

    1985-04-01

    Low concentrations of propachlor (2-chloro-N-isopropylacetanilide) and alachlor [2-chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide] were not mineralized, cycloate (S-ethyl-N-ethylthiocyclohexanecarbamate) was slowly or not mineralized, and aniline and cyclohexylamine were readily mineralized in sewage and lake water. Propachlor, alachlor, and cycloate were extensively metabolized, but the products were organic. Little conversion of propachlor and alachlor was evident in sterilized sewage or lake water. The cometabolism of propachlor was essentially linear with time in lake water and was well fit by zero-order kinetics in short periods and by first-order kinetics in longer periods in sewage. The rate of cometabolism in sewage was directly proportional to propachlor concentration at levels from 63 pg/ml to more than 100 ng/ml. Glucose but not aniline increased the yield of products formed during propachlor cometabolism in sewage. No microorganism able to use propachlor as a sole source of carbon and energy was isolated, but bacteria isolated from sewage and lake water metabolized this chemical. During the metabolism of this herbicide by two of the bacteria, none of the carbon was assimilated. Our data indicate that cometabolism of these pesticides takes place at concentrations of synthetic compounds that commonly occur in natural waters. PMID:4004208

  6. Cometabolism of low concentrations of propachlor, alachlor, and cycloate in sewage and lake water.

    PubMed Central

    Novick, N J; Alexander, M

    1985-01-01

    Low concentrations of propachlor (2-chloro-N-isopropylacetanilide) and alachlor [2-chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide] were not mineralized, cycloate (S-ethyl-N-ethylthiocyclohexanecarbamate) was slowly or not mineralized, and aniline and cyclohexylamine were readily mineralized in sewage and lake water. Propachlor, alachlor, and cycloate were extensively metabolized, but the products were organic. Little conversion of propachlor and alachlor was evident in sterilized sewage or lake water. The cometabolism of propachlor was essentially linear with time in lake water and was well fit by zero-order kinetics in short periods and by first-order kinetics in longer periods in sewage. The rate of cometabolism in sewage was directly proportional to propachlor concentration at levels from 63 pg/ml to more than 100 ng/ml. Glucose but not aniline increased the yield of products formed during propachlor cometabolism in sewage. No microorganism able to use propachlor as a sole source of carbon and energy was isolated, but bacteria isolated from sewage and lake water metabolized this chemical. During the metabolism of this herbicide by two of the bacteria, none of the carbon was assimilated. Our data indicate that cometabolism of these pesticides takes place at concentrations of synthetic compounds that commonly occur in natural waters. PMID:4004208

  7. Degradation mechanism of alachlor during direct ozonation and O(3)/H(2)O(2) advanced oxidation process.

    PubMed

    Qiang, Zhimin; Liu, Chao; Dong, Bingzhi; Zhang, Yalei

    2010-01-01

    The degradation of alachlor by direct ozonation and advanced oxidation process O(3)/H(2)O(2) was investigated in this study with focus on identification of degradation byproducts. The second-order reaction rate constant between ozone and alachlor was determined to be 2.5+/-0.1M(-1)s(-1) at pH 7.0 and 20 degrees C. Twelve and eight high-molecular-weight byproducts (with the benzene ring intact) from alachlor degradation were identified during direct ozonation and O(3)/H(2)O(2), respectively. The common degradation byproducts included N-(2,6-diethylphenyl)-methyleneamine, 8-ethyl-3,4-dihydro-quinoline, 8-ethyl-quinoline, 1-chloroacetyl-2-hydro-3-ketone-7-acetyl-indole, 2-chloro-2',6'-diacetyl-N-(methoxymethyl)acetanilide, 2-chloro-2'-acetyl-6'-ethyl-N-(methoxymethyl)-acetanilide, and two hydroxylated alachlor isomers. In direct ozonation, four more byproducts were also identified including 1-chloroacetyl-2,3-dihydro-7-ethyl-indole, 2-chloro-2',6'-ethyl-acetanilide, 2-chloro-2',6'-acetyl-acetanilide and 2-chloro-2'-ethyl-6'-acetyl-N-(methoxymethyl)-acetanilide. Degradation of alachlor by O(3) and O(3)/H(2)O(2) also led to the formation of low-molecular-weight byproducts including formic, acetic, propionic, monochloroacetic and oxalic acids as well as chloride ion (only detected in O(3)/H(2)O(2)). Nitrite and nitrate formation was negligible. Alachlor degradation occurred via oxidation of the arylethyl group, N-dealkylation, cyclization and cleavage of benzene ring. After O(3) or O(3)/H(2)O(2) treatment, the toxicity of alachlor solution examined by the Daphnia magna bioassay was slightly reduced. PMID:20022076

  8. Experimental design approach to the optimization of ultrasonic degradation of alachlor and enhancement of treated water biodegradability.

    PubMed

    Torres, Ricardo A; Mosteo, Rosa; Pétrier, Christian; Pulgarin, Cesar

    2009-03-01

    This work presents the application of experimental design for the ultrasonic degradation of alachlor which is pesticide classified as priority substance by the European Commission within the scope of the Water Framework Directive. The effect of electrical power (20-80W), pH (3-10) and substrate concentration (10-50mgL(-1)) was evaluated. For a confidential level of 90%, pH showed a low effect on the initial degradation rate of alachlor; whereas electrical power, pollutant concentration and the interaction of these two parameters were significant. A reduced model taking into account the significant variables and interactions between variables has shown a good correlation with the experimental results. Additional experiments conducted in natural and deionised water indicated that the alachlor degradation by ultrasound is practically unaffected by the presence of potential *OH radical scavengers: bicarbonate, sulphate, chloride and oxalic acid. In both cases, alachlor was readily eliminated ( approximately 75min). However, after 4h of treatment only 20% of the initial TOC was removed, showing that alachlor by-products are recalcitrant to the ultrasonic action. Biodegradability test (BOD5/COD) carried out during the course of the treatment indicated that the ultrasonic system noticeably increases the biodegradability of the initial solution. PMID:18930694

  9. Transport of Alachlor, Atrazine, Dicamba, and Bromide through Silt and Loam Soils

    NASA Astrophysics Data System (ADS)

    Tindall, J. A.

    2015-12-01

    The herbicides alachlor, atrazine, and dicamba, as well as bromide were applied to soils overlying the High Plains aquifer in Nebraska, to both macropore and non-macropore sites. Three of 6 study areas (exhibiting a high percentage of macropores) were used for analysis of chemical transport. Twelve intact soil cores (30 cm diameter; 40 cm height), were excavated (two each from 0-40 cm and 40-80 cm depths). The first three study areas and soil cores were used to study preferential flow characteristics using dye staining and to determine hydraulic properties; the remaining cores were treated the same as field macropore sites. Two undisturbed experimental field plots, each with a 1 m2 surface area, were established in each of the three macropore study areas. Each preferential plot was instrumented with suction lysimeters, tensiometers, and neutron access tubes - 10 cm increments to 80 cm - and planted in corn. Three study areas that did not exhibit macropores had alachlor, atrazine, and dicamba and bromide disked into the top 15 cm of soil; concentrations were tracked for 120 days - samples were collected on a grid, distributed within 3 plots measuring 50 m x 50 m each. Core samples were collected prior to and immediately after application, and then at 30, 60, and 120 days after application. Each lab core sample was in 15-cm lengths from 0-15 cm, 15-30 cm, 45-60 cm, and 75-90 cm. For areas exhibiting macropores, herbicides had begun to move between 10-15 days after application with concentrations peaking at various depths after heavy rainfall events. Field lysimeter samples showed increases in concentrations of herbicides at depths where laboratory data indicated greater percentages of preferential flowpaths. Concentrations of atrazine, alachlor and dicamba exceeding 0.30, 0.30, and 0.05 μg m1-1 respectively were observed with depth (10-30 cm and 50-70 cm) after two months following heavy rainfall events indicating that preferential flowpaths were a significant

  10. RESPONSES OF MOLECULAR INDICATORS OF EXPOSURE IN MESOCOSMS: COMMON CARP (CYPRINUS CARPIO) EXPOSED TO THE HERBICIDES ALACHLOR AND ATRAZINE

    EPA Science Inventory

    Common carp (Cyprinus carpio) were treated in aquatic mesocosms with a single pulse of the herbicides atrazine or alachlor to study the bioavailability and biological activity of these herbicides using molecular indicators: Liver vitellogenin gene expression in male fish for estr...

  11. Mineral contributions to atrazine and alachlor sorption in soil mixtures of variable organic carbon and clay content

    NASA Astrophysics Data System (ADS)

    Grundl, Tim; Small, Greg

    1993-09-01

    A sediment mixing approach was taken to systematically vary the organic carbon (oc) and clay content (cm) of a suite of organic-poor, clay-rich sediments. Organic carbon content ranged from 3.2% to 0.4% and clay content ranged from 24% to 51%. Atrazine and alachlor were shown to sorb to both natural organic carbon and clay minerals. Partition coefficients to natural organic carbon ( Koc) were found to be 217 and 412 L/kg organic carbon for atrazine and alachlor, respectively. Partition coefficients to the clay fraction were found to be 3.5 and 4.9 L/kg clay for atrazine and alachlor, respectively. When expressed in terms of surface area, the partition coefficients to clay for atrazine and alachlor were 1.80·10 -5 and 2.51·10 -5 L/m 2 clay, respectively. Critical cm/oc ratios at which mineral phase sorption accounts for 50% of the total are defined. Implications for the modelling of herbicide movement in the subsurface if mineral phase sorption is ignored is discussed.

  12. Determination of alachlor and its sulfonic acid metabolite in water by solid-phase extraction and enzyme-linked immunosorbent assay

    USGS Publications Warehouse

    Aga, D.S.; Thurman, E.M.; Pomes, M.L.

    1994-01-01

    Solid-phase extraction (SPE) and enzyme-linked immunosorbent assay (ELISA) were combined for the trace analysis of the herbicide alachlor and its major soil metabolite, ethanesulfonic acid (ESA). The anti-alachlor antibody cross-reacted with ESA, which produced false-positive detections of alachlor in water samples by immunoassay screens. Alachlor and ESA were isolated from water by SPE on a C18 resin and eluted sequentially with ethyl acetate and methanol. Alachlor is soluble in ethyl acetate while the anionic ESA is not. Thus ESA remained adsorbed on the C18 resin and was eluted later with methanol. The combination of SPE with ELISA effectivety separated and quantified both alachlor and ESA using the same antibody for two ELISA methods. The general method may have applicability for the separation of other herbicides and their ionic metabolites. The SPE-ELISA method has a, detection limit of 0.01 ??g/L for alachlor and 0.05 ??g/L for ESA, with a precision of ?? 10%. Analyses of surface and ground water samples were confirmed by gas chromatography/mass spectrometry and high-performance liquid chromatography with photodiode-array detection. Results showed widespread occurrence of ESA in surface and ground water of the midwestern United States, with concentrations ranging from 10 ??g/L.

  13. A derivative photoelectrochemical sensing platform for herbicide acetochlor based on TiO₂-poly (3-hexylthiophene)-ionic liquid nanocomposite film modified electrodes.

    PubMed

    Jin, Dangqin; Xu, Qin; Wang, Yanjuan; Hu, Xiaoya

    2014-09-01

    Nonelectroactive acetochlor can be indirectly determined through the photocatalytical degradation of acetochlor. A derivative visible light photoelectrochemical sensor for indirect detection of the herbicide acetochlor using TiO2-poly(3-hexylthiophene)-ionic liquid nanocomposite is constructed. Poly(3-hexylthiophene) (P3HT) was synthesized via chemical oxidative polymerization with anhydrous FeCl3 as oxidant, 3-hexylthiophene as monomer, chloroform as solvent, and the functional TiO2 nanoparticles were facilely prepared by blending TiO2 nanoparticles and P3HT at room temperature ionic liquid, 1-Butyl-3-methylimidazolium hexafluorophosphate solution. Operational parameters, including the photolysis time, ratios of TiO2 to P3HT, bias voltage and pH of buffer solution have been optimized. Under optimal conditions, the proposed photoelectrochemical method could detect acetochlor ranging from 0.5 to 20 μmol L(-1) with a detection limit of 0.2 nmol L(-1) at a signal-to-noise ratio of 3. The assay results of acetochlor in water samples with the proposed method were in acceptable agreement with those of the gas chromatograph-mass spectrometer (GC-MS) method. The promising sensor opens a new opportunity for fast, portable, and sensitive analysis of acetochlor in environmental samples. PMID:24913872

  14. The decreasing of corn root biomembrane penetration for acetochlor with vermicompost amendment

    NASA Astrophysics Data System (ADS)

    Sytnyk, Svitlana; Wiche, Oliver

    2016-04-01

    One of the topical environmental security issues is management and control of anthropogenic (artificially synthesized) chemical agents usage and utilization. Protection systems development against toxic effects of herbicides should be based on studies of biological indication mechanisms for identification of stressors effect in organisms. Lipid degradation is non-specific reaction to exogenous chemical agents effects. Therefore it is important to study responses of lipid components depending on the stressor type. We studied physiological and biochemical characteristics of lipid metabolism under action of herbicides of chloracetamide group. Corn at different stages of ontogenesis was used as testing object during model laboratory and microfield experiments. Cattle manure treated with earth worms Essenia Foetida was used as compost fertilizer to add to chain: chernozem (black soil) -corn system. It was found several acetochlor actions as following: -decreasing of sterols, phospholipids, phosphatidylcholines and phosphatidylethanolamines content; -increasing pool of available fatty acids and phosphatidic acids associated with intensification of hydrolysis processes; -lypase activity stimulation under effect of stressor in low concentrations; -lypase activity inhibition under effect of high stressor level; -decreasing of polyenoic free fatty acids indicating biomembrane degradation; -accumulation of phospholipids degradation products (phosphatidic acids); -decreasing of high-molecular compounds (phosphatidylcholin and phosphatidylinositol) concentrations; -change in the index of unsaturated and saturated free fatty acids ratio in biomembranes structure; It was established that incorporation of vermicompost in dose 0.4 kg/m2 in black soil lead to corn roots biomembrane restoration. It was fixed the decreasing roots biomembrane penetration for acetochlor in trial with vermicompost. Second compost substances antidote effect is the soil microorganism's activation

  15. Sorption of acetochlor, S-metolachlor, and atrazine in surface and subsurface soil horizons of Argentina.

    PubMed

    Bedmar, Francisco; Daniel, Peter E; Costa, José L; Giménez, Daniel

    2011-09-01

    Understanding herbicide sorption within soil profiles is the first step to predicting their behavior and leaching potential. Laboratory studies were conducted to determine the influence of surface and subsurface soil properties on acetochlor, atrazine, and S-metolachlor sorption. Soil samples were taken from horizons A, B, and C of two loamy soils of the humid pampas of Argentina under no-till management; horizon A was divided into two layers, A(0) (0-5 cm) and A(1) (5 cm to the full thickness of an A horizon). Sorption isotherms were determined from each sampled horizon using the batch equilibrium method and seven concentrations (0, 0.1, 0.5, 2.0, 5.0, 10.0, and 20.0 mg L(-1)). Sorption affinity of herbicides was approximated by the Freundlich equation. The sorption strength K(f) (mg(1 - 1/n) kg(-1) L(1/n) ) over the soils and horizons studied followed the order S-metolachlor (16.51-29.19) > atrazine (4.85-12.34) ≥ acetochlor (5.17-11.97), which was closely related to the hydrophobicity of herbicides expressed as octanol-water partition coefficient (K(OW) ). The K(f) values of the three herbicides were positively correlated with soil organic carbon, with a significance of p < 0.01. Values of K(f) for the three herbicides decreased with depth in the two soils, indicating greater sorption onto surficial soil horizons and possibly a delayed transport toward subsurface soils and subsequent pollution of groundwater. PMID:21692102

  16. Involvement of the cytochrome P450 system EthBAD in the N-deethoxymethylation of acetochlor by Rhodococcus sp. strain T3-1.

    PubMed

    Wang, Fei; Zhou, Jie; Li, Zhoukun; Dong, Weiliang; Hou, Ying; Huang, Yan; Cui, Zhongli

    2015-03-01

    Acetochlor [2-chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)-acetamide] is a widely applied herbicide with potential carcinogenic properties. N-Deethoxymethylation is the key step in acetochlor biodegradation. N-Deethoxymethylase is a multicomponent enzyme that catalyzes the conversion of acetochlor to 2'-methyl-6'-ethyl-2-chloroacetanilide (CMEPA). Fast detection of CMEPA by a two-enzyme (N-deethoxymethylase-amide hydrolase) system was established in this research. Based on the fast detection method, a three-component enzyme was purified from Rhodococcus sp. strain T3-1 using ammonium sulfate precipitation and hydrophobic interaction chromatography. The molecular masses of the components of the purified enzyme were estimated to be 45, 43, and 11 kDa by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). Based on the results of peptide mass fingerprint analysis, acetochlor N-deethoxymethylase was identified as a cytochrome P450 system, composed of a cytochrome P450 oxygenase (43-kDa component; EthB), a ferredoxin (45 kDa; EthA), and a reductase (11 kDa; EthD), that is involved in the degradation of methyl tert-butyl ether. The gene cluster ethABCD was cloned by PCR amplification and expressed in Escherichia coli BL21(DE3). Resting cells of a recombinant E. coli strain showed deethoxymethylation activity against acetochlor. Subcloning of ethABCD showed that ethABD expressed in E. coli BL21(DE3) has the activity of acetochlor N-deethoxymethylase and is capable of converting acetochlor to CMEPA. PMID:25595756

  17. Involvement of the Cytochrome P450 System EthBAD in the N-Deethoxymethylation of Acetochlor by Rhodococcus sp. Strain T3-1

    PubMed Central

    Wang, Fei; Zhou, Jie; Li, Zhoukun; Dong, Weiliang; Hou, Ying; Huang, Yan

    2015-01-01

    Acetochlor [2-chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)-acetamide] is a widely applied herbicide with potential carcinogenic properties. N-Deethoxymethylation is the key step in acetochlor biodegradation. N-Deethoxymethylase is a multicomponent enzyme that catalyzes the conversion of acetochlor to 2′-methyl-6′-ethyl-2-chloroacetanilide (CMEPA). Fast detection of CMEPA by a two-enzyme (N-deethoxymethylase–amide hydrolase) system was established in this research. Based on the fast detection method, a three-component enzyme was purified from Rhodococcus sp. strain T3-1 using ammonium sulfate precipitation and hydrophobic interaction chromatography. The molecular masses of the components of the purified enzyme were estimated to be 45, 43, and 11 kDa by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). Based on the results of peptide mass fingerprint analysis, acetochlor N-deethoxymethylase was identified as a cytochrome P450 system, composed of a cytochrome P450 oxygenase (43-kDa component; EthB), a ferredoxin (45 kDa; EthA), and a reductase (11 kDa; EthD), that is involved in the degradation of methyl tert-butyl ether. The gene cluster ethABCD was cloned by PCR amplification and expressed in Escherichia coli BL21(DE3). Resting cells of a recombinant E. coli strain showed deethoxymethylation activity against acetochlor. Subcloning of ethABCD showed that ethABD expressed in E. coli BL21(DE3) has the activity of acetochlor N-deethoxymethylase and is capable of converting acetochlor to CMEPA. PMID:25595756

  18. Simultaneous determination of alachlor, metolachlor, atrazine, and simazine in water and soil by isotope dilution gas chromatography/mass spectrometry

    SciTech Connect

    Huang, L.Q.

    1989-03-01

    A multiresidue method was developed for the simultaneous determination of low parts per billion (ppb) concentrations of the herbicides alachlor, metolachlor, atrazine, and simazine in water and soil using isotope dilution gas chromatography/mass spectrometry (GC/MS). Known amounts of /sup 15/N,/sup 13/C-alachlor and /sup 2/H/sub 5/-atrazine were added to each sample as internal standards. The samples were then prepared by a solid phase extraction with no further cleanup. A high resolution GC/low resolution MS system with data acquisition in selected ion monitoring mode was used to quantitate herbicides in the extract. The limit of detection was 0.05 ppb for water and 0.5 ppb for soil. Accuracy greater than 80% and precision better than 4% was demonstrated with spiked samples.

  19. Comparative sensitivity of five species of macrophytes and six species of algae to atrazine, metribuzin, alachlor, and metolachlor

    USGS Publications Warehouse

    Fairchild, J.F.; Ruessler, D.S.; Carlson, A.R.

    1998-01-01

    This study determined the relative sensitivity of five species of aquatic macrophytes and six species of algae to four commonly used herbicides (atrazine, metribuzin, alachlor, and metolachlor). Toxicity tests consisted of 96-h (duckweed and algae) or 14-d (submerged macrophytes) static exposures. The triazine herbicides (atrazine and metribuzin) were significantly more toxic to aquatic plants than were the acetanilide herbicides (alachlor and metolachlor). Toxicity studies ranked metribuzin > atrazine > alachlor > metolachlor in decreasing order of overall toxicity to aquatic plants. Relative sensitivities of macrophytes to these herbicides decreased in the order of Ceratophyllum > Najas > Elodea > Lemna > Myriophyllum. Relative sensitivities of algae to herbicides decreased in the order of Selenastrum > Chlorella > Chlamydomonas > Microcystis > Scenedesmus > Anabaena. Algae and macrophytes were of similar overall sensitivities to herbicides. Data indicated that Selenastrum, a commonly tested green alga, was generally more sensitive compared to other plant species. Lemna minor, a commonly tested floating vascular plant, was of intermediate sensitivity, and was fivefold less sensitive than Ceratophyllum, which was the most sensitive species tested. The results indicated that no species was consistently most sensitive, and that a suite of aquatic plant test species may be needed to perform accurate risk assessments of herbicides.

  20. Kinetic study of heterogeneous ozonolysis of alachlor, trifluralin and terbuthylazine adsorbed on silica particles under atmospheric conditions

    NASA Astrophysics Data System (ADS)

    Pflieger, Maryline; Monod, Anne; Wortham, Henri

    To better understand the atmospheric behaviour of pesticides, heterogeneous ozonolysis of three herbicides (alachlor, terbuthylazine and trifluralin) adsorbed on silica particles were performed in a flow reactor. The experimental setup used in this study and previously validated ( Pflieger et al., 2009) has been specially developed to investigate extremely slow reactivity. The pesticides were adsorbed on particles using a gas/solid adsorption equilibrium, in order to simulate atmospheric conditions. After exposure to ozone concentrations ranging from 5 to 41 ppm during 90 min to 6 h, the kinetics were calculated by comparing the initial and the remaining amounts of pesticides adsorbed on silica particles. This work offers the first results of heterogeneous ozonolysis of alachlor and trifluralin adsorbed on mineral particles. Although alachlor and terbuthylazine were expected to react with ozone, no degradation was observed which leads to a lifetime higher than 8 months towards ozonolysis (for 40 ppb of O 3). A significant degradation of trifluralin adsorbed on silica particles by heterogeneous ozonolysis was observed. The experimental data could be fit by both the Langmuir-Rideal and the Langmuir-Hinshelwood models resulting in atmospheric lifetimes (towards heterogeneous ozonolysis) of 40 and 32 days respectively (for 40 ppb of O 3). These results are discussed and compared to other studies.

  1. Comparative study of photocatalytic and photoelectrocatalytic properties of alachlor using different morphology TiO2/Ti photoelectrodes.

    PubMed

    Xin, Yanjun; Liu, Huiling; Han, Lei; Zhou, Yabin

    2011-09-15

    Wormhole-shaped TiO(2)/Ti (WT) and nanotube-shaped TiO(2)/Ti (TNT) photoelectrodes were prepared by anodic oxidation method. The morphology and structure were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). It was found that both crystal types of WT and TNT photoelectrodes were composed of anatase and rutile TiO(2) phases; however TNT photoelectrodes had highly ordered nanostructure. The photoelectrochemical (PECH) and photoelectrocatalytic (PEC) properties of WT and TNT photoelectrodes were investigated by photocurrent transient, open-circuit potential and degradation rate of alachlor under the artificial solar light illumination. All results showed that TNT photoelectrodes prepared in NaF-Na(2)SO(4) solution have more excellent photoelectron properties than WT photoelectrodes prepared in H(2)SO(4) solution. The photocatalytic (PC) and PEC experiments of alachlor showed that PC and PEC activities of TNT photoelectrodes were superior to WT photoelectrodes. At applied bias potentials the degradation rate of alachlor at TNT photoelectrodes increased significantly to 94.5%. The higher PC and PEC performance of TNT photoelectrodes were ascribed to the long-range ordered structure and short-orientation diffusion distance of photogenerated carries. PMID:21802202

  2. Novel Three-Component Rieske Non-Heme Iron Oxygenase System Catalyzing the N-Dealkylation of Chloroacetanilide Herbicides in Sphingomonads DC-6 and DC-2

    PubMed Central

    Chen, Qing; Wang, Cheng-Hong; Deng, Shi-Kai; Wu, Ya-Dong; Li, Yi; Yao, Li; Jiang, Jian-Dong; Yan, Xin; Li, Shun-Peng

    2014-01-01

    Sphingomonads DC-6 and DC-2 degrade the chloroacetanilide herbicides alachlor, acetochlor, and butachlor via N-dealkylation. In this study, we report a three-component Rieske non-heme iron oxygenase (RHO) system catalyzing the N-dealkylation of these herbicides. The oxygenase component gene cndA is located in a transposable element that is highly conserved in the two strains. CndA shares 24 to 42% amino acid sequence identities with the oxygenase components of some RHOs that catalyze N- or O-demethylation. Two putative [2Fe-2S] ferredoxin genes and one glutathione reductase (GR)-type reductase gene were retrieved from the genome of each strain. These genes were not located in the immediate vicinity of cndA. The four ferredoxins share 64 to 72% amino acid sequence identities to the ferredoxin component of dicamba O-demethylase (DMO), and the two reductases share 62 to 65% amino acid sequence identities to the reductase component of DMO. cndA, the four ferredoxin genes, and the two reductases genes were expressed in Escherichia coli, and the recombinant proteins were purified using Ni-affinity chromatography. The individual components or the components in pairs displayed no activity; the enzyme mixture showed N-dealkylase activities toward alachlor, acetochlor, and butachlor only when CndA-His6 was combined with one of the four ferredoxins and one of the two reductases, suggesting that the enzyme consists of three components, a homo-oligomer oxygenase, a [2Fe-2S] ferredoxin, and a GR-type reductase, and CndA has a low specificity for the electron transport component (ETC). The N-dealkylase utilizes NADH, but not NADPH, as the electron donor. PMID:24928877

  3. Single-step uncalcined N-TiO2 synthesis, characterizations and its applications on alachlor photocatalytic degradations

    NASA Astrophysics Data System (ADS)

    Suwannaruang, Totsaporn; Wantala, Kitirote

    2016-09-01

    The aims of this research were to synthesize nitrogen doped TiO2 (N-TiO2) photocatalysts produced by hydrothermal technique and to test the degradation performance of alachlor by photocatalytic process under UV irradiations in the effect of aging temperature and time in the preparation process. The characterizations of synthesized TiO2 such as specific surface area, particle size, phase structure and elements were analyzed by using the Brunauer-Emmett-Teller (BET) technique, Transmission Electron Microscopy (TEM), X-ray Diffractometer (XRD) and Energy Dispersive X-ray spectrometer (EDX), respectively. The Central Composite Design (CCD) was used to design the experiment to determine the optimal condition, main effects and their interactions by using specific surface area, percent alachlor removal and observed first-order rate constant as responses. The kinetic reactions of alachlor degradation were explained by using Langmuir-Hinshelwood expression to confirm the reaction took place on the surface of photocatalyst. The results showed that the effect of aging temperatures was significant on surface area, whereas aging time was insignificant. Additionally, the square term of aging temperature and interaction term were shown significant on the specific surface area as well. The highest specific surface area from response surface at aging temperature between 150-175 °C and aging time between 6-13 h was found in a range of 100-106 m2/g. The average particle size of TiO2 was similar to crystallite size. Therefore, it can be concluded that one particle has only one crystal. The element analysis has shown 10% of nitrogen in TiO2 structure that the energy band-gap about 2.95 eV was found. Although, the effects of aging temperature and time on percent alachlor removal and observed first-order rate constants were insignificant, both terms were significant in term of the square for alachlor photocatalytic degradation. The optimal condition of both responses was achieved at an

  4. A urinary metabonomics analysis of long-term effect of acetochlor exposure on rats by ultra-performance liquid chromatography/mass spectrometry.

    PubMed

    Li, Longxue; Wang, Maoqing; Chen, Shuhong; Zhao, Wei; Zhao, Yue; Wang, Xu; Zhang, Yang

    2016-03-01

    The study was to assess the long-term toxic effects of acetochlor on rats. Two different doses (42.96 and 107.4 mg/kg body weight/day) of acetochlor were administered to Wistar rats through their food for over 24 weeks. Rat urine samples were collected at two time-points for the measurements of the metabonomics profiles with ultra-performance liquid chromatography-mass spectrometry (UPLC-MSMS). The results of clinical chemistry and histopathology suggested that long-term use of acetochlor in rats caused liver and kidney damage, and dysfunction of antioxidant system. The urinary metabonomics analysis indicated that the high and low-dose exposure of acetochlor could cause alterations of these metabonomics in urine in the rat. Significant changes of the levels of hippuric acid (0.403-fold decrease), citric acid (0.430-fold decrease), pantothenic acid (0.486-fold decrease), uracil (0.419-fold decrease), β-Alanine (0.325-fold decrease), nonanedioic acid (0.445-fold decrease), L-tyrosine (0.410-fold decrease), D-glucuronic acid (8.389-fold increase) and 2-ethyl-6-methyl-N-methyl-2-chloro-acetanilide in urine were observed. In addition, it may interfere with the fatty acid synthesis, the pyrimidine degradation and pantothenate biosynthesis. The level of 2-ethyl-6-methyl-N-methyl-2-chloro-acetanilide is detected in all treated groups which is not found in the control groups, indicating which can be used as an early, sensitive marker of acetochlor exposure in rat. This study illustrates the important utility of metabonomics approaches to understand the toxicity of long-term exposure of acetochlor. PMID:26969444

  5. Alterations in juvenile diploid and triploid African catfish skin gelatin yield and amino acid composition: Effects of chlorpyrifos and butachlor exposures.

    PubMed

    Karami, Ali; Karbalaei, Samaneh; Zad Bagher, Fariba; Ismail, Amin; Simpson, Stuart L; Courtenay, Simon C

    2016-08-01

    Skin is a major by-product of the fisheries and aquaculture industries and is a valuable source of gelatin. This study examined the effect of triploidization on gelatin yield and proximate composition of the skin of African catfish (Clarias gariepinus). We further investigated the effects of two commonly used pesticides, chlorpyrifos (CPF) and butachlor (BUC), on the skin gelatin yield and amino acid composition in juvenile full-sibling diploid and triploid African catfish. In two separate experiments, diploid and triploid C. gariepinus were exposed for 21 days to graded CPF [mean measured: 10, 16, or 31 μg/L] or BUC concentrations [Mean measured: 22, 44, or 60 μg/L]. No differences in skin gelatin yield, amino acid or proximate compositions were observed between diploid and triploid control groups. None of the pesticide treatments affected the measured parameters in diploid fish. In triploids, however, gelatin yield was affected by CPF treatments while amino acid composition remained unchanged. Butachlor treatments did not alter any of the measured variables in triploid fish. To our knowledge, this study is the first to investigate changes in the skin gelatin yield and amino acid composition in any animal as a response to polyploidization and/or contaminant exposure. PMID:27182978

  6. The phenotype of grape leaves caused by acetochlor or fluoroglycofen, and effects of latter herbicide on grape leaves.

    PubMed

    Tan, Wei; Liang, Ting; Li, Qingliang; Du, Yuanpeng; Zhai, Heng

    2014-09-01

    Fluoroglycofen and acetochlor are two different herbicides used in vineyards to eradicate weeds. This present study first characterized the effects of these chemicals on phenotype of grape leaves. Results showed that acetochlor caused the middle- and upper-node grape leaves become yellow at 60th day after treatment, while fluoroglycofen caused the ones became dark green. Then the effects of fluoroglycofen on photosynthetic pigments and chloroplast ultrastructure were characterized. Results showed that fluoroglycofen increased the chlorophyll and carotenoid contents by different extent in different node leaves, while it did not affect the net photosynthesis rate significantly. Chloroplast ultrastructure analysis showed that the gap between thylakoids layers in few chloroplasts of middle-node leaves increased, which was also observed in ones of upper-node leaves; the number and size of chloroplast increased. Analysis on the deformed leaves of grapevines treated with 375 g ai ha(-1) fluoroglycofen showed that the starch grain per cell was much more and larger than that in the same size control leaves; the dark green and yellow parts had more or fewer chloroplast than the control, respectively, but both with more grana per chloroplast and less layers per granum. Chloroplasts went larger and round. Taken together, these results suggested that fluoroglycofen caused the grape leaves become dark green, which might be associated with the changes of chloroplast; the growth inhibition in the second year might be due to accumulation of starch. PMID:25175657

  7. Effect of crop competition and herbicides on yellow nutsedge (Cyperus esculentus L. ) and root absorption, translocation, and metabolism of alachlor and metolachlor by yellow nutsedge

    SciTech Connect

    Chamblee, R.W.

    1985-01-01

    Field studies were conducted in 1980, 1981, and 1982 to compare management programs involving different cultural practices, at-planting herbicides, and postemergence herbicides to reduce yellow nutsedge (Cyperus esculentus L.) populations, in a soybean (Glycine max (L.) Merr. Ransom)-corn (Zea mays L. Pioneer 3161 and Pioneer 3358) rotation. In laboratory studies, alachlor and metolachlor toxicity, absorption, translocation, and metabolism were investigated in different sized yellow nutsedge plants. Exposure to herbicides was restricted to plant roots. Plant sizes evaluated were 4 to 6, 10 to 15, and 18 to 22-cm tall at experiment initiation. Concentrations of greater than 0.1 ppm of both alachlor and metolachlor reduced small yellow nutsedge plant size by more than 50%. At concentrations greater than 0.2 ppm increased growth reduction was seen from metolachlor but not from alachlor. Ten to 15-cm plants exposed to 1.6 ppm of alachlor and metolachlor had plant size reductions of 48 and 62%, respectively, after 12 days. There was no difference in root absorption of /sup 14/C alachlor or /sup 14/C metolachlor from nutrient solutions. After 8 days, greater than 40, 58, and 76% of available /sup 14/C was absorbed by small, medium and large plants, respectively. After 4 and 8 days of exposure, small yellow nutsedge plants had translocated 2.6 times as much /sup 14/C metolachlor to plant shoots than /sup 14/C alachlor. Larger plants translocated the herbicides equally. Small sized plants treated with /sup 14/C metolachlor retained greater than 23% of the parent material.

  8. Relation of Landscape Position and Irrigation to Concentrations of Alachlor, Atrazine, and Selected Degradates in Regolith in Northeastern Nebraska

    USGS Publications Warehouse

    Verstraeten, Ingrid M.; Lewis, D.T.; McCallister, D.L.; Parkhurst, A.; Thurman, E.M.

    1996-01-01

    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 ??g/kg) and ethanesulfonic acid (maximum 10 ??g/kg) were associated with landscape position, but not with irrigation. Alachlor (maximum 24 ??g/kg), deethylatrazine (maximum 1.5 ??g/kg), and deisopropylatrazine (maximum 3.5 ??g/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.

  9. Determination of alachlor and its metabolite 2,6-diethylaniline in microbial culture medium using online microdialysis enriched-sampling coupled to high-performance liquid chromatography.

    PubMed

    Chen, Chi-Zen; Yan, Cheing-Tong; Kumar, Ponnusamy Vinoth; Huang, Jenn-Wen; Jen, Jen-Fon

    2011-08-10

    In this study, a simple and novel microdialysis sampling technique incorporating hollow fiber liquid phase microextraction (HF-LPME) coupled online to high-performance liquid chromatography (HPLC) for the one-step sample pretreatment and direct determination of alachlor (2-chloro-2',6'-diethyl-N -(methoxymethyl)acetanilide) and its metabolite 2,6-diethylaniline (2,6-DEA) in microbial culture medium has been developed. A reversed-phase C-18 column was utilized to separate alachlor and 2,6-DEA from other species using an acetonitrile/water mixture (1:1) containing 0.1 M phosphate buffer solution at pH 7.0 as the mobile phase. Detection was carried out with a UV detector operated at 210 nm. Parameters that influenced the enrichment efficiency of online HF-LPME sampling, including the length of the hollow fiber, the perfusion solvent and its flow rate, the pH, and the salt added in sample solution, as well as chromatographic conditions were thoroughly optimized. Under optimal conditions, excellent enrichment efficiency was achieved by the microdialysis of a sample solution (pH 7.0) using hexane as perfusate at the flow rate of 4 μL/min. Detection limits were 72 and 14 ng/mL for alachlor and 2,6-DEA, respectively. The enrichment factors were 403 and 386 (RSD < 5%) for alachlor and 2,6-DEA, respectively, when extraction was performed by using a 40 cm regenerated cellulose hollow fiber and hexane as perfusion solvent at the flow rate of 0.1 μL/min. The proposed method provides a sensitive, flexible, fast, and eco-friendly procedure to enrich and determine alachlor and its metabolite (2,6-DEA) in microbial culture medium. PMID:21707080

  10. GC-MS(n) and LC-MS/MS couplings for the identification of degradation products resulting from the ozonation treatment of Acetochlor.

    PubMed

    Bouchonnet, Stéphane; Bourcier, Sophie; Souissi, Yasmine; Genty, Christophe; Sablier, Michel; Roche, Pascal; Boireau, Véronique; Ingrand, Valérie

    2012-04-01

    The degradation of the chloracetamide herbicide acetochlor has been studied under simulated ozonation treatment plant conditions. The degradation of acetochlor included the formation of several degradation products that were identified using GC/ion-trap mass spectrometry with EI and CI and HPLC/electrospray-QqTOF mass spectrometry. Thirteen ozonation products of acetochlor have been identified. Ozonation of the deuterated herbicide combined to MS(n) and high-resolution mass measurement allowed effective characterization of the degradation products. At the exception of one of them, the product B (2-chloro-2', ethyl-6', methyl-acetanilide), none of the identified degradation products has been already reported in the literature. Post-ozonation kinetics studies revealed that the concentrations of most degradation products evolved noticeably with time, particularly during the first hours following the ozonation treatment. This raises concerns about the fate of degradation products in the effluents of treatment plants and suggests the need for a better control on these products if their toxicity was demonstrated. PMID:22689619

  11. The role of reactive oxygen species in the herbicide acetochlor-induced DNA damage on Bufo raddei tadpole liver.

    PubMed

    Liu, Yang; Zhang, Yingmei; Liu, Jianghai; Huang, Dejun

    2006-06-10

    After exposure of Bufo raddei tadpoles to acetochlor (ACETO) for 14 days, malondialdehyde (MDA) and DNA-single strand break (DNA-SSB) in livers were analyzed. An enhanced accumulation of MDA suggests that ACETO causes oxidative stress, and the significant increase in the level of DNA-SSB indicates that ACETO induces DNA damage in a dose-dependent manner as well. On the basis of the fact that oxidative stress is caused by excessive production of reactive oxygen species (ROS), and the present results, we speculate that ACETO-induced DNA damage may be a consequence of the generation of ROS. To evaluate this hypothesis, tadpoles were treated with ROS scavenger, N-acetyl-L-cysteine (NAC) or melatonin (MEL), prior to ACETO exposure. The decrease of DNA-SSB level and the increase of total antioxidant capability (TAC) show that ACETO-caused DNA damage can be attenuated by NAC and MEL. In addition, a negative correlation was observed between the extent of DNA damage and the level of TAC in tadpole liver. In conclusion, the results suggest that ACETO-induced DNA damage is mediated by ROS. PMID:16513190

  12. A Novel Aldo-Keto Reductase (AKR17A1) of Anabaena sp. PCC 7120 Degrades the Rice Field Herbicide Butachlor and Confers Tolerance to Abiotic Stresses in E. coli.

    PubMed

    Agrawal, Chhavi; Sen, Sonia; Yadav, Shivam; Rai, Shweta; Rai, Lal Chand

    2015-01-01

    Present study deals with the identification of a novel aldo/keto reductase, AKR17A1 from Anabaena sp. PCC7120 and adds on as 17th family of AKR superfamily drawn from a wide variety of organisms. AKR17A1 shares many characteristics of a typical AKR such as- (i) conferring tolerance to multiple stresses like heat, UV-B, and cadmium, (ii) excellent activity towards known AKR substrates (isatin and 2-nitrobenzaldehyde), and (iii) obligate dependence on NADPH as a cofactor for enzyme activity. The most novel attribute of AKR17A1, first reported in this study, is its capability to metabolize butachlor, a persistent rice field herbicide that adversely affects agro-ecosystem and non-target organisms. The AKR17A1 catalyzed- degradation of butachlor resulted into formation of 1,2-benzene dicarboxylic acid and 2,6 bis (1,1, dimethylethyl) 4,-methyl phenol as the major products confirmed by GC-MS analysis. PMID:26372161

  13. A Novel Aldo-Keto Reductase (AKR17A1) of Anabaena sp. PCC 7120 Degrades the Rice Field Herbicide Butachlor and Confers Tolerance to Abiotic Stresses in E. coli

    PubMed Central

    Agrawal, Chhavi; Sen, Sonia; Yadav, Shivam; Rai, Shweta; Rai, Lal Chand

    2015-01-01

    Present study deals with the identification of a novel aldo/keto reductase, AKR17A1 from Anabaena sp. PCC7120 and adds on as 17th family of AKR superfamily drawn from a wide variety of organisms. AKR17A1 shares many characteristics of a typical AKR such as— (i) conferring tolerance to multiple stresses like heat, UV-B, and cadmium, (ii) excellent activity towards known AKR substrates (isatin and 2-nitrobenzaldehyde), and (iii) obligate dependence on NADPH as a cofactor for enzyme activity. The most novel attribute of AKR17A1, first reported in this study, is its capability to metabolize butachlor, a persistent rice field herbicide that adversely affects agro-ecosystem and non-target organisms. The AKR17A1 catalyzed- degradation of butachlor resulted into formation of 1,2-benzene dicarboxylic acid and 2,6 bis (1,1, dimethylethyl) 4,-methyl phenol as the major products confirmed by GC-MS analysis. PMID:26372161

  14. Determination of Low Concentrations of Acetochlor in Water by Automated Solid-Phase Extraction and Gas Chromatography with Mass-Selective Detection

    USGS Publications Warehouse

    Lindley, C.E.; Stewart, J.T.; Sandstrom, M.W.

    1996-01-01

    A sensitive and reliable gas chromatographic/mass spectrometric (GC/MS) method for determining acetochlor in environmental water samples was developed. The method involves automated extraction of the herbicide from a filtered 1 L water sample through a C18 solid-phase extraction column, elution from the column with hexane-isopropyl alcohol (3 + 1), and concentration of the extract with nitrogen gas. The herbicide is quantitated by capillary/column GC/MS with selected-ion monitoring of 3 characteristic ions. The single-operator method detection limit for reagent water samples is 0.0015 ??g/L. Mean recoveries ranged from about 92 to 115% for 3 water matrixes fortified at 0.05 and 0.5 ??g/L. Average single-operator precision, over the course of 1 week, was better than 5%.

  15. A High-Performance Liquid Chromatography-Based Screening Method for the Analysis of Atrazine, Alachlor, and Ten of Their Transformation Products

    USGS Publications Warehouse

    Schroyer, B.R.; Capel, P.D.

    1996-01-01

    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 ??L) 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 ??g/L for atrazine and its transformation products and from 80 to 320 ng/g and from 80 to 320 ??g/L for alachlor and its transformation products, respectively.

  16. A silica coated paper substrate: development and its application in paper spray mass spectrometry for rapid analysis of pesticides in milk.

    PubMed

    Wang, Qian; Zheng, Yajun; Zhang, Xiaoling; Han, Xiaoxiao; Wang, Teng; Zhang, Zhiping

    2015-12-01

    A novel silica coated paper substrate is developed through a facile vacuum filtration method by using the commercially available silica particles as the coating material and corn starch as the adhesive agent. Unlike the commercial silica coated paper (namely grade SG81 paper), the resulting paper substrate was covered by a layer of silica particles on the top side of the paper, and no cellulosic fibers were exposed at its surface. After loading a solution sample on its surface, the coated silica particles allowed the target analytes to remain at the top side rather than penetration through the substrate. Owing to this effect and the special interactions with analytes, the as-prepared silica coated paper demonstrated superior performance in the analysis of different pesticides in milk using paper spray mass spectrometry to the uncoated filter paper and grade SG81 paper. Compared to the other two papers, paper spray analysis using the as-prepared paper improved the estimated lower limit of quantitation of seven pesticides (alachlor, acetochlor, pretilachlor, butachlor, metolachlor, napropamid and benzeneacetamide) in milk by a factor of 2 to 19-fold depending on the pesticide. This study offers a novel paper substrate for paper spray in high sensitivity analysis of target analytes in a complex foodstuff matrix without any pretreatment. PMID:26491727

  17. Whole genome sequence analysis of an Alachlor and Endosulfan degrading Pseudomonas strain W15Feb9B isolated from Ochlockonee River, Florida.

    PubMed

    Chauhan, Ashvini; Pathak, Ashish; Ewida, Ayman Y I; Griffiths, Zabrenna; Stothard, Paul

    2016-06-01

    We recently isolated a Pseudomonas sp. strain W15Feb9B from Ochlockonee River, Florida and demonstrated potent biodegradative activity against two commonly used pesticides - Alachlor [(2-chloro-2',6'-diethylphenyl-N (methoxymethyl)acetanilide)] and Endosulfan [(6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9methano-2,3,4-benzo(e)di-oxathiepin-3-oxide], respectively. To further identify the repertoire of metabolic functions possessed by strain W15Feb9B, a draft genome sequence was obtained, assembled, annotated and analyzed. The genome sequence of strain 2385 has been deposited in GenBank under accession number JTKF00000000; BioSample number SAMN03151543. The sequences obtained from strain 2385 assembled into 192 contigs with a genome size of 6,031,588, G + C content of 60.34, and 5512 total number of putative genes. RAST annotated a total of 542 subsystems in the genome of strain W15Feb9B along with the presence of 5360 coding sequences. A genome wide survey of strain W15Feb9B indicated that it has the potential to degrade several other pollutants including atrazine, caprolactam, dioxin, PAHs (such as naphthalene) and several chloroaromatic compounds. PMID:27330991

  18. ACETANILIDE HERBICIDE DEGRADATION PRODUCTS BY LC/MS

    EPA Science Inventory

    Acetanilide herbicides are frequently applied in the U.S. on crops (corn, soybeans, popcorn, etc.) to control broadleaf and annual weeds. The acetanilide and acetamide herbicides currently registered for use in the U.S. are alachlor, acetochlor, metolachlor, propachlor, flufen...

  19. Implications of sampling frequency to herbicide conservation effects assessment

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Herbicide losses from row crop agriculture represent potential human health hazards. In particular, atrazine concentrations in drinking water must not exceed its maximum contaminant level (MCL) of 3 'g/L. Atrazine, simazine, alachlor, acetochlor, metolachlor, and glyphosate were monitored along ti...

  20. Herbicide Losses in the Saint Joseph River Watershed: Impacts of Hydrology and Land Management

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Herbicide losses from row crop agriculture represent potential human health hazards, and are a major focus of the Conservation Effects Assessment Project (CEAP). Atrazine, simazine, alachlor, acetochlor, metolachlor, and glyphosate were monitored in tile-fed drainage ditches draining to a drinking ...

  1. 78 FR 13264 - Acetochlor; Pesticide Tolerances

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-02-27

    ... July 25, 2012 (77 FR 43562) (FRL-9353- 6), EPA issued a document pursuant to FFDCA section 408(d)(3... FR 47445) (FRL-8434-1). C. Exposure Assessment 1. Dietary exposure from food and feed uses. In... Review'' (58 FR 51735, October 4, 1993). Because this final rule has been exempted from review...

  2. Novosphingobium chloroacetimidivorans sp. nov., a chloroacetamide herbicide-degrading bacterium isolated from activated sludge.

    PubMed

    Chen, Qing; Zhang, Jun; Wang, Cheng-Hong; Jiang, Jin; Kwon, Soon-Wo; Sun, Li-Na; Shen, Wen-Biao; He, Jian

    2014-08-01

    Strain BUT-14(T), a Gram-reaction-negative, non-spore-forming, ellipse-shaped bacterium, was isolated from activated sludge of a chloroacetamide-herbicides-manufacturing wastewater treatment facility. The strain was able to degrade more than 90% of butachlor, acetochlor and alachlor (100 mg l(-1)) within 5 days of incubation. The taxonomic position was investigated using a polyphasic approach. Phylogenetic analysis based on 16S rRNA gene sequences revealed that strain BUT-14(T) was a member of the genus Novosphingobium and showed the highest sequence similarities to Novosphingobium soli DSM 22821(T) (97.9%), N. naphthalenivorans KACC 15258(T) (97.4%), N. pentaromativorans JCM 12182(T) (97.4%) and N. barchaimii DSM 25411(T) (97.1%) and lower (<97%) sequence similarities to all other species of the genus Novosphingobium. Chemotaxonomic analysis revealed that strain BUT-14(T) possessed Q-10 as the predominant ubiquinone, spermidine as the major polyamine and C(18 : 1)ω7c (46.9%), C(17 : 1)ω6c (17.9%), summed feature 3, C(14 : 0) 2-OH (4.4%), C(15 : 0) 2-OH (3.1%) and C(16 : 0) (5.51%) as the major fatty acids. The polar lipids included lipid, glycolipid, phosphatidylglycerol, phospholipid, phosphatidylethanolamine, phosphatidylcholine, sphingoglycolipid and phospatidyldimethylethanolamine. Strain BUT-14(T) showed low DNA-DNA relatedness with N. soli DSM 22821(T) (41.5±2.9%), N. naphthalenivorans JCM 12182(T) (49.2±4.2%), N. pentaromativorans KACC 12295(T) (53.2±1.9%) and N. barchaimii DSM 25411 (51.2±4.5%). The DNA G+C content was 66±0.3 mol%. The combination of phylogenetic analysis, phenotypic characteristics, chemotaxonomic data and DNA-DNA hybridization supports the suggestion that strain BUT-14(T) represents a novel species of the genus Novosphingobium, for which the name Novosphingobium chloroacetimidivorans sp. nov. is proposed. The type strain is BUT-14(T) ( = CCTCC AB 2013086(T) = KACC 17147(T) = JCM 19923(T)). PMID

  3. Occurrence and distribution of pesticides in streams of the Eastern Iowa Basins, 1996-98

    USGS Publications Warehouse

    Schnoebelen, Douglas J.; Kalkhoff, Stephen J.; Becher, Kent D.

    2001-01-01

    Occurrence of pesticide compounds varied by landform region. The triazine herbicides, atrazine and cyanazine and their degradates were present in significantly greater concentrations in the Southern Iowa Drift Plain (predominantly loess soils) than either the Des Moines Lobe or the Iowan Surface (predominantly till soils). Less atrazine and cyanazine are applied to till soils because of pH and organic carbon content. Alachlor, metolachlor, and acetochlor have often been used to offset triazine pesticide reductions in area with till soils.

  4. Occurrence and load of selected herbicides and metabolites in the lower Mississippi River

    USGS Publications Warehouse

    Clark, G.M.; Goolsby, D.A.

    2000-01-01

    Analyses of water samples collected from the Mississippi River at Baton Rouge, Louisiana, during 1991-1997 indicate that hundreds of metric tons of herbicides and herbicide metabolites are being discharged annually to the Gulf of Mexico. Atrazine, metolachlor, and the ethane-sulfonic acid metabolite of alachlor (alachlor ESA) were the most frequently detected herbicides and, in general, were present in the largest concentrations. Almost 80% of the annual herbicide load to the Gulf of Mexico occurred during the growing season from May to August. The concentrations and loads of alachlor in the Mississippi River decreased dramatically after 1993 in response to decreased use in the basin. In contrast, the concentrations and loads of acetochlor increased after 1994, reflecting its role as a replacement for alachlor. The peak annual herbicide load occurred in 1993, when approximately 640 metric tons (t) of atrazine, 320 t of cyanazine, 215 t of metolachlor, 53 t of simazine, and 50 t of alachlor were discharged to the Gulf of Mexico. The annual loads of atrazine and cyanazine were generally 1-2% of the amount annually applied in the Mississippi River drainage basin; the annual loads of acetochlor, alachlor, and metolachlor were generally less than 1%. Despite a reduction in atrazine use, historical data do not indicate a long-term downward trend in the atrazine load to the Gulf of Mexico. Although a relation (r2=0.62) exists between the atrazine load and stream discharge during May to August, variations in herbicide use and rainfall patterns within subbasins can have a large effect on herbicide loads in the Mississippi River Basin and probably explain a large part of the annual variation in atrazine load to the Gulf of Mexico. Copyright (C) 2000 Elsevier Science B.V.

  5. Changes in herbicide concentrations in Midwestern streams in relation to changes in use, 1989-1998

    USGS Publications Warehouse

    Scribner, E.A.; Battaglin, W.A.; Goolsby, D.A.; Thurman, E.M.

    2000-01-01

    Water samples were collected from Midwestern streams in 1994-1995 and 1998 as part of a study to help determine if changes in herbicide use resulted in changes in herbicide concentrations since a previous reconnaissance study in 1989-1990. Sites were sampled during the first significant runoff period after the application of pre-emergent herbicides in 1989-1990, 1994-1995, and 1998. Samples were analyzed for selected herbicides, two atrazine metabolites, three cyanazine metabolites, and one alachlor metabolite. In the Midwestern USA, alachlor use was much greater in 1989 than in 1995, whereas acetochlor was not used in 1989 but was commonly used in 1995. The use of atrazine, cyanazine, and metolachlor was approximately the same in 1989 and 1995. The median concentrations of atrazine, alachlor, cyanazine, and metolachlor were substantially higher in 1989-1990 than in 1994-1995 or 1998. The median acetochlor concentration was higher in 1998 than in 1994 or 1995. Copyright (C) 2000 Elsevier Science B.V.

  6. Biodegradation and mineralization of metolachlor and alachlor by Candida xestobii

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Metolachlor (2-chloro-6’-ethyl-N-(2-methoxy-1-methylethyl) aceto-o-toluidide) is a pre-emergent chloroacetanilide herbicide used to control broadleaf and annual grassy weeds in a variety of crops. The S enantiomer of metolachlor, S-metolachlor, is the most effective form for weed control. While the ...

  7. 40 CFR 180.249 - Alachlor; tolerances for residues.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., field, forage 2.0 Corn, field, grain 0.2 Corn, field, pop 0.2 Corn, field, stover 2.0 Corn, pop, stover... seed 0.03 Cowpea, forage 5.0 Cowpea, hay 5.0 Egg 0.02 Goat, fat 0.02 Goat, meat byproducts 0.02 Goat..., meat 0.02 Sheep, fat 0.02 Sheep, meat byproducts 0.02 Sheep, meat 0.02 Sorghum grain, forage...

  8. 40 CFR 180.470 - Acetochlor; tolerances for residues.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., stover 2.5 Corn, sweet, forage 1.5 Corn, sweet, kernels plus cob with husks removed 0.05 Corn, sweet..., rice, and wheat, grain 0.05 Pea and bean, dried shelled, except soybean, subgroup 6C 0.05 Potato...

  9. 40 CFR 180.470 - Acetochlor; tolerances for residues.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., stover 2.5 Corn, sweet, forage 1.5 Corn, sweet, kernels plus cob with husks removed 0.05 Corn, sweet... wheat, grain 0.05 Pea and bean, dried shelled, except soybean, subgroup 6C 0.05 Potato 0.05...

  10. 40 CFR 180.470 - Acetochlor; tolerances for residues.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., stover 2.5 Corn, sweet, forage 1.5 Corn, sweet, kernels plus cob with husks removed 0.05 Corn, sweet..., rice, and wheat, grain 0.05 Pea and bean, dried shelled, except soybean, subgroup 6C 0.05 Potato...

  11. 40 CFR 180.470 - Acetochlor; tolerances for residues.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., stover 2.5 Corn, sweet, forage 1.5 Corn, sweet, kernels plus cob with husks removed 0.05 Corn, sweet... wheat, grain 0.05 Pea and bean, dried shelled, except soybean, subgroup 6C 0.05 Potato 0.05...

  12. Acetochlor persistence in surface and subsurface soil samples

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Although degradation data for herbicides are essential in understanding their potential to be environmental contaminants and are indispensable inputs in computer-based modeling of the herbicides’ fate in the environment, most available data only concern surface soils. Soil samples, collected at two ...

  13. Eleven-year trend in acetanilide pesticide degradates in the Iowa River, Iowa.

    PubMed

    Kalkhoff, Stephen J; Vecchia, Aldo V; Capel, Paul D; Meyer, Michael T

    2012-01-01

    Trends in concentration and loads of acetochlor, alachlor, and metolachlor and their ethanasulfonic (ESA) and oxanilic (OXA) acid degradates were studied from 1996 through 2006 in the main stem of the Iowa River, Iowa and in the South Fork Iowa River, a small tributary near the headwaters of the Iowa River. Concentration trends were determined using the parametric regression model SEAWAVE-Q, which accounts for seasonal and flow-related variability. Daily estimated concentrations generated from the model were used with daily streamflow to calculate daily and yearly loads. Acetochlor, alachlor, metolachlor, and their ESA and OXA degradates were generally present in >50% of the samples collected from both sites throughout the study. Their concentrations generally decreased from 1996 through 2006, although the rate of decrease was slower after 2001. Concentrations of the ESA and OXA degradates decreased from 3 to about 23% yr. The concentration trend was related to the decreasing use of these compounds during the study period. Decreasing concentrations and constant runoff resulted in an average reduction of 10 to >3000 kg per year of alachlor and metolachlor ESA and OXA degradates being transported out of the Iowa River watershed. Transport of acetochlor and metolachlor parent compounds and their degradates from the Iowa River watershed ranged from <1% to about 6% of the annual application. These trends were related to the decreasing use of these compounds during the study period, but the year-to-year variability cannot explain changes in loads based on herbicide use alone. The trends were also affected by the timing and amount of precipitation. As expected, increased amounts of water moving through the watershed moved a greater percentage of the applied herbicides, especially the relatively soluble degradates, from the soils into the rivers through surface runoff, shallow groundwater inflow, and subsurface drainage. PMID:23099949

  14. Eleven-year trend in acetanilide pesticide degradates in the Iowa River, Iowa

    USGS Publications Warehouse

    Kalkhoff, Stephen J.; Vecchia, Aldo V.; Capel, Paul D.; Meyer, Michael T.

    2012-01-01

    Trends in concentration and loads of acetochlor, alachlor, and metolachlor and their ethanasulfonic (ESA) and oxanilic (OXA) acid degradates were studied from 1996 through 2006 in the main stem of the Iowa River, Iowa and in the South Fork Iowa River, a small tributary near the headwaters of the Iowa River. Concentration trends were determined using the parametric regression model SEAWAVE-Q, which accounts for seasonal and flow-related variability. Daily estimated concentrations generated from the model were used with daily streamflow to calculate daily and yearly loads. Acetochlor, alachlor, metolachlor, and their ESA and OXA degradates were generally present in >50% of the samples collected from both sites throughout the study. Their concentrations generally decreased from 1996 through 2006, although the rate of decrease was slower after 2001. Concentrations of the ESA and OXA degradates decreased from 3 to about 23% yr-1. The concentration trend was related to the decreasing use of these compounds during the study period. Decreasing concentrations and constant runoff resulted in an average reduction of 10 to >3000 kg per year of alachlor and metolachlor ESA and OXA degradates being transported out of the Iowa River watershed. Transport of acetochlor and metolachlor parent compounds and their degradates from the Iowa River watershed ranged from <1% to about 6% of the annual application. These trends were related to the decreasing use of these compounds during the study period, but the year-to-year variability cannot explain changes in loads based on herbicide use alone. The trends were also affected by the timing and amount of precipitation. As expected, increased amounts of water moving through the watershed moved a greater percentage of the applied herbicides, especially the relatively soluble degradates, from the soils into the rivers through surface runoff, shallow groundwater inflow, and subsurface drainage.

  15. Herbicide concentrations in the Mississippi River Basin-the importance of chloroacetanilide herbicide degradates.

    PubMed

    Rebich, R A; Coupe, R H; Thurman, E M

    2004-04-01

    The proportion of chloroacetanilide herbicide degradates, specifically the ethane sulfonic (ESA) and oxanilic (OA) acids, averaged 70% of the total herbicide concentration in samples from the Upper Mississippi River. In samples from the Missouri River and the Ohio River, the proportion of chloroacetanilide degradates in the total herbicide concentration was much less, 24% and 41%, respectively. The amount of tile drainage throughout the Mississippi River Basin appeared to be related to the occurrence and distribution of chloroacetanilide degradates in water samples. Pesticide concentrations in streams of the Mississippi River Basin have been well characterized. However, recent research demonstrates that in order to more fully understand the fate and transport of pesticides, the major pesticide degradates need to be included in the analysis. From March 1999 through May 2001, water samples from four major junctures of the Mississippi River Basin were collected and analyzed for a suite of herbicides and their degradate compounds. Each sampling site was selected to represent a major part of the Mississippi River: upper and lower Mississippi, Missouri and Ohio Rivers. Each basin has unique landscape variables, geology, hydrology, precipitation, and land use, which is reflected in the pesticide content at the most downstream sample site near the mouth of the Mississippi River. Atrazine was the most frequently detected herbicide (detected in 97% of the samples), followed by metolachlor (60%), and acetochlor (31%). The most frequently detected degradates were metolachlor ESA (69%), followed by deethylatrazine (62%), metolachlor OA (37%), and alachlor ESA (37%). Metolachlor ESA was detected more frequently than its parent compound (69 vs. 60%), as was alachlor ESA (37 vs. 9%). After an improvement was made in the analytical method, metolachlor ESA was detected in every sample, metolachlor OA in 89% of the samples, alachlor ESA in 84%, acetochlor ESA in 71%, and acetochlor

  16. Herbicide concentrations in the Mississippi River Basin - The importance of chloroacetanilide herbicide degradates

    USGS Publications Warehouse

    Rebich, R.A.; Coupe, R.H.; Thurman, E.M.

    2004-01-01

    The proportion of chloroacetanilide herbicide degradates, specifically the ethane sulfonic (ESA) and oxanilic (OA) acids, averaged 70% of the total herbicide concentration in samples from the Upper Mississippi River. In samples from the Missouri River and the Ohio River, the proportion of chloroacetanilide degradates in the total herbicide concentration was much less, 24% and 41%, respectively. The amount of tile drainage throughout the Mississippi River Basin appeared to be related to the occurrence and distribution of chloroacetanilide degradates in water samples. Pesticide concentrations in streams of the Mississippi River Basin have been well characterized. However, recent research demonstrates that in order to more fully understand the fate and transport of pesticides, the major pesticide degradates need to be included in the analysis. From March 1999 through May 2001, water samples from four major junctures of the Mississippi River Basin were collected and analyzed for a suite of herbicides and their degradate compounds. Each sampling site was selected to represent a major part of the Mississippi River: upper and lower Mississippi, Missouri and Ohio Rivers. Each basin has unique landscape variables, geology, hydrology, precipitation, and land use, which is reflected in the pesticide content at the most downstream sample site near the mouth of the Mississippi River. Atrazine was the most frequently detected herbicide (detected in 97% of the samples), followed by metolachlor (60%), and acetochlor (31%). The most frequently detected degradates were metolachlor ESA (69%), followed by deethylatrazine (62%), metolachlor OA (37%), and alachlor ESA (37%). Metolachlor ESA was detected more frequently than its parent compound (69 vs. 60%), as was alachlor ESA (37 vs. 9%). After an improvement was made in the analytical method, metolachlor ESA was detected in every sample, metolachlor OA in 89% of the samples, alachlor ESA in 84%, acetochlor ESA in 71%, and acetochlor

  17. Degradation of chloroacetanilide herbicides and bacterial community composition in lab-scale wetlands.

    PubMed

    Elsayed, Omniea Fawzy; Maillard, Elodie; Vuilleumier, Stéphane; Millet, Maurice; Imfeld, Gwenaël

    2015-07-01

    Degradation of chloroacetanilide herbicides rac-metolachlor, acetochlor, and alachlor, as well as associated bacterial populations, were evaluated in vertical upflow wetland columns using a combination of hydrochemical and herbicide analyses, and DNA-based approaches. Mass dissipation of chloroacetanilides, continuously supplied at 1.8-1.9 μM for 112 days, mainly occurred in the rhizosphere zone under nitrate and sulphate-reducing conditions, and averaged 61±14%, 52±12% and 29±19% for acetochlor, alachlor and rac-metolachlor, respectively. Metolachlor enantiomer fractions of 0.494±0.009 in the oxic zone and 0.480±0.005 in the rhizosphere zone indicated preferential biodegradation of the S-enantiomer. Chloroacetanilide ethane sulfonic acid and oxanilic acid degradates were detected at low concentrations only (0.5 nM), suggesting extensive degradation and the operation of yet unknown pathways for chloroacetanilide degradation. Hydrochemical parameters and oxygen concentration were major drivers of bacterial composition, whereas exposure to chloroacetanilides had no detectable impact. Taken together, the results underline the importance of anaerobic degradation of chloroacetanilides in wetlands, and highlight the potential of complementary chemical and biological approaches to characterise processes involved in the environmental dissipation of chloroacetanilides. PMID:25817759

  18. Methods of analysis by the U.S. Geological Survey Organic Geochemistry Research Group; determination of chloroacetanilide herbicide metabolites in water using high-performance liquid chromatography-diode array detection and high-performance liquid chromatography/mass spectrometry

    USGS Publications Warehouse

    Zimmerman, L.R.; Hostetler, K.A.; Thurman, E.M.

    2000-01-01

    Analytical methods using high-performance liquid chromatography-diode array detection (HPLC-DAD) and high-performance liquid chromatography/mass spectrometry (HPLC/MS) were developed for the analysis of the following chloroacetanilide herbicide metabolites in water: acetochlor ethanesulfonic acid (ESA), acetochlor oxanilic acid (OXA), alachlor ESA, alachlor OXA, metolachlor ESA, and metolachlor OXA. Good precision and accuracy were demonstrated for both the HPLC-DAD and HPLC/MS methods in reagent water, surface water, and ground water. The mean HPLC-DAD recoveries of the chloroacetanilide herbicide metabolites from water samples spiked at 0.25, 0.50, and 2.0 mg/L (micrograms per liter) ranged from 84 to 112 percent, with relative standard deviations of 18 percent or less. The mean HPLC/MS recoveries of the metabolites from water samples spiked at 0.05, 0.20, and 2.0 mg/L ranged from 81 to 125 percent, with relative standard deviations of 20 percent or less. The limit of quantitation (LOQ) for all metabolites using the HPLC-DAD method was 0.20 mg/L, whereas the LOQ using the HPLC/MS method was 0.05 mg/L. These metabolite-determination methods are valuable for acquiring information about water quality and the fate and transport of the parent chloroacetanilide herbicides in water.

  19. Determination of chloroacetanilide herbicide metabolites in water using high-performance liquid chromatography-diode array detection and high-performance liquid chromatography/mass spectrometry

    USGS Publications Warehouse

    Hostetler, K.A.; Thurman, E.M.

    2000-01-01

    Analytical methods using high-performance liquid chromatography-diode array detection (HPLC-DAD) and high-performance liquid chromatography/mass spectrometry (HPLC/MS) were developed for the analysis of the following chloroacetanilide herbicide metabolites in water: alachlor ethanesulfonic acid (ESA); alachlor oxanilic acid; acetochlor ESA; acetochlor oxanilic acid; metolachlor ESA; and metolachlor oxanilic acid. Good precision and accuracy were demonstrated for both the HPLC-DAD and HPLC/MS methods in reagent water, surface water, and ground water. The average HPLC-DAD recoveries of the chloroacetanilide herbicide metabolites from water samples spiked at 0.25, 0.5 and 2.0 ??g/l ranged from 84 to 112%, with relative standard deviations of 18% or less. The average HPLC/MS recoveries of the metabolites from water samples spiked at 0.05, 0.2 and 2.0 ??g/l ranged from 81 to 118%, with relative standard deviations of 20% or less. The limit of quantitation (LOQ) for all metabolites using the HPLC-DAD method was 0.20 ??g/l, whereas the LOQ using the HPLC/MS method was at 0.05 ??g/l. These metabolite-determination methods are valuable for acquiring information about water quality and the fate and transport of the parent chloroacetanilide herbicides in water. Copyright (C) 2000 Elsevier Science B.V.

  20. Degradation of chloroacetanilide herbicides: The prevalence of sulfonic and oxanilic acid metabolites in Iowa groundwaters and surface waters

    USGS Publications Warehouse

    Kalkhoff, S.J.; Kolpin, D.W.; Thurman, E.M.; Ferrer, I.; Barcelo, D.

    1998-01-01

    Water samples were collected from 88 municipal wells throughout Iowa during the summer and were collected monthly at 12 stream sites in eastern Iowa from March to December 1996 to study the occurrence of the sulfonic and oxanilic metabolites of acetochlor, alachlor, and metolachlor. The sulfonic and oxanilic metabolites were present in almost 75% of the groundwater samples and were generally present from 3 to 45 times more frequently than their parent compounds. In groundwater, the median value of the summed concentrations of acetochlor, alachlor, and metolachlor was less than 0.05 μg/L, and the median value of the summed concentrations of the six metabolites was 1.2 μg/L. All surface water samples contained at least one detectable metabolite compound. Individual metabolites were detected from 2 to over 100 times more frequently than the parent compounds. In surface water, the median value of the summed concentrations of the three parent compounds was 0.13 μg/L, and the median value of the summed concentrations of the six metabolites was 6.4 μg/L. These data demonstrate the importance of analyzing both parent compounds and metabolites to more fully understand the environmental fate and transport of herbicides in the hydrologic system.

  1. Water purification from organic pollutants by optimized micelle-clay systems.

    PubMed

    Polubesova, Tamara; Nir, Shlomo; Zadaka, Dikla; Rabinovitz, Onn; Serban, Carina; Groisman, Ludmila; Rubin, Baruch

    2005-04-01

    Removal of anionic pollutants (imazaquin, sulfentrazone, sulfosulfuron) and neutral pollutants (alachlor, acetochlor, chlorotoluron, bromacil) from water by micelles preadsorbed on montmorillonite was studied. Micelles of octadecyltrimethylammonium and benzyldimethylhexadecylammonium (BDMHDA) were used. The micelle-clay systems (1% w/w) removed 87-99% of the pollutants from their water solutions containing 1-33 mg/L of herbicide. The nature of the headgroup of the organic cation, which forms the micelles, is critical. Desorption of imazaquin and acetochlor from 0.3% (w/w) suspension of BDMHDA-clay complex after 24 h was around 7% in the range of adsorbed amounts from 0.6 to 15.3 mg/g. These results indicate rather slow rates and small extents of release of pollutants from micelle-clay complexes. Column filters (25 cm) made of a mixture of quartz sand and BDMHDA micelle-clay complex at 100:1 w/w ratio removed at least 99% of above pollutants from initial solutions containing 10 mg/L; 99.5 and 97% of sulfosulfuron and alachlor were removed from their initial solutions containing 200 and 5 microg/L, respectively. These data indicate that micelle-clay complexes are very efficient for water purification from organic contaminants. PMID:15871274

  2. Are shifts in herbicide use reflected in concentration changes in Midwestern rivers?

    USGS Publications Warehouse

    Battaglin, W.A.; Goolsby, D.A.

    1999-01-01

    In many Midwestern rivers, elevated concentrations of herbicides occur during runoff events for 1-3 months following application. The highest or 'peak' herbicide concentration often occurs during one of these runoff events. Herbicide concentrations in rivers are affected by a number of factors, including herbicide use patterns within the associated basin. Changing agricultural practices, reductions in recommended and permitted herbicide applications, shifts to new herbicides, and greater environmental awareness in the agricultural community have resulted in changes to herbicide use patterns. In the Midwestern United States, alachlor use was much larger in 1989 than in 1995, while acetochlor was not used in 1989, and commonly used in 1995. Use of atrazine, cyanazine, and metolachlor was about the same in 1989 and 1995. Herbicide concentrations were measured in samples from 53 Midwestern rivers during the first major runoff event that occurred after herbicide application (postapplication) in 1989, 1990, 1994, and 1995. The median concentrations of atrazine, alachlor, cyanazine, metribuzin, metolachlor, propazine, and simazine all were significantly higher in 1989/90 than in 1994/95. The median acetochlor concentration was higher in 1995 than in 1994. Estimated daily yields for all herbicides and degradation products measured, with the exception of acetochlor, were higher in 1989/90 than in 1994/95. The differences in concentration and yield do not always parallel changes in herbicide use, suggesting that other changes in herbicide or crop management are affecting concentrations in Midwestern rivers during runoff events.In many Midwestern rivers, elevated concentrations of herbicides occur during runoff events for 1-3 months following application. The highest or `peak' herbicide concentration often occurs during one of these runoff events. Herbicide concentrations in rivers are affected by a number of factors, including herbicide use patterns within the associated

  3. ALACHLOR AND ATRAZINE BIODEGRADATION UNDER DENITRIFYING ELECTRON ACCEPTOR CONDITIONS. (R825549C037)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  4. Methods of Analysis by the U.S. Geological Survey Organic Geochemistry Research Group-Update and Additions to the Determination of Chloroacetanilide Herbicide Degradation Compounds in Water Using High-Performance Liquid Chromatography/Mass Spectrometry

    USGS Publications Warehouse

    Lee, E.A.; Kish, J.L.; Zimmerman, L.R.; Thurman, E.

    2001-01-01

    An analytical method using high-performance liquid chromatography/mass spectrometry (HPLC/MS) was developed by the U.S. Geological Survey in 1999 for the analysis of selected chloroacetanilide herbicide degradation compounds in water. These compounds were acetochlor ethane sulfonic acid (ESA), acetochlor oxanilic acid (OXA), alachlor ESA, alachlor OXA, metolachlor ESA, and metolachlor OXA. The HPLC/MS method was updated in 2000, and the method detection limits were modified accordingly. Four other degradation compounds also were added to the list of compounds that can be analyzed using HPLC/MS; these compounds were dimethenamid ESA, dimethenamid OXA, flufenacet ESA, and flufenacet OXA. Except for flufenacet OXA, good precision and accuracy were demonstrated for the updated HPLC/MS method in buffered reagent water, surface water, and ground water. The mean HPLC/MS recoveries of the degradation compounds from water samples spiked at 0.20 and 1.0 ?g/L (microgram per liter) ranged from 75 to 114 percent, with relative standard deviations of 15.8 percent or less for all compounds except flufenacet OXA, which had relative standard deviations ranging from 11.3 to 48.9 percent. Method detection levels (MDL's) using the updated HPLC/MS method varied from 0.009 to 0.045 ?g/L, with the flufenacet OXA MDL at 0.072 ?g/L. The updated HPLC/MS method is valuable for acquiring information about the fate and transport of the parent chloroacetanilide herbicides in water.

  5. Reconnaissance data for glyphosate, other selected herbicides, their degradation products, and antibiotics in 51 streams in nine midwestern states, 2002

    USGS Publications Warehouse

    Scribner, Elisabeth A.; Battaglin, William A.; Dietze, Julie E.; Thurman, E.M.

    2003-01-01

    Since 1989, the U.S. Geological Survey has conducted periodic reconnaissance studies of streams in the Midwestern United States to determine the geographic and seasonal distribution of herbicide compounds. These studies have documented that large amounts of acetochlor, alachlor, atrazine, cyanazine, metolachlor, and their degradation products are flushed into streams during post-application runoff. Additional studies show that peak herbicide concentrations tend to occur during the first runoff after herbicide application and that herbicide flushes can occur during runoff for several weeks to months following application. Since the first stream study conducted in 1989, several significant changes in herbicide use have occurred. The most substantial change is the tripling in the use of glyphosate during the past 5 years. Over this same time period (1997-2001), usage of acetochlor and atrazine increased slightly, whereas alachlor, cyanazine, and metolachlor usage decreased. During 2002, 154 samples were collected from 51 streams in nine Midwestern States during three periods of runoff. This report provides a compilation of the analytical results of five laboratory methods. Results show that glyphosate was detected in 55 (36 percent) of the samples, and aminomethylphosphonic acid (a degradation product of glyphosate) was detected in 107 (69 percent) of the samples. Atrazine, the most frequently detected herbicide, was found in 93 percent of the samples, followed by metolachlor, found in 73 percent of the samples; metolachlor ethanesulfonic acid (ESA) and oxanilic acid (OXA) were the most frequently detected herbicide degradation products, both being found in more than 95 percent of the samples. The data presented here are valuable for comparison with results from the earlier reconnaissance studies.

  6. Methods of Analysis by the U.S. Geological Survey Organic Geochemistry Research Group?Determination of acetamide herbicides and their degradation products in water using online solid-phase extraction and liquid chromatography/mass spectrometry

    USGS Publications Warehouse

    Lee, E.A.; Strahan, A.P.

    2003-01-01

    An analytical method for the determination of 6 acetamide herbicides (acetochlor, alachlor, dimethenamid, flufenacet, metolachlor, and propachlor) and 16 of their degradation products in natural water samples using solid-phase extraction and liquid chromatography/mass spectrometry is described in this report. Special consideration was given during the development of the method to prevent the formation of degradation products during the analysis. Filtered water samples were analyzed using octadecylsilane as the solid-phase extraction media on online automated equipment followed by liquid chromatography/mass spectrometry. The method uses only 10 milliliters of sample per injection. Three different water-sample matrices, a reagent-water, a ground-water, and a surface-water sample spiked at 0.10 and 1.0 microgram per liter, were analyzed to determine method performance. Method detection limits ranged from 0.004 to 0.051 microgram per liter for the parent acetamide herbicides and their degradation products. Mean recoveries for the acetamide compounds in the ground- and surface-water samples ranged from 62.3 to 117.4 percent. The secondary amide of acetochlor/metolachlor ethanesulfonic acid (ESA) was recovered at an average rate of 43.5 percent. The mean recoveries for propachlor and propachlor oxanilic acid (OXA) were next lowest, ranging from 62.3 to 95.5 percent. Mean recoveries from reagent-water samples ranged from 90.3 to 118.3 percent for all compounds. Overall the mean of the mean recoveries of all compounds in the three matrices spiked at 0.10 and 1.0 microgram per liter ranged from 89.9 to 100.7 percent, including the secondary amide of acetochlor/metolachlor ESA and the propachlor compounds. The acetamide herbicides and their degradation products are reported in concentrations ranging from 0.05 to 2.0 micrograms per liter. The upper concentration limit is 2.0 micrograms per liter for all compounds without dilution. With the exception of the secondary amide of

  7. Simulated ground-water flow and water quality of the Mississippi River alluvium near Burlington, Iowa, 1999

    USGS Publications Warehouse

    Boyd, Robert A.

    2001-01-01

    Water samples collected from the alluvium indicated ground water can be classified as a calcium-magnesium-bicarbonate type. Reducing conditions likely occur in some localized areas of the alluvium, as suggested by relatively large concentrations of dissolved iron (4,390 micrograms per liter) and manganese (2, 430 micrograms per liter) in some ground-water samples. Nitrite plus nitrate was detected at concentrations greater than or equal to 8 milligrams per liter in three samples collected from observation wells completed in close proximity to cropland; the nitrite plus nitrate concentration in one groundwater sample exceeded the U.S. Environmental Protection Agency Maximum Contaminant Level for nitrate in drinking water (10 milligrams per liter as N). Triazine herbicides (atrazine, cyanazine, propazine, simazine, and selected degradation products) and chloroacetanilide herbicides (acetochlor, alachlor, and metolachlor) were detected in some water samples. A greater number of herbicide compounds were detected in surface-water samples than in ground-water samples. Herbicide concentrations typically were at least an order of magnitude greater in surfacewater samples than in ground-water samples. The Maximum Contaminant Level for alachlor (2 micrograms per liter) was exceeded in a sample from Dry Branch Creek at Tama Road and for atrazine (3 micrograms per liter) was exceeded in samples collected from Dry Branch Creek at Tama Road and the county drainage ditch at Tama Road.

  8. Herbicides in the Pecatonica, Trempealeau, and Yahara Rivers in Wisconsin, May 1997-July 1998

    USGS Publications Warehouse

    Graczyk, David J.; Vanden Brook, James P.; Rheineck, Bruce D.

    1999-01-01

    In 1997, Wisconsin farmers applied 8.7 million pounds of herbicides on corn. The five most commonly applied herbicides (in lb (pounds) of active ingredient per acre) on corn in 1997 were atrazine, metolachlor, acetochlor, alachlor and cyanazine. A 1996 study by the U.S. Geological Survey (USGS) and the Wisconsin Department of Agriculture, Trade and Consumer Protection (DATCP) found that the most heavily applied agricultural herbicides were detected more frequently and at higher concentrations in the Pecatonica and Yahara Rivers in southern Wisconsin than the less heavily applied herbicides (Graczyk and Vanden Brook, 1997). The calculated herbicide loads a from May 15 to July 15, 1996 at the Pecatonica River ranged from 47.2 lb of alachlor to 484 lb of atrazine. For the Yahara River, loads ranged from 36.1 lb of alachlor to 289 lb of atrazine. The yields b (load per square mile) for atrazine were similar in the two water- sheds. This result was unexpected because the use of atrazine is prohibited on 94 percent of the Yahara River Watershed, but on only 4 percent of the Pecatonica River watershed. The unexpected atrazine result led to a continuation of the study in 1997 and 1998, when samples were collected again at the two sites sampled in 1996, and at a site in the upper third of the Yahara River Watershed that is entirely under atrazine use prohibition. For comparison purposes, a site in west-central Wisconsin also was sampled to determine herbicide loads and yields in another geographic area in the state

  9. Trends in Pesticide Concentrations in Corn-Belt Streams, 1996-2006

    USGS Publications Warehouse

    Sullivan, Daniel J.; Vecchia, Aldo V.; Lorenz, David L.; Gilliom, Robert J.; Martin, Jeffrey D.

    2009-01-01

    Trends in the concentrations of commonly occurring pesticides in the Corn Belt of the United States were assessed, and the performance and application of several statistical methods for trend analysis were evaluated. Trends in the concentrations of 11 pesticides with sufficient data for trend assessment were assessed at up to 31 stream sites for two time periods: 1996-2002 and 2000-2006. Pesticides included in the trend analyses were atrazine, acetochlor, metolachlor, alachlor, cyanazine, EPTC, simazine, metribuzin, prometon, chlorpyrifos, and diazinon. The statistical methods applied and compared were (1) a modified version of the nonparametric seasonal Kendall test (SEAKEN), (2) a modified version of the Regional Kendall test, (3) a parametric regression model with seasonal wave (SEAWAVE), and (4) a version of SEAWAVE with adjustment for streamflow (SEAWAVE-Q). The SEAKEN test is a statistical hypothesis test for detecting monotonic trends in seasonal time-series data such as pesticide concentrations at a particular site. Trends across a region, represented by multiple sites, were evaluated using the regional seasonal Kendall test, which computes a test for an overall trend within a region by computing a score for each season at each site and adding the scores to compute the total for the region. The SEAWAVE model is a parametric regression model specifically designed for analyzing seasonal variability and trends in pesticide concentrations. The SEAWAVE-Q model accounts for the effect of changing flow conditions in order to separate changes caused by hydrologic trends from changes caused by other factors, such as pesticide use. There was broad, general agreement between unadjusted trends (no adjustment for streamflow effects) identified by the SEAKEN and SEAWAVE methods, including the regional seasonal Kendall test. Only about 10 percent of the paired comparisons between SEAKEN and SEAWAVE indicated a difference in the direction of trend, and none of these had

  10. Semen quality in relation to biomarkers of pesticide exposure.

    PubMed Central

    Swan, Shanna H; Kruse, Robin L; Liu, Fan; Barr, Dana B; Drobnis, Erma Z; Redmon, J Bruce; Wang, Christina; Brazil, Charlene; Overstreet, James W

    2003-01-01

    We previously reported reduced sperm concentration and motility in fertile men in a U.S. agrarian area (Columbia, MO) relative to men from U.S. urban centers (Minneapolis, MN; Los Angeles, CA; New York, NY). In the present study we address the hypothesis that pesticides currently used in agriculture in the Midwest contributed to these differences in semen quality. We selected men in whom all semen parameters (concentration, percentage sperm with normal morphology, and percentage motile sperm) were low (cases) and men in whom all semen parameters were within normal limits (controls) within Missouri and Minnesota (sample sizes of 50 and 36, respectively) and measured metabolites of eight current-use pesticides in urine samples provided at the time of semen collection. All pesticide analyses were conducted blind with respect to center and case-control status. Pesticide metabolite levels were elevated in Missouri cases, compared with controls, for the herbicides alachlor and atrazine and for the insecticide diazinon [2-isopropoxy-4-methyl-pyrimidinol (IMPY)]; for Wilcoxon rank test, p = 0.0007, 0.012, and 0.0004 for alachlor, atrazine, and IMPY, respectively. Men from Missouri with high levels of alachlor or IMPY were significantly more likely to be cases than were men with low levels [odds ratios (ORs) = 30.0 and 16.7 for alachlor and IMPY, respectively], as were men with atrazine levels higher than the limit of detection (OR = 11.3). The herbicides 2,4-D (2,4-dichlorophenoxyacetic acid) and metolachlor were also associated with poor semen quality in some analyses, whereas acetochlor levels were lower in cases than in controls (p = 0.04). No significant associations were seen for any pesticides within Minnesota, where levels of agricultural pesticides were low, or for the insect repellent DEET (N,N-diethyl-m-toluamide) or the malathion metabolite malathion dicarboxylic acid. These associations between current-use pesticides and reduced semen quality suggest that

  11. Surface water-ground water interaction: Herbicide transport into municipal collector wells

    USGS Publications Warehouse

    Verstraeten, Ingrid M.; Carr, J.D.; Steele, G.V.; Thurman, E.M.; Bastian, K.C.; Dormedy, D.F.

    1999-01-01

    During spring runoff events, herbicides in the Platte River are transported through an alluvial aquifer into collector wells located on an island in the river in 6 to 7 d. During two spring runoff events in 1995 and 1996, atrazine [2-chloro-4-ethylamino-6-isopropylamino-s-triazine] concentrations in water from these wells reached approximately 7 ??g/L, 70 times more than the background concentration in ground water. Concentrations of herbicides and metabolites in the collector wells generally were one-half to one-fifth the concentrations of herbicides in the river for atrazine, alachlor [2-chloro-2'-6'-diethyl-N-(methoxymethyl)-acetanilide], alachlor ethane-sulfonic acid (ESA) [2-((2,6-diethylphenyl) (methoxymethyl)amino)-2- oxoethane-sulfonic acid], metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N- (2-methoxy-1-methylethyl)acetamide], cyanazine [2-((4-chloro-6-(ethyl-amino)- 1,3,5 triazin-2-yl)-amino)-2-methylpropionitrile], and acetochlor [2-chloro- N-(ethoxymethyl)-N-(2-ethyl-6methyl-phenyl) acetamide], suggesting that 20 to 50% river water could be present in the water from the collector wells, assuming no degradation. The effect of the river on the quality of water from the collector wells can be reduced through selective management of horizontal laterals of the collector wells. The quality of the water from the collector wells is dependent on the (i) selection of the collector well used, (ii) number and selection of laterals used, (iii) chemical characteristics of the contaminant, and (iv) relative mixing of the Platte River and a major upstream tributary.

  12. Pesticide monitoring in surface water and groundwater using passive samplers

    NASA Astrophysics Data System (ADS)

    Kodes, V.; Grabic, R.

    2009-04-01

    Passive samplers as screening devices have been used within a czech national water quality monitoring network since 2002 (SPMD and DGT samplers for non polar substances and metals). The passive sampler monitoring of surface water was extended to polar substances, in 2005. Pesticide and pharmaceutical POCIS samplers have been exposed in surface water at 21 locations and analysed for polar pesticides, perfluorinated compounds, personal care products and pharmaceuticals. Pesticide POCIS samplers in groundwater were exposed at 5 locations and analysed for polar pesticides. The following active substances of plant protection products were analyzed in surface water and groundwater using LC/MS/MS: 2,4,5-T, 2,4-D, Acetochlor, Alachlor, Atrazine, Atrazine_desethyl, Azoxystrobin, Bentazone, Bromacil, Bromoxynil, Carbofuran, Clopyralid, Cyanazin, Desmetryn, Diazinon, Dicamba, Dichlobenil, Dichlorprop, Dimethoat, Diuron, Ethofumesate, Fenarimol, Fenhexamid, Fipronil, Fluazifop-p-butyl, Hexazinone, Chlorbromuron, Chlorotoluron, Imazethapyr, Isoproturon, Kresoxim-methyl, Linuron, MCPA, MCPP, Metalaxyl, Metamitron, Methabenzthiazuron, Methamidophos, Methidathion, Metobromuron, Metolachlor, Metoxuron, Metribuzin, Monolinuron, Nicosulfuron, Phorate, Phosalone, Phosphamidon, Prometryn, Propiconazole, Propyzamide, Pyridate, Rimsulfuron, Simazine, Tebuconazole, Terbuthylazine, Terbutryn, Thifensulfuron-methyl, Thiophanate-methyl and Tri-allate. The POCIS samplers performed very well being able to provide better picture than grab samples. The results show that polar pesticides and also perfluorinated compounds, personal care products and pharmaceuticals as well occur in hydrosphere of the Czech republic. Acknowledgment: Authors acknowledge the financial support of grant No. 2B06095 by the Ministry of Education, Youth and Sports.

  13. Identification of ionic chloroacetanilide-herbicide metabolites in surface water and groundwater by HPLC/MS using negative ion spray

    USGS Publications Warehouse

    Ferrer, I.; Thurman, E.M.; Barcelo, D.

    1997-01-01

    Solid-phase extraction (SPE) was combined with high-performance liquid chromatography/high-flow pneumatically assisted electrospray mass spectrometry (HPLC/ESP/MS) for the trace analysis of oxanilic and sulfonic acids of acetochlor, alachlor, and metolachlor. The isolation procedure separated the chloroacetanilide metabolites from the parent herbicides during the elution from C18 cartridges using ethyl acetate for parent compounds, followed by methanol for the anionic metabolites. The metabolites were separated chromatographically using reversed-phase HPLC and analyzed by negative-ion MS using electrospray ionization in selected ion mode. Quantitation limits were 0.01 ??g/L for both the oxanilic and sulfonic acids based on a 100-mL water sample. This combination of methods represents an important advance in environmental analysis of chloroacetanilide-herbicide metabolites in surface water and groundwater for two reasons. First, anionic chloroacetanilide metabolites are a major class of degradation products that are readily leached to groundwater in agricultural areas. Second, anionic metabolites, which are not able to be analyzed by conventional methods such as liquid extraction and gas chromatography/mass spectrometry, are effectively analyzed by SPE and high-flow pneumatically assisted electrospray mass spectrometry. This paper reports the first HPLC/MS identification of these metabolites in surface water and groundwater.

  14. Herbicide and degradate flux in the Yazoo River Basin

    USGS Publications Warehouse

    Coupe, R.H.; Welch, H.L.; Pell, A.B.; Thurman, E.M.

    2005-01-01

    During 1996-1997, water samples were collected from five sites in the Yazoo River Basin and analysed for 14 herbicides and nine degradates. These included acetochlor, alachlor, atrazine, cyanazine, fluometuron, metolachlor, metribuzin, molinate, norflurazon, prometryn, propanil, propazine, simazine, trifluralin, three degradates of fluometuron, two degradates of atrazine, one degradate of cyanazine, norflurazon, prometryn, and propanil. Fluxes generally were higher in 1997 than in 1996 due to a greater rainfall in 1997 than 1996. Fluxes were much larger from streams in the alluvial plain (an area of very productive farmland) than from the Skuna River in the bluff hills (an area of small farms, pasture, and forest). Adding the flux of the atrazine degradates to the atrazine flux increased the total atrazine flux by an average of 14.5%. The fluometuron degradates added about 10% to the total fluometuron flux, and adding the norflurazon degradate flux to the norflurazon flux increased the flux by 82% in 1996 and by 171% in 1997. ?? 2005 Taylor & Francis.

  15. Acetamide herbicides and their degradation products in ground water and surface water of the United States, 1993-2003

    USGS Publications Warehouse

    Scribner, Elisabeth A.; Dietze, Julie E.; Thurman, Michael

    2004-01-01

    During 1993 through 2003, the U.S. Geological Survey conducted a number of studies to investigate and document the occurrence, fate, and transport of acetamide herbicides and their degradation products in ground and surface water. As part of these studies, approximately 5,100 water samples were collected and analyzed for the acetamide parent herbicides acetochlor, alachlor, dimethenamid, flufenacet, and metolachlor and their degradation products ethanesulfonic acid, oxanilic acid, and sulfinyl acetic acid. During this period, various analytical methods were developed to detect and measure concentrations of acetamide herbicides and their degradation products in ground water and surface water. Results showed that the degradation products of acetamide herbicides in ground water were detected more frequently and occurred at higher concentrations than their parent compounds. Further study showed that the acetamide herbicides and their degradation products were detected more frequently in surface water than in ground water. In general, the parent compounds were detected at similar or greater frequencies than the degradation products in surface water. The developed methods and data were valuable for acquiring information about the occurrence, fate, and transport of the herbicides and their degradation products and the importance of analyzing for both parent compounds and their degradate products in water-quality studies.

  16. Application of herbicides is likely to reduce greenhouse gas (N2O and CH4) emissions from rice-wheat cropping systems

    NASA Astrophysics Data System (ADS)

    Jiang, Jingyan; Chen, Linmei; Sun, Qing; Sang, Mengmeng; Huang, Yao

    2015-04-01

    Herbicides have been widely used to control weeds in croplands; however, their effects on greenhouse gas emissions remain unclear. The effects of three wheat herbicides (acetochlor, AC; tribenuron-methyl, TBM; fenoxaprop-p-ethyl, FE) and two rice herbicides (butachlor, BC; bensulfuron-methyl, BSM) on N2O and CH4 emissions were investigated in this study. In the wheat growing season, applications of AC and FE + TBM significantly reduced N2O emissions by 31% compared with no herbicide use (p = 0.001). In the rice growing season, the application of BC significantly reduced CH4 emissions by 58% (p = 0.022), and BSM significantly reduced N2O emissions by 27% (p = 0.040); however, no significant difference among treatments with regard to the aggregate emissions of N2O and CH4 in the CO2 equivalent for the 100-year horizon was observed (p > 0.05). Relative to control plots, which were not treated with herbicides, the combined application of the herbicides FE and TBM in the wheat season led to a significant decrease in greenhouse gas intensity (GHGI) by ∼41% (p = 0.002), and the application of BC together with BSM reduced GHGI by 22% in the rice season, although this reduction was not statistically significant (p = 0.158). Further investigation suggested that the inhibitory effect of herbicides on N2O emissions in the wheat field could be ascribed to low soil ammonium nitrogen and less abundance of denitrifying bacteria. The inhibitory effects of separate applications of BC on CH4 emissions in rice fields, in contrast, were linked to high soil nitrate nitrogen and urease activity.

  17. Pesticides in rain in four agricultural watersheds in the United States

    USGS Publications Warehouse

    Vogel, J.R.; Majewski, M.S.; Capel, P.D.

    2008-01-01

    Rainfall samples were collected during the 2003 and 2004 growing seasons at four agricultural locales across the USA in Maryland, Indiana, Nebraska, and California. The samples were analyzed for 21 insecticides, 18 herbicides, three fungicides, and 40 pesticide degradates. Data from all sites combined show that 7 of the 10 most frequently detected pesticides were herbicides, with atrazine (70%) and metolachlor (83%) detected at every site. Dacthal, acetochlor, simazine, alachlor, and pendimethalin were detected in more than 50% of the samples. Chlorpyrifos, carbaryl, and diazinon were the only insecticides among the 10 most frequently detected compounds. Of the remaining pesticide parent compounds, 18 were detected in fewer than 30% of the samples, and 13 were not detected. The most frequently detected degradates were deethylatrazine; the oxygen analogs (OAs) of the organophosphorus insecticides chlorpyrifos, diazinon, and malathion; and 1-napthol (degradate of carbaryl). Deethylatrazine was detected in nearly 70% of the samples collected in Maryland, Indiana, and Nebraska but was detected only once in California. The OAs of chlorpyrifos and diazinon were detected primarily in California. Degradates of the acetanilide herbicides were rarely detected in rain, indicating that they are not formed in the atmosphere or readily volatilized from soils. Herbicides accounted for 91 to 98% of the total pesticide mass deposited by rain except in California, where insecticides accounted for 61% in 2004. The mass of pesticides deposited by rainfall was estimated to be less than 2% of the total applied in these agricultural areas. Copyright ?? 2008 by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. All rights reserved.

  18. Pesticide fate and transport throughout unsaturated zones in five agricultural settings, USA

    USGS Publications Warehouse

    Hancock, T.C.; Sandstrom, M.W.; Vogel, J.R.; Webb, R.M.T.; Bayless, E.R.; Barbash, J.E.

    2008-01-01

    Pesticide transport through the unsaturated zone is a function of chemical and soil characteristics, application, and water recharge rate. The fate and transport of 82 pesticides and degradates were investigated at five different agricultural sites. Atrazine and metolachlor, as well as several of the degradates of atrazine, metolachlor, acetochlor, and alachlor, were frequently detected in soil water during the 2004 growing season, and degradates were generally more abundant than parent compounds. Metolachlor and atrazine were applied at a Nebraska site the same year as sampling, and focused recharge coupled with the short time since application resulted in their movement in the unsaturated zone 9 m below the surface. At other sites where the herbicides were applied 1 to 2 yr before sampling, only degradates were found in soil water. Transformations of herbicides were evident with depth and during the 4-mo sampling time and reflected the faster degradation of metolachlor oxanilic acid and persistence of metolachor ethanesulfonic acid. The fraction of metolachlor ethanesulfonic acid relative to metolachlor and metolachlor oxanilic acid increased from 0.3 to > 0.9 at a site in Maryland where the unsaturated zone was 5 m deep and from 0.3 to 0.5 at the shallowest depth. The flux of pesticide degradates from the deepest sites to the shallow ground water was greatest (3.0–4.9 μmol m−2 yr−1) where upland recharge or focused flow moved the most water through the unsaturated zone. Flux estimates based on estimated recharge rates and measured concentrations were in agreement with fluxes estimated using an unsaturated-zone computer model (LEACHM).

  19. Occurrence of sulfonylurea, sulfonamide, imidazolinone, and other herbicides in rivers, reservoirs and ground water in the Midwestern United States, 1998

    USGS Publications Warehouse

    Battaglin, W.A.; Furlong, E.T.; Burkhardt, M.R.; Peter, C.J.

    2000-01-01

    Sulfonylurea (SU), sulfonamide (SA), and imidazolinone (IMI) herbicides are relatively new classes of chemical compounds that function by inhibiting the action of a plant enzyme, stopping plant growth, and eventually killing the plant. These compounds generally have low mammalian toxicity, but plants demonstrate a wide range in sensitivity to SUs, SAs, and IMIs with over a 10000-fold difference in observed toxicity levels for some compounds. SUs, SAs, and IMIs are applied either pre- or post-emergence to crops commonly at 1/50th or less of the rate of other herbicides. Little is known about their occurrence, fate, or transport in surface water or ground water in the USA. To obtain information on the occurrence of SU, SA, and IMI herbicides in the Midwestern United States, 212 water samples were collected from 75 surface-water and 25 ground-water sites in 1998. These samples were analyzed for 16 SU, SA and IMI herbicides by USGS Methods Research and Development Program staff using high-performance liquid chromatography/mass spectrometry. Samples were also analyzed for 47 pesticides or pesticide degradation products. At least one of the 16 SUs, SAs or IMIs was detected above the method reporting limit (MRL) of 0.01 ??g/l in 83% of 130 stream samples. Imazethapyr was detected most frequently (71% of samples) followed by flumetsulam (63% of samples) and nicosulfuron (52% of samples). The sum of SU, SA and IMI concentrations exceeded 0.5 ??g/l in less than 10% of stream samples. Acetochlor, alachlor, atrazine, cyanazine and metolachlor were all detected in 90% or more of 129 stream samples. The sum of the concentration of these five herbicides exceeded 50 ??g/l in approximately 10% of stream samples. At least one SU, SA, or IMI herbicide was detected above the MRL in 24% of 25 ground-water samples and 86% of seven reservoir samples. Copyright (C) 2000 Elsevier Science B.V.

  20. Pesticide fate and transport throughout unsaturated zones in five agricultural settings, USA.

    PubMed

    Hancock, Tracy C; Sandstrom, Mark W; Vogel, Jason R; Webb, Richard M T; Bayless, E Randall; Barbash, Jack E

    2008-01-01

    Pesticide transport through the unsaturated zone is a function of chemical and soil characteristics, application, and water recharge rate. The fate and transport of 82 pesticides and degradates were investigated at five different agricultural sites. Atrazine and metolachlor, as well as several of the degradates of atrazine, metolachlor, acetochlor, and alachlor, were frequently detected in soil water during the 2004 growing season, and degradates were generally more abundant than parent compounds. Metolachlor and atrazine were applied at a Nebraska site the same year as sampling, and focused recharge coupled with the short time since application resulted in their movement in the unsaturated zone 9 m below the surface. At other sites where the herbicides were applied 1 to 2 yr before sampling, only degradates were found in soil water. Transformations of herbicides were evident with depth and during the 4-mo sampling time and reflected the faster degradation of metolachlor oxanilic acid and persistence of metolachor ethanesulfonic acid. The fraction of metolachlor ethanesulfonic acid relative to metolachlor and metolachlor oxanilic acid increased from 0.3 to >0.9 at a site in Maryland where the unsaturated zone was 5 m deep and from 0.3 to 0.5 at the shallowest depth. The flux of pesticide degradates from the deepest sites to the shallow ground water was greatest (3.0-4.9 micromol m(-2) yr(-1)) where upland recharge or focused flow moved the most water through the unsaturated zone. Flux estimates based on estimated recharge rates and measured concentrations were in agreement with fluxes estimated using an unsaturated-zone computer model (LEACHM). PMID:18453430

  1. Composition, distribution, and characterization of suspected endocrine-disrupting pesticides in Beijing GuanTing Reservoir (GTR).

    PubMed

    Xue, Nandong; Xu, Xiaobai

    2006-05-01

    GuanTing Reservoir (GTR) is one of two main water resources for the agriculture, industry, and living uses of Beijing (China). As a result of extensive pollution over the last few decades (particularly the 1980s), the reservoir has not supplied potable water to Beijing city since 1997. Composition, distribution, and characterization of 31 suspected endocrine-disrupting pesticides in surface water, pore water, and surface sediments from the reservoir are reported in this study. An analytical procedure based on solid-phase extraction (SPE) technology and capillary gas chromatography with electron-capture detection has been developed for the simultaneous determination of the 31 suspected endocrine-disrupting pesticides including the compounds hexachlorocyclohexane, cyclodiene, diphenyl aliphatic, chlordane, and other selected pesticides (hexachlorobenzene, heptachlor, endrin aldehyde, hepachlor epoxide, dicofol, acetochlor, alachlor, metolachlor, chlorpyriphos, nitrofen, trifluralin, cypermethrin, fenvalerate, and deltamethrin). The result shows that the pesticide pollution is moderate in GTR and its tributaries, although pesticide residue values in a few sites are quite high when considering their endocrine-disrupting effects and chronic health effects. Among the analyzed pesticides, p,p'-DDE, o,p'-DDT, beta-HCH, endosulfan sulfate, and aldrin were the most abundant pesticides in water while o,p'-DOT, delta-HCH, beta-HCH, p,p'-DDE, p,p'-DDT, and endosulfan sulfate were the most abundant in sediment. The variation in concentration of pesticides among sites can be expected to be caused by several factors such as contaminants in the rivers and drainage of contaminated water from the surrounding agricultural fields. To reduce exposure to these endocrine-disrupting compounds, the abundant current use of pesticides in the area should be minimized. Regular monitoring is needed to manage the environmental hazards due to these pesticides. PMID:16446992

  2. Ultra-pressure liquid chromatography-electrospray tandem mass spectrometry for multiresidue determination of pesticides in water.

    PubMed

    Gervais, G; Brosillon, S; Laplanche, A; Helen, C

    2008-08-22

    A multiresidue analysis method has been developed for the determination of pesticides in water by ultra-performance liquid chromatography (UPLC) combined with tandem mass spectrometry (MS/MS). The selected pesticides represent a broad range of polarity and volatility [benzoylcyclohexanedione (mesotrione and sulcotrione); chloroacetamide (acetochlor, alachlor, dimethenamide, and metolachlor); phenoxyacetic acid (2,4-D and MCPA); phenoxypropionic (dichloprop and mecoprop); phenylurea (chlortoluron, diuron, isoproturon, linuron, and metoxuron); sulfonylurea (foramsulfuron, iodosulfuron, and nicolsulfuron); triazine (atrazine, cyanazine, desethylatrazine (DEA), desisopropylatrazine (DIA), simazine, and terbutylazine)]. The analytes were extracted using solid-phase extraction (SPE). The separation was carried out on an acquity UPLC BEH C18 column (1.7 microm, 50 mm x 1 mm ID) using a gradient elution profile and mobile phase consisting of 0.1% formic acid in water and acetonitrile. The pesticides were detected with a tandem mass spectrometer after being ionised positively or negatively (depending on the molecule) using an electrospray ionisation (ESI) source. To achieve the suitable extraction conditions for sample preparation, several parameters affecting the efficiency of SPE such as the nature of the sorbent and the eluent, extractant volume and pH were studied. The best recovery was obtained by the extraction with an Oasis HLB cartridge and 3 mL of a solution of acetonitrile/dichloromethane (1:1, v/v) at pH 2. The average recoveries of the pesticides in different samples ranged from 82 to 109%. The weight least squares (WLS) linear regression was used to calculate the limits of detection and quantification (LOD and LOQ) because the dispersion was heteroskedastic. All the pesticides could be correctly quantified at a concentration level of 50 ng L(-1) and most of them could be detected at a concentration inferior or equal to 8 ng L(-1). Efficiency and robustness of

  3. Pesticides in ground water in selected agricultural land-use areas and hydrogeologic settings in Pennsylvania, 2003-07

    USGS Publications Warehouse

    Loper, Connie A.; Breen, Kevin J.; Zimmerman, Tammy M.; Clune, John W.

    2009-01-01

    absence of bacteria only for the 10 wells representing the Blue Ridge crystalline and Triassic Lowland siliciclastic setting. Results of Spearman’s rank test showed strong positive correlations in the Devonian-Silurian carbonate setting between 1) the number of pesticides above the MRLs and nitrate concentration, and 2) concentrations of atrazine and nitrate. Atrazine concentration and nitrate concentration also showed a statistically significant positive correlation in the Great Valley siliciclastic setting. An additional component of baseline monitoring was to evaluate changes in pesticide concentration in water from wells representing hydrogeologic settings most vulnerable to contamination from pesticides. In 2003, 16 wells originally sampled in the 1990s were resampled—4 each in the Appalachian Mountain carbonate, Triassic Lowland siliciclastic, Great Valley carbonate, and Piedmont carbonate settings. Nine of these wells, where pesticide concentrations from 1993 and 2003 were analyzed at the NWQL, were chosen for a paired-sample analysis using concentrations of atrazine and metolachlor. A statistically significant decrease in atrazine concentration was identified using the Wilcoxon signed-rank test (p = 0.004); significant temporal changes in metolachlor concentrations were not observed (p = 0.625). Monitoring in three areas of special ground-water protection, where selected pesticide concentrations in well water were at or above the PPGWS action levels, was done at wells BE 1370 (Berks County, Oley Township), BA 437 (Blair County, North Woodbury Township), and LN 1842 (Lancaster County, Earl Township). Co-occurrence of pesticide-degradation products with parent compounds was documented for the first time in ground-water samples collected from these three wells. Degradation products of atrazine, cyanazine, acetochlor, alachlor, and metolachlor were commonly at larger concentrations than the parent compound in the same water sample. Pesticide occurrence in water

  4. Removal of Pesticides and Inorganic Contaminants in Anaerobic and Aerobic Biological Contactors

    EPA Science Inventory

    This presentation contains data on the removal of pesticides (acetochlor, clethodim, dicrotophos), ammonia, nitrate, bromate and perchlorate through aerobic and anaerobic biological treatment processes.

  5. Herbicide Transport and Transformations in the Unsaturated Zone of Three Small Agricultural Basins with Corn and Soybean Row Crops

    NASA Astrophysics Data System (ADS)

    Hancock, T. C.; Vogel, J. R.; Sandstrom, M. W.; Capel, P. D.; Bayless, R. E.; Webb, R. M.

    2006-05-01

    locations this fraction increased over time. At the Maple Creek sites, atrazine, metalochlor, acetochlor, and alachlor were detected, typically at concentrations higher than their metabolites. The Maple Creek site is influenced by focused recharge, macropore flow, and variable soil-moisture retention properties in soils that transition from loess to sand.

  6. Risk assessment of herbicides and booster biocides along estuarine continuums in the Bay of Vilaine area (Brittany, France).

    PubMed

    Caquet, Th; Roucaute, M; Mazzella, N; Delmas, F; Madigou, C; Farcy, E; Burgeot, Th; Allenou, J-P; Gabellec, R

    2013-02-01

    A 2-year study was implemented to characterize the contamination of estuarine continuums in the Bay of Vilaine area (NW Atlantic Coast, Southern Brittany, France) by 30 pesticide and biocide active substances and metabolites. Among these, 11 triazines (ametryn, atrazine, desethylatrazine, desethylterbuthylazine, desisopropyl atrazine, Irgarol 1051, prometryn, propazine, simazine, terbuthylazine, and terbutryn), 10 phenylureas (chlortoluron, diuron, 1-(3,4-dichlorophenyl)-3-methylurea, fenuron, isoproturon, 1-(4-isopropylphenyl)-3-methylurea, 1-(4-isopropylphenyl)-urea, linuron, metoxuron, and monuron), and 4 chloroacetanilides (acetochlor, alachlor, metolachlor, and metazachlor) were detected at least once. The objectives were to assess the corresponding risk for aquatic primary producers and to provide exposure information for connected studies on the responses of biological parameters in invertebrate sentinel species. The risk associated with contaminants was assessed using risk quotients based on the comparison of measured concentrations with original species sensitivity distribution-derived hazardous concentration values. For EU Water Framework Directive priority substances, results of monitoring were also compared with regulatory Environmental Quality Standards. The highest residue concentrations and risks for primary producers were recorded for diuron and Irgarol 1051 in Arzal reservoir, close to a marina. Diuron was present during almost the all survey periods, whereas Irgarol 1051 exhibited a clear seasonal pattern, with highest concentrations recorded in June and July. These results suggest that the use of antifouling biocides is responsible for a major part of the contamination of the lower part of the Vilaine River course for Irgarol 1051. For diuron, agricultural sources may also be involved. The presence of isoproturon and chloroacetanilide herbicides on some dates indicated a significant contribution of the use of plant protection products in

  7. Characterization of Ground-Water Quality, Upper Republican Natural Resources District, Nebraska, 1998-2001

    USGS Publications Warehouse

    Frankforter, Jill D.; Chafin, Daniele T.

    2004-01-01

    south-central Dundy, and south-central Perkins Counties. Generally, these concentrations were detected in samples from wells located in upland areas with permeable soils and a high percentage of cropland. In 1999, 31 of the ground-water samples collected from irrigation wells were analyzed for pesticides, and 14 samples (45 percent) had detectable concentrations of at least one pesticide compound. In 2000, all of the 23 irrigation-well samples analyzed had one or more pesticides present at detectable concentrations. In 2001, 12 of 26 domestic-well samples (46 percent) had detectable concentrations. Although the analytical method used during the study was changed to increase the number of pesticides included in the analyses, the pesticides detected in the ground-water samples from domestic and irrigation wells were limited to the commonly used herbicide compounds acetochlor, alachlor, atrazine, metolachlor, prometon, propachlor, propazine, trifluralin, and the atrazine degradation product deethylatrazine. Of the compounds detected, only atrazine (3.0 micrograms per liter) and alachlor (2.0 micrograms per liter) have MCLs established by the U.S. Environmental Protection Agency. None of the ground-water samples from the URNRD study area had concentrations that exceeded either MCL. Tritium age-dating analyses indicate water from about one-third of the sites entered the ground-water system prior to 1952. Because the increase in agricultural practices occurred during the 1950s and 1960s, it can be assumed that this water was not influenced by agricultural practices. Nitrogen-isotope speciation analyses for samples from three irrigation wells indicated that the source of nitrates in the ground water probably is synthetic fertilizer; however, the source at most irrigation wells probably is either naturally occurring or a mixture of water from various anthropogenic sources (such as synthetic fertilizer and animal waste).

  8. Evaluating the Influence of Drainage, Application, and Tillage Practices on the Dissipation of Chloroacetanilide Herbicides in Minnesota Soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Acetochlor and metolachlor are herbicides used in Minnesota and the United States for the control of broadleaf and annual weeds in corn, soybean and other crops. Water monitoring studies have reported the occurrences of acetochlor, metolachlor and their breakdown products in both ground and surface ...

  9. IMPROVING STRUCTURE-LINKED ACCESS TO PUBLICLY AVAILABLE CHEMICAL TOXICITY INFORMATION

    EPA Science Inventory

    Hepatotoxicity of the Herbicide Alachlor Associated with Glutathione Depletion, Oxidative Damage and Protein S-Cysteinyl Adduction.

    Toxicity of the herbicide alachlor (2-chloro-2',6'-diethtl-N-[methoxtmethtl]-acetanilide) has been attributed to cytochrome P450-dependent me...

  10. Hydrogeology, Chemical Characteristics, and Transport Processes in the Zone of Contribution of a Public-Supply Well in York, Nebraska

    USGS Publications Warehouse

    Landon, Matthew K.; Clark, Brian R.; McMahon, Peter B.; McGuire, Virginia L.; Turco, Michael J.

    2008-01-01

    aquifers (hereinafter, confined unmixed wells). Delta 18O and delta D values for a minority of wells in the confined aquifers were intermediate between those for the unconfined shallow wells and those for the confined unmixed wells. These intermediate values were consistent with mixing of water from unconfined and confined aquifers (hereinafter, confined mixed wells). Oxidation-reduction conditions were primarily oxic in the unconfined aquifer and variably reducing in the confined aquifers. Trace amounts of volatile organic compounds (VOC), particularly tetrachloroethylene (PCE) and trichloroethylene (TCE), were widely detected in unconfined shallow urban wells and indicated the presence of young urban recharge waters in most confined mixed wells. The presence of degradation products of agricultural pesticides (acetochlor and alachlor) in some confined mixed wells suggests that some fraction of the water in these wells also was the result of recharge in agricultural areas. In the unconfined aquifer, age-tracer data (chlorofluorocarbon and sulfur hexafluoride data, and tritium to helium-3 ratios) fit a piston-flow model, with apparent recharge ages ranging from 7 to 48 years and generally increasing with depth. Age-tracer data for the confined aquifers were consistent with mixing of 'old' water, not containing modern tracers recharged in the last 60 years, and exponentially-mixed 'young' water with modern tracers. Confined unmixed wells contained less than (=) 97% of old water. Confined mixed wells contained >30% young water and mean ages ranged from 12 to 14 years. Median concentrations of nitrate (as nitrogen, hereinafter, nitrate-N) were 17.3 and 16.0 mg/L (milligram per liter) in unconfined shallow urban and agricultural wells, respectively, indicating a range of likely nitrate sources. Septic systems are most numerous near the edge of the urban area and appear to be

  11. Environmental and human risk hierarchy of pesticides: A prioritization method, based on monitoring, hazard assessment and environmental fate.

    PubMed

    Tsaboula, Aggeliki; Papadakis, Emmanouil-Nikolaos; Vryzas, Zisis; Kotopoulou, Athina; Kintzikoglou, Katerina; Papadopoulou-Mourkidou, Euphemia

    2016-05-01

    A pesticide prioritization approach was developed and implemented in the Pinios River Basin of Central Greece. It takes under consideration the Level of Environmental Risk containing information on the frequency of occurrence of pesticides above environmental thresholds, the intensity of this occurrence and the spatial distribution as well as information about the fate and behavior of pesticides in the environment and the potential to have adverse impact on humans' health. Original 3-year monitoring data from 102 Stationary Sampling Sites located on rivers and their tributaries, reservoirs, streams and irrigation/drainage canals giving rise to a collection of 2382 water samples resulting in 7088 data sets, were included in this integrated prioritization study. Among 302 monitored active ingredients, 119 were detected at least once and the concentrations found in the aquatic systems for 41% of compounds were higher than the respective lowest Predicted Non-Effect Concentration (PNEC) values. Sixteen and 5 pesticides were found with risk ratios (MECmax/PNEC) above 10 (high concern) and 100 (very high concern), respectively. However, pesticides with maximum Measured Environmental Concentration (MECmax) values exceeding by 1000 times the respective lowest PNEC values were also found which were considered of extremely high concern; in the latter group were included prometryn, chlorpyrifos, diazinon, λ-cyhalothrin, cypermethrin, α-cypermethrin deltamethrin, ethalfluralin and phosmet. The sensitivity of the analytical methods used in the monitoring study was considered inadequate to meet the toxicological endpoints for 32 pesticides. The widest distribution of occurrence in the Stationary Sampling Sites of the monitoring program was found for the pesticides, prometryn, fluometuron, terbuthylazine, S-metolachlor, chlorpyrifos, diphenylamine, acetochlor, alachlor, 2,4-D, etridiazole, imidacloprid and lindane (γ-ΗCH). Among the 27 priority pesticides included in the

  12. Effects of urbanization on water quality in the Kansas River, Shunganunga Creek Basin, and Soldier Creek, Topeka, Kansas, October 1993 through September 1995

    USGS Publications Warehouse

    Pope, L.M.; Putnam, J.E.

    1997-01-01

    , respectively, before treatment-plant discharge to a calculated 4,900 and 4,700 colonies per 100 milliliters of water, respectively, after discharge. Median concentrations of dissolved solids were not significantly different between three sampling sites in the Shunganunga Creek Basin. Median concentrations of dissolved nitrate as nitrogen, total phosphorus, and dissolved orthophosphate were significantly larger in water from the upstream- most Shunganunga Creek sampling site than in water from either of the other sampling sites in the Shunganunga Creek Basin probably because of the site's proximity to a wastewater-treatment plant.Median concentrations of dissolved nitrate as nitrogen and total phosphorus during 1993-95 at upstream sampling sites were either significantlylarger than during 1979-81 in response to increase of wastewater-treatment plant discharge or smaller because of the elimination of wastewater-treatment plant discharge. Median concentrations of dissolved ammonia as nitrogen were significantly less during 1993-95 than during 1979-81. Median concentrations of total aluminum, iron, maganese, and molybdenum were significantly larger in water from the downstream-mostShunganunga Creek sampling site than in water from the upstream-most sampling site. This probably reflects their widespread use in the urbanenvironment between the upstream and downstream Shunganunga Creek sampling sites. Little water-quality effect from the urbanization was indicated by results from the Soldier Creek sampling site. Median concentrations of most water-quality constituents in water from this sampling site were the smallest in water from any sampling site in the study area. Herbicides were detected in water from all sampling sites. Some of the more frequently detected herbicides included acetochlor, alachlor,atrazine, cyanazine, EPTC, metolachlor, prometon, simazine, and tebuthiuron. Detected insecticides including chlordane,

  13. Anthropogenic Organic Compounds in Source Water of Selected Community Water Systems that Use Groundwater, 2002-05

    USGS Publications Warehouse

    Hopple, Jessica A.; Delzer, Gregory C.; Kingsbury, James A.

    2009-01-01

    Source water, defined as groundwater collected from a community water system well prior to water treatment, was sampled from 221 wells during October 2002 to July 2005 and analyzed for 258 anthropogenic organic compounds. Most of these compounds are unregulated in drinking water and include pesticides and pesticide degradates, gasoline hydrocarbons, personal-care and domestic-use products, and solvents. The laboratory analytical methods used in the study have detection levels that commonly are 100 to 1,000 times lower than State and Federal standards and guidelines for protecting water quality. Detections of anthropogenic organic compounds do not necessarily indicate a concern to human health but rather help to identify emerging issues and track changes in occurrence and concentrations over time. Less than one-half (120) of the 258 compounds were detected in at least one source-water sample. Chloroform, in 36 percent of samples, was the most commonly detected of the 12 compounds that were in about 10 percent or more of source-water samples. The herbicides atrazine, metolachlor, prometon, and simazine also were among the commonly detected compounds. The commonly detected degradates of atrazine - deethylatrazine and deisopropylatrazine - as well as degradates of acetochlor and alachlor, generally were detected at concentrations similar to or greater than concentrations of the parent herbicide. The compounds perchloroethene, trichloroethene, 1,1,1-trichloroethane, methyl tert-butyl ether, and cis-1,2-dichloroethene also were detected commonly. The most commonly detected compounds in source-water samples generally were among those detected commonly across the country and reported in previous studies by the U.S. Geological Survey's National Water-Quality Assessment Program. Relatively few compounds were detected at concentrations greater than human-health benchmarks, and 84 percent of the concentrations were two or more orders of magnitude less than benchmarks. Five

  14. VERIFICATION OF A TOXIC ORGANIC SUBSTANCE TRANSPORT AND BIOACCUMULATION MODEL

    EPA Science Inventory

    A field verification of the Toxic Organic Substance Transport and Bioaccumulation Model (TOXIC) was conducted using the insecticide dieldrin and the herbicides alachlor and atrazine as the test compounds. The test sites were two Iowa reservoirs. The verification procedure include...

  15. TREATING SOIL SOLUTION SAMPLERS TO PREVENT MICROBIAL REMOVAL OF ANALYTES

    EPA Science Inventory

    Soil microorganisms colonizing soil water sampling devices (lysimeters) reduced concentrations of biodegradable organic chemicals, including 2,4-dichlorophenoxy-acetic acid methyl ester, alachlor, methyl m-chlorobenzoate, and metolachlor as water entered through porous ceramic cu...

  16. Monitoring of herbicide effect in maize based on electrical measurements

    NASA Astrophysics Data System (ADS)

    Cseresnyés, I.; Fekete, G.; Végh, K.; Székács, A.; Mörtl, M.; Rajkai, K.

    2012-07-01

    The effect of the herbicide acetochlor on root growth was studied by a non-destructive electrical impedance and capacitance method in pot experiments on maize. Acetochlor was applied both as single active ingredient and mixed with safener AD-67 in two dosages. Without safener addition, acetochlor had a permanent inhibiting effect on plant root expansion. The safener AD-67 was capable of providing protective effect against herbicide application. High correlations between root electrical impedance or capacitance and the root dry mass or surface area under our laboratory conditions were confirmed by plant harvest method. Root electrical impedance and capacitance measurements proved to be valid for monitoring the effect of the herbicide influencing root development and for distinguishing plant groups subjected to different stress conditions.

  17. Agricultural chemicals in groundwater of the midwestern United States: Relations to land use

    USGS Publications Warehouse

    Kolpin, D.W.

    1997-01-01

    To determine the relations between land use and concentrations of selected agricultural chemicals (nitrate, atrazine residue [atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) + deethylatrazinc (2-amino-4-chloro-6-isopropylamino-s-triazine) + deisopropylatrazine (2-amino-4-chloro-6-ethylamino-s-triazine)], and alachlor residue [alachlor, [2-chloro-2′,6′-diethyl-N-(methoxymethyl) acetanilide] + alachlor ethanesulfonic acid (alachlor-ESA; 2-[(2,6-diethylphenyl)(methoxymethyl)amino]-2-oxoethanesulfonic acid)] in groundwater, detailed land use information based on accurate measurements from aerial photographs for the 1991 growing season was obtained within a 2-km radius surrounding 100 wells completed in near-surface unconsolidated aquifers in the midwestern USA. The most significant land use factors to the agricultural chemicals examined were: nitrate (amount of irrigated crop production, positive relation), atrazine residue (amount of irrigated crop production, positive relation), and alachlor residue (amount of highly erodible land, inverse relation). The investigation of smaller buffer sizes (size of circular area around sampled wells) proved insightful for this study. Additional land use factors having significant relations to all three agricultural chemicals were identified using these smaller buffer radii. The most significant correlations (correlation maxima) generally occurred at ≤500-m for nitrate and ≥1000-m for atrazine residue and alachlor residue. An attempt to improve the statistical relations to land use by taking hydrologic considerations into account (removing land outside the estimated most probable recharge area from the statistical analysis) was not as successful as anticipated. Only 45% of the nitrate, 32% of the atrazine residue, and 20% of the alachlor residue correlations were improved by a consideration of the estimated most probable recharge area.

  18. Changes in tolerance to herbicide toxicity throughout development stages of phototrophic biofilms.

    PubMed

    Paule, A; Roubeix, V; Lauga, B; Duran, R; Delmas, F; Paul, E; Rols, J L

    2013-11-15

    Ecotoxicological experiments have been performed in laboratory-scale microcosms to investigate the sensitivity of phototrophic biofilm communities to the alachlor herbicide, in relation to the stages of phototrophic biofilm maturation (age of the phototrophic biofilms) and physical structure (intact biofilm versus recolonization). The phototrophic biofilms were initially cultivated on artificial supports in a prototype rotating annular bioreactor (RAB) with Taylor-Couette type flow under constant operating conditions. Biofilms were collected after 1.6 and 4.4 weeks of culture providing biofilms with different maturation levels, and then exposed to nominal initial alachlor concentration of 10 μg L(-1) in either intact or recolonized biofilms for 15 days in microcosms (mean time-weighted average concentration - TWAC of 5.52 ± 0.74 μg L(-1)). At the end of the exposure period, alachlor effects were monitored by a combination of biomass descriptors (ash-free dry mass - AFDM, chlorophyll a), structural molecular fingerprinting (T-RFLP), carbon utilization spectra (Biolog) and diatom species composition. We found significant effects that in terms of AFDM, alachlor inhibited growth of the intact phototrophic biofilms. No effect of alachlor was observed on diatom composition or functional and structural properties of the bacterial community regardless of whether they were intact or recolonized. The intact three-dimensional structure of the biofilm did not appear to confer protection from the effects of alachlor. Bacterial community structure and biomass level of 4.4 weeks - intact phototrophic biofilms were significantly influenced by the biofilm maturation processes rather than alachlor exposure. The diatom communities which were largely composed of mobile and colonizer life-form populations were not affected by alachlor. This study showed that the effect of alachlor (at initial concentration of 10 μg L(-1) or mean TWAC of 5.52 ± 0.74 μg L(-1)) is mainly limited to

  19. Herbicides and their metabolites in rainfall: Origin, transport, and deposition patterns across the midwestern and northeastern United States, 1990-1991

    USGS Publications Warehouse

    Goolsby, D.A.; Thurman, E.M.; Pomes, M.L.; Meyer, M.T.; Battaglin, W.A.

    1997-01-01

    Herbicides were detected in rainfall throughout the midwestern and northeastern United States during late spring and summer of 1990 and 1991. Herbicide concentrations exhibited distinct geographic and seasonal patterns. The highest concentrations occurred in midwestern cornbelt states following herbicide application to cropland. Volume-weighted concentrations of 0.2- 0.4??g/L for atrazine and alachlor were typical in this area during mid- April through mid-July, and weighted concentrations as large as 0.6-0.9 ??g/L occurred at several sites. Concentrations of 1-3 ??g/L were measured in a few individual samples. Atrazine was detected most often followed by alachlor, deethylatrazine, metolachlor, cyanazine, and deisopropyl-atrazine. The high ratio (~0.5) of deethylatrazine to atrazine in rainfall suggests atmospheric degradation of atrazine. Mass deposition of herbicides was greatest in areas where herbicide use was high and decreased with distance from the cornbelt. Estimated deposition rates for both atrazine and alachlor ranged from more than 240 ??g m-2 yr-1 for some areas in the midwestern states to less than 10 ??g m-2 yr-1 for the New England states. The estimated annual deposition of atrazine on the Great Lakes ranged from about 12 to 63 ??g m-2 yr-1. The total amounts of atrazine and alachlor deposited annually in rainfall in the study area represent about 0.6% of the atrazine and 0.4% of the alachlor applied annually to crops in the study area.

  20. Effect of rice husk gasification residue application on herbicide behavior in micro paddy lysimeter.

    PubMed

    Ok, Junghun; Pisith, Sok; Watanabe, Hirozumi; Thuyet, Dang Quoc; Boulange, Julien; Takagi, Kazuhiro

    2015-06-01

    Effects of rice husk gasification residues (RHGR) application on the fate of herbicides, butachlor and pyrazosulfuron-ethyl, in paddy water were investigated using micro paddy lysimeters (MPLs). The dissipation of both herbicides in paddy water was faster in the RHGR treated MPL than in the control MPL. The average concentrations of butachlor and pyrazosulfuron-ethyl in paddy water in the lysimeter treated with RHGR during 21 days were significantly reduced by 51% and 48%, respectively, as compared to those in the lysimeter without RHGR application. The half-lives (DT50) of butachlor in paddy water for control and treatment were 3.1 and 2.3 days respectively, and these values of pyrazosulfuron-ethyl were 3.0 and 2.2 days, respectively. Based on this study, RHGR application in rice paddy environment is an alternative method to reduce the concentration of herbicide in paddy field water and consequently to reduce potential pollution to aquatic environment. PMID:25763539

  1. SOC REJECTION BY NANOFILTRATION

    EPA Science Inventory

    A study was conducted to evaluate the rejection of six synthetic organic compounds (SOCs) from a potable water source by a nanofiltration membrane process. The S0Cs were ethylene dibromide (EDB), dibromochloropropane (DBCP), chlordane, heptachlor, methoxychlor and alachlor. To in...

  2. TOXICITY, BIOCONCENTRATION, AND METABOLISM OF FIVE HERBICIDES IN FRESHWATER FISH

    EPA Science Inventory

    Acute and early life-stage toxicities were determined for the herbicides alachlor, bromacil, dinoseb, diuron, and propanil with the fathead minnow (Pimephales promelas). Uptake, bioconcentration potential, and elimination of 14C-labeled herbicides were studied in the same species...

  3. Hydrologic data for a study of pre-Illinoian glacial till in Linn County, Iowa, water year 1991

    USGS Publications Warehouse

    Bowman, P.R.

    1992-01-01

    Herbicide concentrations in rainfall ranged from 0.05 to 1.3 micrograms per liter. Herbicides detected in the largest concentrations included alachlor, atrazine, and metolachlor. Metribuzin was the only herbicide detected in ground-water samples at a concentration of 0.10 micrograms per liter in water from one observation well.

  4. CURRENT-USE PESTICIDES: ASSESSING EXPOSURE AND SPERMATOXICITY

    EPA Science Inventory

    We recently reported that higher levels of urinary metabolite (mercapturates) of the current-use pesticides alachlor, atrazine and diazinon were significantly associated with decreased semen quality in fertile men from mid-Missouri. The primary goal of this stud...

  5. EVALUATION OF GENETIC DAMAGE IN FISH EXPOSED TO PESTICIDES IN FIELD AQUATIC MICROCOSMS

    EPA Science Inventory

    Single cell gel electrophoresis (SCG) and micronucleus (MN) assays were used to measure DNA strand breaks and chromosomal damage in fish blood erythrocytes as biological indicators of exposure to alachlor and atrazine in a surrogate aquatic ecosystem. Caged common carp (Cyprinus...

  6. Herbicide interchange between a stream and the adjacent alluvial aquifer

    USGS Publications Warehouse

    Wang, W.; Squillace, P.

    1994-01-01

    Herbicide interchange between a stream and the adjacent alluvial aquifer and quantification of herbicide bank storage during high streamflow were investigated at a research site on the Cedar River flood plain, 10 km southeast of Cedar Rapids, Iowa. During high streamflow in March 1990, alachlor, atrazine, and metolachlor were detected at concentrations above background in water from wells as distant as 20, 50, and 10 m from the river's edge, respectively. During high streamflow in May 1990, alachlor, atrazine, cyanazine, and metolachlor were detected at concentrations above background as distant as 20, 50, 10, and 20 m from the river's edge, respectively. Herbicide bank storage took place during high streamflow when hydraulic gradients were from the river to the alluvial aquifer and the laterally infiltrating river water contained herbicide concentrations larger than background concentrations in the aquifer. The herbicide bank storage can be quantified by multiplying herbicide concentration by the "effective area" that a well represented and an assumed porosity of 0.25. During March 1990, herbicide bank storage values were calculated to be 1.7,79, and 4.0 mg/m for alachlor, atrazine, and metolachlor, respectively. During May 1990, values were 7.1, 54, 11, and 19 mg/m for alachlor, atrazine, cyanazine, and metolachlor, respectively. ?? 1994 American Chemical Society.

  7. DEVELOPMENT OF METHOD 535 FOR THE DETERMINATION OF CHLOROACETANILIDE AND OTHER ACETAMIDE HERBICIDE DEGRADATES IN DRINKING WATER BY SOLID PHASE EXTRACTION AND LIQUID CHROMATOGRAPHY/TANDEM MASS SPECTROMETRY

    EPA Science Inventory

    EPA Method 535 has been developed in order to provide a method for the analysis of "Alachlor ESA and other acetanilide degradation products" which are listed on U.S. EPA's 1998 Drinking Water Contaminant Candidate List. Method 535 uses solid phase extraction with a nonporous gr...

  8. NOVEL CHROMATOGRAPHIC SEPARATION AND CARBON SOLID PHASE EXTRACTION OF ACETANILIDE HERBICIDE DEGRADATION PRODUCTS

    EPA Science Inventory

    Six acetanilide herbicides are currently registered for use in the U.S. Over the past several years, ethanesufonic acid (ESA) and oxanilic acid (OA) degradatoin products of these acetanilide herbicides have been found in U.S. ground waters and surface waters. "Alachlor ESA and ...

  9. Overexpression of a specific soybean GmGSTU4 isoenzyme improves diphenyl ether and chloroacetanilide herbicide tolerance of transgenic tobacco plants.

    PubMed

    Benekos, Kostantinos; Kissoudis, Christos; Nianiou-Obeidat, Irini; Labrou, Nikolaos; Madesis, Panagiotis; Kalamaki, Mary; Makris, Antonis; Tsaftaris, Athanasios

    2010-10-01

    Plant glutathione transferases (GSTs) superfamily consists of multifunctional enzymes and forms a major part of the plants herbicide detoxification enzyme network. The tau class GST isoenzyme GmGSTU4 from soybean, exhibits catalytic activity towards the diphenyl ether herbicide fluorodifen and is active as glutathione-dependent peroxidase (GPOX). Transgenic tobacco plants of Basmas cultivar were generated via Agrobacterium transformation. The aim was to evaluate in planta, GmGSTU4's role in detoxifying the diphenyl ether herbicides fluorodifen and oxyfluorfen and the chloroacetanilides alachlor and metolachlor. Transgenic tobacco plants were verified by PCR and Southern blot hybridization and expression of GmGSTU4 was determined by RT-PCR. Leaf extracts from transgenic plants showed moderate increase in GST activity towards CDNB and a significant increase towards fluorodifen and alachlor, and at the same time an increased GPOX activity towards cumene hydroperoxide. GmGSTU4 overexpressing plants when treated with 200 μM fluorodifen or oxyfluorfen exhibited reduced relative electrolyte leakage compared to wild type plants. Moreover all GmGSTU4 overexpressing lines exhibited significantly increased tolerance towards alachlor when grown in vitro at 7.5 mg/L alachlor compared to wild type plants. No significant increased tolerance was observed to metolachlor. These results confirm the contribution of this particular GmGSTU4 isoenzyme from soybean in the detoxification of fluorodifen and alachlor, and provide the basis towards the development of transgenic plants with improved phytoremediation capabilities for future use in environmental cleanup of herbicides. PMID:20638428

  10. Effect of systemic herbicides on N2-fixing and phosphate solubilizing microorganisms in relation to availability of nitrogen and phosphorus in paddy soils of West Bengal.

    PubMed

    Das, Amal Chandra; Debnath, Anjan

    2006-11-01

    A field experiment has been conducted with four systemic herbicides viz., butachlor [N-(butoxymethyl)-2-chloro-2',6'-diethyl-acetanilide], fluchloralin [N-(2-chloroethyl)-(2,6-dinitro-N-propyl-4-trifluoromethyl) aniline], oxadiazon [5-terbutyl-3-(2,4-dichloro-5-isopro poxyphenyl)-1,3,4-oxadiazol-2-one] and oxyfluorfen [2-chloro-1-(3-ethoxy-4-nitrophenyl)-4-(trifluoromethyl) benzene] at their recommended field rates (2.0, 1.5, 0.4 and 0.12kga.i.ha(-1), respectively) to investigate their effects on growth and activities of aerobic non-symbiotic N(2)-fixing bacteria and phosphate solubilizing microorganisms in relation to availability of nitrogen and phosphorus in the rhizosphere soils as well as yield of the rice crop (Oryza sativa L cv. IR-36). Application of herbicides, in general, highly stimulated the population and activities of the target microorganisms, which resulted in a greater amount of atmospheric nitrogen fixation and phosphate solubilization in the rhizosphere soils of the test crop. The greater microbial activities subsequently augmented the mineralization and availability of nitrogen and phosphorus in the soil solution, which in turn increased the yield of the crop. Among the herbicides, oxyfluorfen was most stimulative followed by fluchloralin and oxadiazon in augmenting the microbial activities in soil. Butachlor also accentuated the mineralization and availability of nitrogen due to higher incitement of non-symbiotic N(2)-fixing bacteria in paddy soil. The grain and straw yields of the crop were also significantly increased due to the application of oxyfluorfen (20.2% and 21%) followed by fluchloralin (13.1% and 15.4%) and butachlor (9.1% and 10.2%), respectively. PMID:16630642

  11. Cytotoxicity of sulfurous acid on cell membrane and bioactivity of Nitrosomonas europaea.

    PubMed

    Jiang, Ruiyu; Wang, Mingqing; Xue, Jianliang; Xu, Ning; Hou, Guihua; Zhang, Wubing

    2015-01-01

    Nitrosomonas europaea, an ammonia oxidizing bacterium, was chosen as a research model to study the alteration of cell membrane in the presence of sulfurous acid and biodegradation of acetochlor. Significant changes of the outer cell membrane were observed in the presence of sulfurous acid using scanning electron microscopy (SEM) and Atomic Force Microscopy (AFM). The fluorescence polarization has shown a significant decrease in membrane fluidity and the increase of permeability of cell membrane. Lysozyme experiment show the cell becomes easily influenced by substance in medium. Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) measurements show considerable amount of Ca(2+) and Mg(2+) in the supernatant from the sulfurous acid exposed cells. Sulfurous acid treatment enhanced the ability of N. europaea to degrade acetochlor. On this basis, it can be concluded that the increased cell permeability is favor for the absorbability of nutrition. As a result, N. europaea grows faster and the biodegradation efficiency was improved. PMID:25240954

  12. Optimization of the polar organic chemical integrative sampler for the sampling of acidic and polar herbicides.

    PubMed

    Fauvelle, Vincent; Mazzella, Nicolas; Belles, Angel; Moreira, Aurélie; Allan, Ian J; Budzinski, Hélène

    2014-05-01

    This paper presents an optimization of the pharmaceutical Polar Organic Chemical Integrative Sampler (POCIS-200) under controlled laboratory conditions for the sampling of acidic (2,4-dichlorophenoxyacetic acid (2,4-D), acetochlor ethanesulfonic acid (ESA), acetochlor oxanilic acid, bentazon, dicamba, mesotrione, and metsulfuron) and polar (atrazine, diuron, and desisopropylatrazine) herbicides in water. Indeed, the conventional configuration of the POCIS-200 (46 cm(2) exposure window, 200 mg of Oasis® hydrophilic lipophilic balance (HLB) receiving phase) is not appropriate for the sampling of very polar and acidic compounds because they rapidly reach a thermodynamic equilibrium with the Oasis HLB receiving phase. Thus, we investigated several ways to extend the initial linear accumulation. On the one hand, increasing the mass of sorbent to 600 mg resulted in sampling rates (R s s) twice as high as those observed with 200 mg (e.g., 287 vs. 157 mL day(-1) for acetochlor ESA). Although detection limits could thereby be reduced, most acidic analytes followed a biphasic uptake, proscribing the use of the conventional first-order model and preventing us from estimating time-weighted average concentrations. On the other hand, reducing the exposure window (3.1 vs. 46 cm(2)) allowed linear accumulations of all analytes over 35 days, but R s s were dramatically reduced (e.g., 157 vs. 11 mL day(-1) for acetochlor ESA). Otherwise, the observation of biphasic releases of performance reference compounds (PRC), though mirroring acidic herbicide biphasic uptake, might complicate the implementation of the PRC approach to correct for environmental exposure conditions. PMID:24691721

  13. Herbicides and degradates in shallow aquifers of Illinois: Spatial and temporal trends

    USGS Publications Warehouse

    Mills, P.C.; Kolpin, D.W.; Scribner, E.A.; Thurman, E.M.

    2005-01-01

    During the fall of 2000, the occurrence was examined of 16 herbicides and 13 herbicide degradates in samples from 55 wells in shallow aquifers underlying grain producing regions of Illinois. Herbicide compounds with concentrations above 0.05 ??g/L were detected in 56 percent of the samples. No concentrations exceeded regulatory drinking water standards. The six most frequently detected compounds were degradates. Water age was an important factor in determining vulnerability of ground water to transport of herbicide compounds. Unconsolidated aquifers, which were indicated to generally contain younger ground water than bedrock aquifers, had a higher occurrence of herbicides (73 percent of samples) than bedrock aquifers (22 percent). Temporal analysis to determine if changes in concentrations of selected herbicides and degradates could be observed over a near decadal period indicated a decrease in detection frequency (25 to 18 percent) between samplings in 1991 and 2000. Over this period, significant differences in concentrations were observed for atrazine (decrease) and total acetochlor (increase). The increase in acetochlor compound concentrations corresponds to an increase in acetochlor use during the study period, while the decrease in atrazine concentrations corresponds to relatively consistent use of atrazine. Changes in frequency of herbicide detection and concentration do not appear related to changes in land use near sampled wells.

  14. [Preparation and application of solid phase extraction packing of zirconia microsphere coated with sulfonated crosslinked polystyrene].

    PubMed

    Shen, Shuchang; Liu, Yuhui; Xiao, Xiaoxing

    2013-08-01

    Zirconia microsphere was prepared by polymerization-induced colloid aggregation (PICA) method and carbon-carbon double bond was grafted onto its surface by titanic acid ester coupling reagent. Poly(styrene-divinylbenzene) was synthesized by free radical polymerization by using styrene, divinylbenzene and carbon-carbon double bond on the microsphere surface in solution system, so the polymer was coated on the microsphere surface. After the benzene ring of the polymer was sulfonated, the cation exchange packing for solid phase extraction (SPE) was obtained. The material was characterized by Fourier transform infrared spectroscopy, scanning electron microscope and X-ray energy dispersive spectroscopy. Three herbicides of mesotrione, atrazine and acetochlor in water were determined by the SPE cartridge coupled with high performance liquid chromatography (HPLC). In the range of 0.5 - 3.0 mg/L, the relationships between the peak areas and mass concentrations of mesotrione, atrazine and acetochlor were linear with the correlation coefficients of 0.9936, 0.9925, 0.9919, respectively. The limits of detection were 5.41, 6.72 and 13.4 microg/L for mesotrione, atrazine and acetochlor, respectively. The results showed that the zirconium dioxide microspheres coated with polymer have diameters in the range of about 6 to 8 microm, the SPE cartridges of which have high adsorption rate for the targets. PMID:24369611

  15. Comparative responses of river biofilms at the community level to common organic solvent and herbicide exposure.

    PubMed

    Paule, A; Roubeix, V; Swerhone, G D W; Roy, J; Lauga, B; Duran, R; Delmas, F; Paul, E; Rols, J L; Lawrence, J R

    2016-03-01

    Residual pesticides applied to crops migrate from agricultural lands to surface and ground waters. River biofilms are the first aquatic non-target organisms which interact with pesticides. Therefore, ecotoxicological experiments were performed at laboratory scale under controlled conditions to investigate the community-level responses of river biofilms to a chloroacetanilide herbicide (alachlor) and organic solvent (methanol) exposure through the development referenced to control. Triplicate rotating annular bioreactors, inoculated with river water, were used to cultivate river biofilms under the influence of 1 and 10 μg L(-1) of alachlor and 25 mg L(-1) of methanol. For this purpose, functional (thymidine incorporation and carbon utilization spectra) and structural responses of microbial communities were assessed after 5 weeks of development. Structural aspects included biomass (chlorophyll a, confocal laser scanning microscopy) and composition (fluor-conjugated lectin binding, molecular fingerprinting, and diatom species composition). The addition of alachlor resulted in a significant reduction of bacterial biomass at 1 μg L(-1), whereas at 10 μg L(-1), it induced a significant reduction of exopolymer lectin binding, algal, bacterial, and cyanobacterial biomass. However, there were no changes in biofilm thickness or thymidine incorporation. No significant difference between the bacterial community structures of control and alachlor-treated biofilms was revealed by terminal restriction fragment length polymorphism (T-RFLP) analyses. However, the methanol-treated bacterial communities appeared different from control and alachlor-treated communities. Moreover, methanol treatment resulted in an increase of bacterial biomass and thymidine incorporation as well. Changes in dominant lectin binding suggested changes in the exopolymeric substances and community composition. Chlorophyll a and cyanobacterial biomass were also altered by methanol. This study suggested

  16. Transport and attenuation of chloroacetanilides in an agricultural headwater catchment

    NASA Astrophysics Data System (ADS)

    Lefrancq, Marie; Imfeld, Gwenaël; Millet, Maurice; Payraudeau, Sylvain

    2015-04-01

    Chloroacetanilides (e.g., S-metolachlor and acetochlor) are pre-emergent herbicides used on corn and sugar beet and are applied to bare soil, which is prone to runoff and erosion. Some of these herbicides are chiral and the commercial products can be isomerically enriched in the enantiomer-S compared to the enantiomer-R as an example S-metolachlor 80/20% S to R . Determination of the transport of these herbicides in the dissolved and particulate phases of runoff water and degradation in agricultural catchments is currently lacking. The objectives of this study were i) to quantify over an corn growing season the export of chloroacetanilides and their main degradation products (ethane sulfonic (ESA) and oxanilic acid (OXA) degradates of metolachlor (MESA and MOXA) and acetochlor (AcESA and AcOXA)) in an 47 ha agricultural head-catchment in the dissolved and particulate phases, and ii) to evaluate S-metolachlor biodegradation from its application on the field to its export from the catchment using enantiomer analysis. Runoff, erosion, hydrochemistry and chloroacetanilide transport were evaluated at both the plot and catchment scales. Our results showed that an important amount of the pesticide load is missed when only the dissolved concentration of the parent compound is analysed. The total export coefficients for S-metolachlor and acetochlor and their degradation products were 11.4 and 11.8%, respectively, which includes both the dissolved and particulate loads. The partitioning of S-metolachlor and acetochlor between the dissolved and particulate phases varied widely over time and was linked to the suspended solid concentrations. Detection of S-metolachlor degradation products in runoff water was more frequent compared to that of acetochlor degradation products. Enrichment up to 37% of R-metolachlor was observed during the corn growing season, supporting enantioselective degradation of S-metolachlor. Our field study indicates the potential of enantiomer analyses for

  17. Evaluating Microtox as a tool for biodegradability assessment of partially treated solutions of pesticides using Fe3+ and TiO2 solar photo-assisted processes.

    PubMed

    Lapertot, Milena; Ebrahimi, Sirous; Oller, Isabel; Maldonado, Manuel I; Gernjak, Wolfgang; Malato, Sixto; Pulgarín, César

    2008-03-01

    To shorten phototreatment time is of major concern for the cost and energy benefits of the xenobiotics degradation performed by photocatalytic processes. Using photo-Fenton and TiO(2) phototreatments, partially photodegraded solutions of 6 separate pesticides (alachlor, atrazine, chlorfenvinphos, diuron, isoproturon and pentachlorophenol) were tested for biocompatibility, which was evaluated according to the Zahn-Wellens procedure. This study investigated if Microtox could be considered as a suitable global indicator capable of giving information on the evolution of biocompatibility of the water solution contaminated with organic pollutants during the phototreatment in order to promote biotreatment. The obtained results demonstrated that biodegradability increased significantly after short photo-Fenton treatment times for alachlor, diuron and pentachlorophenol. Uncertain results were obtained with atrazine and isoproturon. Microtox acute toxicity testing was shown to correctly represent dynamics and efficiency of phototreatment. PMID:18155146

  18. Detection of Pesticides and Pesticide Metabolites Using the Cross Reactivity of Enzyme Immunoassays

    USGS Publications Warehouse

    Thurman, E.M.; Aga, D.S.

    2001-01-01

    Enzyme immunoassay is an important environmental analysis method that may be used to identify many pesticide analytes in water samples. Because of similarities in chemical structure between various members of a pesticide class, there often may be an unwanted response that is characterized by a percentage of cross reactivity. Also, there may be cross reactivity caused by degradation products of the target analyte that may be present in the sample. In this paper, the concept of cross reactivity caused by degradation products or by nontarget analytes is explored as a tool for identification of metabolites or structurally similar compounds not previously known to be present in water samples. Two examples are examined in this paper from various water quality studies. They are alachlor and its metabolite, alachlor ethane sulfonic acid, and atrazine and its class members, prometryn and propazine. A method for using cross reactivity for the detection of these compounds is explained in this paper.

  19. Uptake of polycyclic aromatic hydrocarbon compounds by the gills of the bivalve mollusk Elliptio complanata.

    PubMed

    Birdsall, K; Kukor, J J; Cheney, M A

    2001-02-01

    Polycyclic aromatic hydrocarbons (PAHs) and herbicides are important contaminants of world water systems with effects on aquatic organisms. The uptake of naphthalene, anthracene, and chrysene by gills of the bivalve mollusk Elliptio complanata was determined. Additionally, the effects of paraquat, atrazine, alachlor, 2,4-dichlorophenoxyacetic acid (2,4-D), and 2,4-dinitrophenol on the uptake of these compounds were also determined. The results indicate (1) the uptake of anthracene is approximately equivalent to that of chrysene and the uptake of either of these compounds is higher than that of naphthalene; (2) comparisons of uptakes with that of inulin, which occupies only extracellular space, show that all compounds studied are taken up; (3) the uptakes of naphthalene, anthracene, and chrysene are initially altered by the presence of herbicides such as paraquat, alachlor, 2,4-D, atrazine, and 2,4-dinitrophenol. PMID:11351430

  20. Organochlorine and organophosphorus pesticide residues in raw buffalo milk from agroindustrial areas in Assiut, Egypt.

    PubMed

    Shaker, Eman M; Elsharkawy, Eman E

    2015-01-01

    Raw buffalo milk samples from the agroindustrial zone in upper Egypt were analyzed for the presence of organochlorine and organophosphorus pesticides using gas chromatography-mass spectroscopy. Five organochlorine pesticides namely, alachlor, dieldrin, hexachlorobenzene, lindane and methoxychlor and three organophosphorus pesticides chlorpyrifos, malathion, and parathion-methyl were detected in the milk samples. In 44% of the samples, the concentrations of lindane and malathion residues exceeded tolerance levels set by the European Commission (EC) in 2008. In addition, the concentrations of chlorpyrifos, methoxychlor, and hexachlorobenzene residues exceeded the 2008 EC maximum residual limits (MRLs) by 33, 66, and 88% of the examined samples, respectively. However, the levels of alachlor, dieldrin, and parathion-methyl residues were below EC MRLs. The results of this study confirm the risks of pesticide residues exposure that threaten consumer health in Egypt. Thus, we recommend that pesticide residue monitoring programs be instituted in all the developing countries. PMID:25575291

  1. A reconnaissance study of herbicides and their metabolites in surface water of the midwestern united states using immunoassay and gas chromatography/mass spectrometry

    USGS Publications Warehouse

    Michael, Thurman E.; Goolsby, D.A.; Meyer, M.T.; Mills, M.S.; Pomes, M.L.

    1992-01-01

    Preemergent herbicides and their metabolites, particularly atrazine, deethylatrazine, and metolachlor, persisted from 1989 to 1990 in the majority of rivers and streams in the midwestern United States. In spring, after the application of herbicides, the concentrations of atrazine, alachlor, and simazine were frequently 3-10 times greater than the U.S. Environmental Protection Agency maximum contaminant level (MCL). The concentration of herbicides exceeded the MCLs both singly and in combination. Two major degradation products of atrazine (deisopropylatrazine and deethylatrazine) also were found in many of the streams. The order of persistence of the herbicides and their metabolites in surface water was atrazine > deethylatrazine > metolachlor > alachlor > deisopropylatrazine > cyanazine. Storm runoff collected at several sites exceeded the MCL multiple times during the summer months as a function of stream discharge, with increased concentrations during times of increased streamflow. It is proposed that metabolites of atrazine may be used as indicators of surface-water movement into adjacent alluvial aquifers.

  2. Selection and analysis of sites highly vulnerable to groundwater contamination in southwestern Michigan. Final technical report, 1 April 1991-31 March 1992

    SciTech Connect

    Ervin, J.L.; Lusch, D.P.

    1992-04-01

    An ongoing study in central Cass County has demonstrated extensive nitrate contamination of the glacial drift aquifer in the Donnell Lake watershed. In addition, about 20% of 121 wells sampled showed detectable herbicides (atrazine, alachlor/metolachlor, and/or alachlor soil metabolite). Monthly monitoring of these wells in 1991 demonstrated stable water quality in the deeper wells, with some shallow wells showing from 30 to 300% increases in nitrate concentration over the summer. One well showed an 80% decrease in nitrate concentration. Herbicide concentrations were quite stable and consistent with previous findings. Generally the deeper wells (over 50 feet) demonstrated less contamination, but one 80 foot deep well demonstrated substantial nitrate and herbicide concentrations.

  3. Herbicides and nitrates in the Iowa River alluvial aquifer prior to changing land use, Iowa County, Iowa, 1996

    USGS Publications Warehouse

    Savoca, Mark E.; Tobias, Jennifer L.; Sadorf, Eric M.; Birkenholtz, Trevor L.

    1997-01-01

    Four herbicides (alachlor, atrazine, cyanazine, and metolachlor) and one nutrient (nitrate) were selected for study on the basis of frequent usage in Iowa and high detection rates in ground water (Detroy and Kuzniar, 1988). Alachlor was not detected at concentrations greater than the method detection limit (MDL). Atrazine was detected at concentrations greater than the MDL in samples from 48 percent of the 23 wells, cyanazine from 13 percent, metolachlor from 26 percent, and nitrate from 91 percent. None of the four herbicides were detected at concentrations greater than the respective U.S. Environmental Protection Agency's (USEPA) Maximum Contaminant Level (MCL) for drinking water. Thirteen percent of the samples had nitrate concentrations above the USEPA's MCL of 10 mg/L (milligrams per liter). Relations between constituent concentration and well depth were observed for specific constituents at individual well nests.

  4. Controlled release of water-soluble herbicides

    SciTech Connect

    Riggle, B.D.

    1985-01-01

    Pine kraft lignin was used to control the release of metribuzin (4-amino-6-tert-butyl-3-(methylthio)-as-triazin-5(4H)-one) and alachlor (2-chloro-2',6'-diethyl-N-methoxy-methyl acetanalide). Soil thin layer chromatography (TLC) analysis using /sup 14/C-metribuzin and /sup 14/C-alachlor demonstrated that NB-5203-58 series and PC940 series kraft lignins could retard the mobility of both herbicides after multiple soil TLC plate developments with water. Soil column chromatography analysis demonstrated that PC940C could retard the mobility of both herbicides after soil column water leaching by positioning the herbicides in the top portion of the soil column where the PC940C-herbicide mixture had been applied. There was a concentration effect where, as more PC940C was used, more /sup 14/C-labelled herbicide was retained in the top portion of the soil columns. Soil column chromatography and soil TLC plate analysis demonstrated that /sup 3/H-PC940C was immobile. Finally, PC940C significantly reduced metribuzin related phytotoxicity to field and greenhouse grown soybeans (Glycine max (L.) Merr.) which had been treated with PC940C rates of 0.77 and 1.15 L/ha and metribuzin rates of 0.42 and 0.84 kg/ha. The results for /sup 14/C-metribuzin and /sup 14/C-alachlor as well as the reduction in metribuzin related phytotoxicity to soybeans suggests that PC940C can effectively control the release of metribuzin and alachlor.

  5. Use of enzyme immunoassay for large water-quality surveys of major herbicides

    SciTech Connect

    Thurman, E.M.; Aga, D.S.; Zimmerman, L.R.; Goolsby, D.A.

    1996-10-01

    Commercially available enzyme-linked immunosorbent assay (ELISA) was used for the determination of major herbicides in several large water-quality surveys of surface water, rainwater, and ground water throughout the United States. The ELISA results were compared with gas chromatography/mass spectrometry (GC/MS) for accuracy and cross reactivity. In total, five compounds were analyzed: alachlor, atrazine, cyanazine, metolachlor, and (2,4-dichlorophenoxy) acetic acid (2,4-D). Results indicated that the ELISA and GC/MS results were comparable for cyanazine and metolachlor. The atrazine ELISA correlated well with GC/MS for surface- and ground-water samples from the central United States but did not correlate with samples from Texas where the cotton triazine, prometryn, is used. Results using the alachlor ELISA were poor because of cross reactivity with the metabolite, alachlor ethane-sulfonic acid. The ELISA for (2,4-dichlorophenoxy) acetic acid was insensitive at concentrations that occur in most surface water.

  6. Herbicide and nitrate variation in alluvium underlying a cornfield at a site in Iowa County, Iowa

    USGS Publications Warehouse

    Kalkhoff, S.J.; Detroy, M.G.; Cherryholmes, K.; Kuzniar, R.L.

    1992-01-01

    A hydrologic investigation to determine vertical and seasonal variation of atrazine, alachlor, cyanazine, and nitrate at one location and to relate the variation to ground-water movement in the Iowa River alluvium was conducted in Iowa County, Iowa, from March 1986 to December 1987. Water samples were collected at discrete intervals through the alluvial sequence from the soil zone to the base of the aquifer. Alachlor, atrazine, and cyanazine were detected most frequently in the soil zone but also were present in the upper part of the alluvial aquifer. Alachlor was detected sporadically, whereas, atrazine, cyanazine, and nitrate were present throughout the year. In the alluvial aquifer, the herbicides generally were not detected during 1986 and were present in detectable concentrations for only a short period of time in the upper 1.6 meters of the aquifer during 1987. Nitrate was present throughout the alluvium and was stratified in the alluvial aquifer. The largest nitrate concentrations were detected in the middle part of the aquifer. Nitrate concentrations were variable only in the upper 2 meters of the aquifer. Vertical movement of herbicides and nitrate in the soil correlated with precipitation and degree of saturation. A clay layer retarded vertical movement of atrazine but not nitrate from the soil layer to the aquifer. Vertical movement could not account for the chemical variation in the alluvial aquifer.

  7. Occurrence of selected pesticides and their metabolites in near-surface aquifers of the midwestern United States

    USGS Publications Warehouse

    Kolpin, D.W.; Michael, Thurman E.; Goolsby, D.A.

    1996-01-01

    The occurrence and distribution of selected pesticides and their metabolites were investigated through the collection of 837 water-quality samples from 303 wells across the Midwest. Results of this study showed that five of the six most frequently detected compounds were pesticide metabolites. Thus, it was common for a metabolite to be found more frequently in groundwater than its parent compound. The metabolite alachlor ethanesulfonic acid (alachlor-ESA; 2-[(2,6-diethylphenyl)(methoxymethyl)amino]-2-oxoethanesulfonic acid) was detected almost 10 times as frequently and at much higher concentrations than its parent compound alachlor (2-chloro-2‘,6‘-diethyl-N-(methoxymethyl)acetamide). The median detectable atrazine (2-chloro-4-ethylamino-6- isopropylamino-s-triazine) concentration was almost half that of atrazine residue (atrazine plus the two atrazine metabolites analyzed). Cyanazine amide [2-chloro-4-(1-carbamoyl-1-methylethylamino)-6-ethylamino-s-triazine] was detected almost twice as frequently as cyanazine (2-chloro-4-ethylamino-6-methylpropionitrileamino-s-triazine). Results show that information on pesticide metabolites is necessary to understand the environmental fate of pesticides. Consequently, if pesticide metabolites are not quantified, the effects of chemical use on groundwater quality would be substantially underestimated. Thus, continued research is needed to identify major degradation pathways for all pesticides and to develop analytical methods to determine their concentrations in water and other environmental media.

  8. Human skin binding and absorption of contaminants from ground and surface water during swimming and bathing

    SciTech Connect

    Wester, R.C.; Maibach, H.I. )

    1989-10-01

    Contaminants exist in ground and surface water. Human skin has the capacity to bind and then absorb these contaminants into the body during swimming and bathing. Powdered human stratum corneum will bind both lipid-soluble (alachlor, polychlorinated biphenyls (PCBs), benzene) and water-soluble (nitroaniline) chemicals. In vitro (Human skin) and in vivo (Rhesus monkey) studies show that these chemicals readily distribute into skin, and then some of the chemical is absorbed into the body. Linearity in binding and absorption exists for nitroaniline over a 10-fold concentration range. Multiple exposure to benzene is at least cumulative. Binding and adsorption can be significant for exposures as short as 30 minutes, and will increase with time. Adsorption with water dilution increased for alachlor, but not for dinoseb. Soap reversed the partitioning of alachlor between human stratum corneum and water. The PCBs could be removed from skin by soap and water for up to 3 hours and the decontamination potential decreased, due to continuing skin absorption. The model that in vitro and in vivo systems used should permit easy estimation of this area of extensive human exposure effect on risk assessment. 5 refs., 9 tabs.

  9. A clay-vesicle system for water purification from organic pollutants.

    PubMed

    Undabeytia, Tomas; Nir, Shlomo; Sánchez-Verdejo, Trinidad; Villaverde, Jaime; Maqueda, Celia; Morillo, Esmeralda

    2008-02-01

    Vesicle-clay complexes in which positively charged vesicles composed of didodecyldimethylammonium bromide (DDAB) were adsorbed on montmorillonite removed efficiently anionic (sulfentrazone, imazaquin) and neutral (alachlor, atrazine) pollutants from water. These complexes (0.5% w:w) removed 92-100% of sulfentrazone, imazaquin and alachlor and 60% of atrazine from a solution containing 10mg/L of it. A synergistic effect on the adsorption of atrazine was observed when all pollutants were present simultaneously (30 mg/L each), its percentage of removal being 85.5. Column filters (18 cm) filled with a mixture of quartz sand and vesicle-clay (100:1, w:w) were tested. For the passage of 1L (25 pore volumes) of a solution including all the pollutants at 10mg/L each, removal was complete for sulfentrazone and imazaquin, 94% for alachlor and 53.1% for atrazine, whereas removal was significantly less efficient when using activated carbon. A similar advantage of the vesicle-clay filter was observed for the capacities of removal. PMID:17915281

  10. Herbicide leaching as affected by macropore flow and within-storm rainfall intensity variation: a RZWQM simulation.

    PubMed

    Malone, Robert W; Weatherington-Rice, Julie; Shipitalo, Martin J; Fausey, Norman; Ma, Liwang; Ahuja, Lajpat R; Wauchope, R Don; Ma, Qingli

    2004-03-01

    Within-event variability in rainfall intensity may affect pesticide leaching rates in soil, but most laboratory studies of pesticide leaching use a rainfall simulator operating at constant rainfall intensity, or cover the soil with ponded water. This is especially true in experiments where macropores are present--macroporous soils present experimental complexities enough without the added complexity of variable rainfall intensity. One way to get around this difficulty is to use a suitable pesticide transport model, calibrate it to describe accurately a fixed-intensity experiment, and then explore the affects of within-event rainfall intensity variation on pesticide leaching through macropores. We used the Root Zone Water Quality Model (RZWQM) to investigate the effect of variable rainfall intensity on alachlor and atrazine transport through macropores. Data were used from an experiment in which atrazine and alachlor were surface-applied to 30 x 30 x 30 cm undisturbed blocks of two macroporous silt loam soils from glacial till regions. One hour later the blocks were subjected to 30-mm simulated rain with constant intensity for 0.5 h. Percolate was collected and analyzed from 64 square cells at the base of the blocks. RZWQM was calibrated to describe accurately the atrazine and alachlor leaching data, and then a median Mid-west variable-intensity storm, in which the initial intensity was high, was simulated. The variable-intensity storm more than quadrupled alachlor losses and almost doubled atrazine losses in one soil over the constant-intensity storm of the same total depth. Also rainfall intensity may affect percolate-producing macroporosity and consequently pesticide transport through macropores. For example, under variable rainfall intensity RZWQM predicted the alachlor concentration to be 2.7 microg ml(-1) with an effective macroporosity of 2.2 E(-4) cm(3) cm(-3) and 1.4 microg ml(-1) with an effective macroporosity of 4.6 E(-4) cm(3) cm(-3). Percolate

  11. Impact of glyphosate-tolerant soybean and glufosinate-tolerant corn production on herbicide losses in surface runoff.

    PubMed

    Shipitalo, Martin J; Malone, Robert W; Owens, Lloyd B

    2008-01-01

    Residual herbicides used in the production of soybean [Glycine max (L.) Merr] and corn (Zea mays L.) are often detected in surface runoff at concentrations exceeding their maximum contaminant levels (MCL) or health advisory levels (HAL). With the advent of transgenic, glyphosate-tolerant soybean and glufosinate-tolerant corn this concern might be reduced by replacing some of the residual herbicides with short half-life, strongly sorbed, contact herbicides. We applied both herbicide types to two chiseled and two no-till watersheds in a 2-yr corn-soybean rotation and at half rates to three disked watersheds in a 3-yr corn/soybean/wheat (Triticum aestivum L.)-red clover (Trifolium pratense L.) rotation and monitored herbicide losses in runoff water for four crop years. In soybean years, average glyphosate loss (0.07%) was approximately 1/7 that of metribuzin (0.48%) and about one-half that of alachlor (0.12%), residual herbicides it can replace. Maximum, annual, flow-weighted concentration of glyphosate (9.2 microg L(-1)) was well below its 700 microg L(-1) MCL and metribuzin (9.5 microg L(-1)) was well below its 200 microg L(-1) HAL, whereas alachlor (44.5 microg L(-1)) was well above its 2 microg L(-1) MCL. In corn years, average glufosinate loss (0.10%) was similar to losses of alachlor (0.07%) and linuron (0.15%), but about one-fourth that of atrazine (0.37%). Maximum, annual, flow-weighted concentration of glufosinate (no MCL) was 3.5 microg L(-1), whereas atrazine (31.5 microg L(-1)) and alachlor (9.8 microg L(-1)) substantially exceeded their MCLs of 3 and 2 microg L(-1), respectively. Regardless of tillage system, flow-weighted atrazine and alachlor concentrations exceeded their MCLs in at least one crop year. Replacing these herbicides with glyphosate and glufosinate can reduce the occurrence of dissolved herbicide concentrations in runoff exceeding drinking water standards. PMID:18268303

  12. Cross-resistance pattern and alternative herbicides for Cyperus difformis resistant to sulfonylurea herbicides in Korea.

    PubMed

    Kuk, Yong In; Kim, Kyung Hyun; Kwon, Oh Do; Lee, Do Jin; Burgos, Nilda R; Jung, Sunyo; Guh, Ja Ock

    2004-01-01

    A Cyperus difformis L accession from Chonnam province, Korea was tested for resistance to the sulfonylurea herbicide, imazosulfuron. The accession was confirmed to be resistant (R) and was cross-resistant to other sulfonylurea herbicides, bensulfuron-methyl, cyclosulfamuron and pyrazosulfuron-ethyl, the pyrimidinyl thiobenzoate herbicide, bispyribac-sodium, and the imidazolinone herbicide imazapyr, but not to imazaquin. Multiple resistance was tested using twelve herbicides with target sites other than acetolactate synthase (ALS). The R biotype could be controlled by other herbicides with different modes of action such as butachlor, carfentrazone-ethyl, clomeprop, dithiopyr, esprocarb, mefenacet, oxadiazon, pretilachlor, pyrazolate and thiobencarb, applied to soil at recommended rates. Several sulfonylurea herbicide-based mixtures can control both the R and S biotypes of C difformis, except sulfonylurea plus dimepiperate, molinate or pyriftalid, and pyrazolate plus butachlor. Although mixtures of sulfonylurea herbicides might be more effective, they should be avoided and used only in special cases. In terms of in vitro ALS activity, the R biotype was 1139-, 3583-, 1482-, 416-, 5- and 9-fold more resistant to bensulfuron-methyl, cyclosulfamuron, imazosulfuron, pyrazosulfuron-ethyl, bispyribac-sodium and imazapyr, respectively, than the S biotype. The in vivo ALS activity of the R biotype was also less affected by the sulfonylurea herbicides, imazosulfuron and pyrazosulfuron-ethyl, than the S biotype. Results of in vitro and in vivo ALS assays indicated that the resistance mechanism of C difformis to ALS inhibitor herbicides was primarily due to an alteration in the target enzyme, ALS. Greenhouse experiments showed delayed flowering and reduced seed production of the R biotype, which could possibly result in reduced fitness. This unusual observation needs to be confirmed in field situations. PMID:14727745

  13. Distribution and risk assessment of 82 pesticides in Jiulong River and estuary in South China.

    PubMed

    Zheng, Senllin; Chen, Bin; Qiu, Xiaoyan; Chen, Meng; Ma, Zhiyuan; Yu, Xingguang

    2016-02-01

    To discover the distribution and risk of pesticides in Jiulong River and estuary, the residues of 102 pesticides were analyzed in water, sediment and clam samples collected from 35 sites in different seasons. A total number of 82 pesticides were detected and the occurrence and the risk to human and fish were assessed. Most of pesticides with high frequency were medium or low toxic except for DDTs. DDTs were the significant contaminant and the widely used dicofol was the new source of DDTs. The spatial and seasonal variation of pesticide distribution was linked with the distribution of orchards and farmlands. Health risk from river water consumption was low (RQ < 0.1) while that from clam consumption was medium (RQ = 0.84). Pesticides in water posed great risk to fish and among the 76 water samples analyzed, 65 of them showed high risk (RQ > 1) and 6 showed medium risk (0.1 ≤ QR < 1). The single chemical posed high risk to fish included DDTs, triazophos, fenvalerate, bifenthrin and cyfluthrin, and those showed medium risk included dicofol, butachlor, isocarbophos, terbufos and cyhalothrin. There were 14 single pesticides detected with concentration above 100 ng L(-1) in this study and the pesticide with the highest concentration was procymidone (3904 ng L(-1)). Further experiments illustrated that procymidone could disrupt the expression of vitellogenin in the estuarine fish even at environmental concentrations. DDTs, dicofol, triazophos, isocarbophos, terbufos, cyfluthrin, bifenthrin, fenvalerate, cyhalothrin, butachlor and procymidone have become the significant pesticides and should be considered in aquatic ecosystem risk management. PMID:26461443

  14. Use of rice straw biochar simultaneously as the sustained release carrier of herbicides and soil amendment for their reduced leaching.

    PubMed

    Lü, Jinhong; Li, Jianfa; Li, Yimin; Chen, Baozhu; Bao, Zhangfeng

    2012-07-01

    The sustained release and reduced leaching of herbicides is expected for enhancing their efficacy and minimizing their pollution. For this purpose, the rice straw biochar made at a relatively low temperature (350 °C) (RS350) was used simultaneously as the carrier for incorporating herbicides besides as the soil amendment. In this way, the sustained release of herbicides acetochlor and 2,4-D was obtained in the release experiments, due to the high and reversible sorption by RS350 biochar. Besides, the RS350 biochar significantly reduced the leached amount of herbicides by 25.4%-40.7% for acetochlor, and by 30.2%-45.5% for 2,4-D, depending on the depth (50 or 100 mm) of biochar-amended soil horizon. The high retention of both herbicides in the biochar-amended topsoil makes it possible to extend their efficacy. The results suggest a potential way of using low temperature biochars to reduce the leaching of herbicides without impacting their efficacy. PMID:22686323

  15. Contaminant-mediated photobleaching of wetland chromophoric dissolved organic matter.

    PubMed

    Langlois, Maureen C; Weavers, Linda K; Chin, Yu-Ping

    2014-09-20

    Photolytic transformation of organic contaminants in wetlands can be mediated by chromophoric dissolved organic matter (CDOM), which in turn can lose its reactivity from photobleaching. We collected water from a small agricultural wetland (Ohio), Kawai Nui Marsh (Hawaii), the Everglades (Florida), and Okefenokee Swamp (Georgia) to assess the effect of photobleaching on the photofate of two herbicides, acetochlor and isoproturon. Analyte-spiked water samples were irradiated using a solar simulator and monitored for changes in CDOM light absorbance and dissolved oxygen. Photobleaching did not significantly impact the indirect photolysis rates of either herbicide over 24 hours of irradiation. Surprisingly, the opposite effect was observed with isoproturon, which accelerated DOM photobleaching. This phenomenon was more pronounced in higher-CDOM waters, and we believe that the redox pathway between triplet-state CDOM and isoproturon may be responsible for our observations. By contrast, acetochlor indirect photolysis was dependent on reaction with the hydroxyl radical and did not accelerate photobleaching of wetland water as much as isoproturon. Finally, herbicide indirect photolysis rate constants did not correlate strongly to any one chemical or optical property of the sampled waters. PMID:24828085

  16. [Study on usage of pesticides in various countries].

    PubMed

    Yamamoto, Miyako; Toda, Miou; Tanaka, Keiko; Sugita, Takiko; Sasaki, Shiho; Uneyama, Chikako; Morikawa, Kaoru

    2007-01-01

    Usage of pesticides in food items in export countries was studied, focusing items which Japan imports in large quantity. Japan has imported field crops such as wheat, corn and soy bean, and also grapefruit in large quantity on a weight base, mainly from United States, Australia and Canada. While, Japan has imported various kinds of vegetables in which China had the largest share. We collected usage data of pesticides for 44 food items of 17 countries of 2004. Pesticides which were used frequently (usage rank within top ten in each item/country) were dichlorvos, carbofuran, chlorpyrifos, dimethoate (insecticides), mancozeb, carbendazim, thiophanate-methyl, chlorthalonil (fungicides), glyphosate, 2,4-D, paraquat, acetochlor (herbicides). Carbendazim, thiophanate-methyl, acetochlor and dichlorvos were mainly used in China. Dithiocarbamates are used frequently in various food items in various countries, and also frequently detected in monitoring in foreign countries. Some pesticides such as bisultap, monosultap, etaboxam and triazmate were used only in certain countries, and available information on toxicity or analytical method was very limited. Some of pesticides described above have not been analyzed in the pesticide residue monitoring in Japan before 2005,however, many of them are subjects of analysis for import food after 2006 with the enforcement of positivelist system for residues of pesticide and veterinary medicines in food in Japan. PMID:18220053

  17. Comparative losses of glyphosate and selected residual herbicides in surface runoff from conservation-tilled watersheds planted with corn or soybean.

    PubMed

    Shipitalo, Martin J; Owens, Lloyd B

    2011-01-01

    Residual herbicides regularly used in conjunction with conservation tillage to produce corn ( L.) and soybean [ (L.) Merr] are often detected in surface water at concentrations that exceed their U.S. maximum contaminant levels (MCL) and ecological standards. These risks might be reduced by planting glyphosate-tolerant varieties of these crops and totally or partially replacing the residual herbicides alachlor, atrazine, linuron, and metribuzin with glyphosate, a contact herbicide that has a short half-life and is strongly sorbed to soil. Therefore, we applied both herbicide types at typical rates and times to two chisel-plowed and two no-till watersheds in a 2-yr corn/soybean rotation and at half rates to three disked watersheds in a 3-yr corn/soybean/wheat-red clover ( L.- L.) rotation and monitored herbicide losses in surface runoff for three crop years. Average dissolved glyphosate loss for all tillage practices, as a percentage of the amount applied, was significantly less ( ≤ 0.05) than the losses of atrazine (21.4x), alachlor (3.5x), and linuron (8.7x) in corn-crop years. Annual, flow-weighted, concentration of atrazine was as high as 41.3 μg L, much greater than its 3 μg L MCL. Likewise, annual, flow-weighted alachlor concentration (MCL = 2 μg L) was as high as 11.2 and 4.9 μg L in corn- and soybean-crop years, respectively. In only one runoff event during the 18 watershed-years it was applied did glyphosate concentration exceed its 700 μg L MCL and the highest, annual, flow-weighted concentration was 3.9 μg L. Planting glyphosate-tolerant corn and soybean and using glyphosate in lieu of some residual herbicides should reduce the impact of the production of these crops on surface water quality. PMID:21712598

  18. Pesticide sorption and leaching potential on three Hawaiian soils.

    PubMed

    Hall, Kathleen E; Ray, Chittaranjan; Ki, Seo Jin; Spokas, Kurt A; Koskinen, William C

    2015-08-15

    On the Hawaiian Islands, groundwater is the principal source of potable water and contamination of this key resource by pesticides is of great concern. To evaluate the leaching potential of four weak acid herbicides [aminocyclopyrachlor, picloram, metsulfuron-methyl, biologically active diketonitrile degradate of isoxaflutole (DKN)] and two neutral non-ionizable herbicides [oxyfluorfen, alachlor], their sorption coefficients were determined on three prevalent soils from the island of Oahu. Metsulfuron-methyl, aminocylcopyrachlor, picloram, and DKN were relatively low sorbing herbicides (K(oc) = 3-53 mL g(-1)), alachlor was intermediate (K(oc) = 120-150 mL g(-1)), and oxyfluorfen sorbed very strongly to the three soils (K(oc) > 12,000 mL g(-1)). Following determination of K(oc) values, the groundwater ubiquity score (GUS) indices for these compounds were calculated to predicted their behavior with the Comprehensive Leaching Risk Assessment System (CLEARS; Tier-1 methodology for Hawaii). Metsulfuron-methyl, aminocyclopyrachlor, picloram, and DKN would be categorized as likely leachers in all three Hawaiian soils, indicating a high risk of groundwater contamination across the island of Oahu. In contrast, oxyfluorfen, regardless of the degradation rate, would possess a low and acceptable leaching risk due to its high sorption on all three soils. The leaching potential of alachlor was more difficult to classify, with a GUS value between 1.8 and 2.8. In addition, four different biochar amendments to these soils did not significantly alter their sorption capacities for aminocyclopyrachlor, indicating a relatively low impact of black carbon additions from geologic volcanic inputs of black carbon. Due to the fact that pesticide environmental risks are chiefly dependent on local soil characteristics, this work has demonstrated that once soil specific sorption parameters are known one can assess the potential pesticide leaching risks. PMID:26024994

  19. Nitrate and herbicide loading in two groundwater basins of Illinois' sinkhole plain

    USGS Publications Warehouse

    Panno, S.V.; Kelly, W.R.

    2004-01-01

    This investigation was designed to estimate the mass loading of nitrate (NO3-) and herbicides in spring water discharging from groundwater basins in an agriculturally dominated, mantled karst terrain. The loading was normalized to land use and NO3- and herbicide losses were compared to estimated losses in other agricultural areas of the Midwestern USA. Our study area consisted of two large karst springs that drain two adjoining groundwater basins (total area of 37.7 km2) in southwestern Illinois' sinkhole plain, USA. The springs and stream that they form were monitored for almost 2 years. Nitrate-nitrogen (NO3-N) concentrations at three monitoring sites were almost always above the background concentration (1.9 mg/l). NO3-N concentrations at the two springs ranged from 1.08 to 6.08 with a median concentration of 3.61 mg/l. Atrazine and alachlor concentrations ranged from <0.01 to 34 ??g/l and <0.01 to 0.98 ??g/l, respectively, with median concentrations of 0.48 and 0.12 ??g/l, respectively. Approximately 100,000 kg/yr of NO3-N, 39 kg/yr of atrazine, and 2.8 kg/yr of alachlor were discharged from the two springs. Slightly more than half of the discharged NO3- came from background sources and most of the remainder probably came from fertilizer. This represents a 21-31% loss of fertilizer N from the groundwater basins. The pesticide losses were 3.8-5.8% of the applied atrazine, and 0.05-0.08% of the applied alachlor. The loss of atrazine adsorbed to the suspended solid fraction was about 2 kg/yr, only about 5% of the total mass of atrazine discharged from the springs. ?? 2004 Elsevier B.V. All rights reserved.

  20. New insights into the interactions between cork chemical components and pesticides. The contribution of π-π interactions, hydrogen bonding and hydrophobic effect.

    PubMed

    Olivella, M À; Bazzicalupi, C; Bianchi, A; Fiol, N; Villaescusa, I

    2015-01-01

    The role of chemical components of cork in the sorption of several pesticides has been investigated. For this purpose raw cork and three cork extracted fractions (i.e. cork free of aliphatic extractives, cork free of all extractives and cork free of all extractives and suberin) were used as sorbent of three ionic pesticides (propazine, 2,4-dichlorophenoxy acetic acid (2,4-D) and alachlor) and five non-ionic pesticides (chlorpyrifos, isoproturon, metamitron, methomyl and oxamyl) with a logKow within the range -0.47 to 4.92. The effect of cations on the ionic pesticides, propazine and 2,4-D sorption was also analyzed. Results indicated that the highest yields were obtained for chlorpyrifos and alachlor sorption onto raw cork (>55%). After removal of aliphatic extractives sorption of all pesticides increased that ranged from 3% for propazine to 31% for alachlor. In contrast, removal of phenolic extractives caused a sorption decrease. Low sorption yields were obtained for hydrophobic pesticides such as metamitron, oxamyl and methomyl (<11%) by using all cork fractions and extremely low when using raw cork (<1%). FTIR analysis was useful to indicate that lignin moieties were the main components involved on the sorption process. Modelling calculations evidenced that π-stacking interactions with the aromatic groups of lignin play a major role in determining the adsorption properties of cork toward aromatic pesticides. Results presented in this paper gain insights into the cork affinities for pesticides and the interactions involved in the sorption process and also enables to envisage sorption affinity of cork for other organic pollutants. PMID:25240950

  1. Synthetic organic agrochemicals in the lower Mississippi River and its major tributaries: Distribution, transport and fate

    USGS Publications Warehouse

    Pereira, W.E.; Rostad, C.E.; Leiker, T.J.

    1992-01-01

    The Mississippi River and its major tributaries transport herbicides and their degradation products from agricultural areas in the mid-western U.S.A. These compounds include atrazine and its degradation products (desethyl- and desisopropylatrazine), simazine, cyanazine, metolachlor, and alachlor and its degradation products (2-chloro-2',6'-diethylacetanilide, 2-hydroxy-2',6'-diethylacetanilide and 2,6-diethylaniline). These compounds were identified and confirmed by gas chromatography-ion trap mass spectrometry. Loads of these compounds were determined during five sampling trips in 1987-1989. Stream loads of these compounds indicated that atrazine and metolachlor were relatively conservative in downstream transport. Alachlor and its degradation products were generated from point and non-point sources. Seasonal variations and hydrologic conditions controlled the loads of these compounds in the Mississippi River. Cross-channel mixing was slow downstream from major river confluences, possibly requiring several hundred kilometers of downriver transit for completion. The annual transport of these compounds into the Gulf of Mexico was estimated to be < 2% of the annual application of each herbicide in the Midwest.The Mississippi River and its major tributaries transport herbicides and their degradation products from agricultural areas in the mid-western U.S.A. These compounds include atrazine and its degradation products (desethyl- and desisopropylatrazine), simazine, cyanazine, metolachlor, and alachlor and its degradation products (2-chloro-2???,6???-diethylacetanilide, 2-hydroxy-2???,6???-diethylacetanilide and 2,6-diethylaniline). These compounds were identified and confirmed by gas chromatography-ion trap mass spectrometry. Loads of these compounds were determined during five sampling trips in 1987-1989. Stream loads of these compounds indicated that atrazine and metolachlor were relatively conservative in downstream transport. Alachlor and its degradation products

  2. A summary of pesticides in ground-water data collected by government agencies in Indiana, December 1985 to April 1991

    USGS Publications Warehouse

    Risch, M.R.

    1994-01-01

    More than 1 pesticide was present in 16 of the 51 samples that had detections, for a total of 90 individual pesticide detections. Concentrations of the detected pesticides ranged from 0.04 to 49 micrograms per liter, and two-thirds of the detected concentrations were less than 1 microgram per liter. In about 29 percent of all detections, the concentration of 9 pesticides alachlor, aldrin, atrazine, dieldrin, EDB, heptachlor, heptachlor epoxide, simazine, and terbufos exceeded either the U.S. Environmental Protection Agency's Maximum Contaminant Level or adult lifetime Health Advisory.

  3. The occurrence and transport of agricultural pesticides in the Tuttle Creek lake-stream system, Kansas and Nebraska

    USGS Publications Warehouse

    Bevans, Hugh E.; Fromm, Carla Hyde; Watkins, Sharon A.

    1995-01-01

    Median monthly atrazine concentrations detected in surface-water samples from the Big Blue River basin (1977-86) exceeded the U.S. Environmental Protection Agency health-advisory level (3.0 micrograms per liter) during May through September. Herbicide loads transported from the basin in 1986, expressed in tons and in percentage of amount applied, were alachlor (1.2 tons, 0.23 percent), atrazine (19 tons, 2.2 percent), and metolachlor (2.2 tons, 2.7 percent).

  4. Natural attenuation of chloroacetinilide herbicides in aquatic systems

    USGS Publications Warehouse

    Graham, D.W.; Graham, W.H.; DeNoyelles, F., Jr.; Smith, V.H.

    1999-01-01

    A 4-yr research program that studied the transformation of alachlor and metolachlor in aquatic systems using field microcosms is presented. The field microcosms provided an accurate simulation of natural ecosystems while also permitting the controlled creation of numerous contamination scenarios and sufficient replication to allow statistical evaluation of the results. Different treatments were assessed including conditions as diverse as anaerobic, eutrophic waters typical of nutrient-rich wetland to aerobic, oligotrophic waters typical of the epilimnion of Canadian glacial lake. Herbicide transformation rate was most strongly affected by water temperature, oxygen conditions, nutrient levels within the system, and the specific herbicide assessed.

  5. Laboratory and quality assurance protocols for the analysis of herbicides in ground water from the Management Systems Evaluation Area, Princeton, Minnesota

    USGS Publications Warehouse

    Larson, S.J.; Capel, P.D.; VanderLoop, A.G.

    1996-01-01

    Laboratory and quality assurance procedures for the analysis of ground-water samples for herbicides at the Management Systems Evaluation Area near Princeton, Minnesota are described. The target herbicides include atrazine, de-ethylatrazine, de-isopropylatrazine, metribuzin, alachlor, 2,6-diethylaniline, and metolachlor. The analytical techniques used are solid-phase extraction, and analysis by gas chromatography with mass-selective detection. Descriptions of cleaning procedures, preparation of standard solutions, isolation of analytes from water, sample transfer methods, instrumental analysis, and data analysis are included.

  6. Residual and contact herbicide transport through field lysimeters via preferential flow.

    PubMed

    Malone, R W; Shipitalo, M J; Wauchope, R D; Sumner, H

    2004-01-01

    Usage of glyphosate [N-(phosphonomethyl)-glycine] and glufosinate [2-amino-4-(hydroxy-methylphosphinyl)butanoic acid] may reduce the environmental impact of agriculture because they are more strongly sorbed to soil and may be less toxic than many of the residual herbicides they replace. Preferential flow complicates the picture, because due to this process, even strongly sorbed chemicals can move quickly to ground water. Therefore, four monolith lysimeters (8.1 m(2) by 2.4 m deep) were used to investigate leaching of contact and residual herbicides under a worst-case scenario. Glufosinate, atrazine (6-chloro-N(2)-ethyl-N(4)-isopropyl-1,3,5-triazine-2,4-diamine), alachlor [2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl) acetamide], and linuron (3-3,4-dichlorophenyl-1-methoxy-1-methylurea) were applied in 1999 before corn (Zea mays L.) planting and glyphosate, alachlor, and metribuzin [4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)-one] were applied in 2000 before soybean [Glycine max (L.) Merr.] planting. A high-intensity rainfall was applied shortly after herbicide application both years. Most alachlor, metribuzin, atrazine, and linuron losses occurred within 1.1 d of rainfall initiation and the peak concentration of the herbicides coincided (within 0.1 d of rainfall initiation in 2000). More of the applied metribuzin leached compared with alachlor during the first 1.1 d after rainfall initiation (2.2% vs. 0.035%, P < 0.05). In 1999, 10 of 24 discrete samples contained atrazine above the maximum contaminant level (atrazine maximum contaminant level [MCL] = 3 mug L(-1)) while only one discrete sample contained glufosinate (19 mug L(-1), estimated MCL = 150 mug L(-1)). The results indicate that because of preferential flow, the breakthrough time of herbicides was independent of their sorptive properties but the transport amount was dependent on the herbicide properties. Even with preferential flow, glyphosate and glufosinate were not transported to

  7. Relations of water-quality constituent concentrations to surrogate measurements in the lower Platte River corridor, Nebraska, 2007 through 2011

    USGS Publications Warehouse

    Schaepe, Nathaniel J.; Soenksen, Philip J.; Rus, David L.

    2014-01-01

    The lower Platte River, Nebraska, provides drinking water, irrigation water, and in-stream flows for recreation, wildlife habitat, and vital habitats for several threatened and endangered species. The U.S. Geological Survey (USGS), in cooperation with the Lower Platte River Corridor Alliance (LPRCA) developed site-specific regression models for water-quality constituents at four sites (Shell Creek near Columbus, Nebraska [USGS site 06795500]; Elkhorn River at Waterloo, Nebr. [USGS site 06800500]; Salt Creek near Ashland, Nebr. [USGS site 06805000]; and Platte River at Louisville, Nebr. [USGS site 06805500]) in the lower Platte River corridor. The models were developed by relating continuously monitored water-quality properties (surrogate measurements) to discrete water-quality samples. These models enable existing web-based software to provide near-real-time estimates of stream-specific constituent concentrations to support natural resources management decisions. Since 2007, USGS, in cooperation with the LPRCA, has continuously monitored four water-quality properties seasonally within the lower Platte River corridor: specific conductance, water temperature, dissolved oxygen, and turbidity. During 2007 through 2011, the USGS and the Nebraska Department of Environmental Quality collected and analyzed discrete water-quality samples for nutrients, major ions, pesticides, suspended sediment, and bacteria. These datasets were used to develop the regression models. This report documents the collection of these various water-quality datasets and the development of the site-specific regression models. Regression models were developed for all four monitored sites. Constituent models for Shell Creek included nitrate plus nitrite, total phosphorus, orthophosphate, atrazine, acetochlor, suspended sediment, and Escherichia coli (E. coli) bacteria. Regression models that were developed for the Elkhorn River included nitrate plus nitrite, total Kjeldahl nitrogen, total phosphorus

  8. Effect of prairie grass on the dissipation, movement, and bioavailability of selected herbicides in prepared soil columns.

    PubMed

    Belden, Jason B; Phillips, Todd A; Coats, Joel R

    2004-01-01

    Phytoremediation of pesticide-contaminated sites using a prairie grass mixture (big bluestem, yellow indiangrass, and switch grass) has been suggested as a low-cost in situ remediation strategy. In this study, the proposed phytoremediation technique was applied to artificially prepared soil columns that were fortified with high concentrations of four herbicides (atrazine, alachlor, metolachlor, and pendimethalin). The fate and toxicity of the herbicides were compared with results from soil columns lacking vegetation. After either 150 or 240 d of phytoremediation, soils were watered with 7.5 cm of water, and leachate was collected. Columns were then divided into three sections (top, middle, bottom). For each section of the column, chemical analysis (ethyl acetate and water extractions), earthworm accumulation tests, and lettuce seedling growth tests were performed. The leachate was chemically analyzed and tested for chronic toxicity to algae. Atrazine and alachlor degraded rapidly in the column, and the total amount recoverable was less than 2% of applied. After 250 d, vegetation reduced the total recoverable amounts of metolachlor and pendimethalin by 78 and 39%, respectively. Metolachlor was the only compound found in leachate, and the amounts recovered were reduced 5- to 20-fold by vegetation. Vegetation decreased the bioavailability of pendimethalin as measured by 8-d, earthworm bioaccumulation factors (BAFs) and lettuce seedling growth assays. Decreases in mobility and bioavailability indicate that this technique may stabilize pesticide residues in addition to increasing dissipation rates. PMID:14768876

  9. Occurrence of herbicides, nitrite plus nitrate, and selected trace elements in ground water from northwestern and northeastern Missouri, July 1991 and 1992

    USGS Publications Warehouse

    Wilkison, Donald H.; Maley, Randall D.

    1994-01-01

    The U.S. Geological Survey and the Missouri Department of Health collected water samples for analysis of nitrite plus nitrate and herbicides from rural domestic wells in northwestern and northeastern Missouri in 1991 and 1992. In July 1991, samples were collected from 130 wells in Caldwell, Clinton, Daviess, Gentry, and Nodaway Counties in northwestern Missouri. Nitrite plus nitrate concentrations as nitrogen ranged from less than 0.05 to 63 milligrams per liter. Nitrite plus nitrate concentrations exceeded the State drinking-water standard of 10 milligrams per liter in water samples from 28 wells. One or more of the herbicides--alachlor, atrazine, cyanazine; metribuzin, metolachlor, and trifluralin--were detected at concentrations greater than or equal to 0.05 micrograms per liter in 19 samples. Atrazine was detected in water samples from 16 wells. In July 1992, water samples were collected from 147 wells in Audrain, Clark, Lewis, Monroe, Scotland, and Shelby Counties in northeastern Missouri. Nitrite plus nitrate as nitrogen concentrations in samples ranged from less than 0.05 to 60 milligrams per liter and exceeded 10 milligrams per liter in samples from 28 wells. One or more of the herbicides-alachlor, atrazine, cyanazine, metribuzin, and metolachlor-were detected at concentrations greater than 0.10 microgram per liter in water samples from 19 of the wells sampled. Atrazine was detected in water from 18 wells.

  10. Ecotoxicological hazards of herbicides on biological attributes of Zygogramma bicolorata Pallister (Coleoptera: Chrysomelidae).

    PubMed

    Hasan, Fazil; Ansari, M Shafiq

    2016-07-01

    Ecotoxic effects of commonly used herbicides i.e. glyphosate, atrazine, metribuzin, alachlor and 2, 4-D were evaluated on the biological and demographic parameters of Zygogramma bicolorata Pallister on parthenium in laboratory. The herbicides used in the bioassay were within a minimum range of their recommended field dose. In direct toxicity experiment, 2,4-D and alachlor caused the highest mortality of 3rd instars and prolonged the development time. Fecundity and eggs viability were also significantly reduced in all treatments. Indirect toxicity (carryover effect) was evaluated through life table analysis of F1 progenies developed from surviving 3rd instars treated for direct toxicity experiment. Incubation period and overall development time was considerably prolonged in all treatments especially in 2, 4-D treated group. Daily fecundity and population growth parameters were significantly lowest in 2, 4-D treated groups compared to other tested herbicides. A significantly greater number of females were produced in glyphosate treatment than other treatments. Based on the present study, none of the tested herbicide can be classified as safe to Zygogramma bicolorata, while glyphosate was found to be least toxic. Therefore, it can be concluded that application of field recommended dose of glyphosate might be used in integration with Z. bicolorata for effective management of parthenium, however this needs to be conducted under natural field conditions. PMID:27077536

  11. Variability of atmospheric pesticide concentrations between urban and rural areas during intensive pesticide application

    NASA Astrophysics Data System (ADS)

    Scheyer, Anne; Morville, Stéphane; Mirabel, Philippe; Millet, Maurice

    Intensive pesticide use leads to the contamination of water, soil and atmosphere. Atmospheric transport is responsible for pesticide dispersal over long distances. In this study, we evaluate the local dispersal of pesticides from agricultural to urban areas. For this purpose, three high-volume samplers, each equipped with a glass fiber filter and XAD-2 resin for the sampling of particulate and gas phase have been placed in a south-west transect (predominant wind direction) characteristic of rural and urban areas. The urban site (Strasbourg centre) is situated in the middle of two rural sites. Samples were taken simultaneously at three sites during pesticide treatments in autumn and spring 2002-2003. Sampling took place for 24 h at a flow rate of 10-15 m 3 h -1. The pesticides studied were those commonly used in the Alsace region for all crops (maize, cereal, vines …). Many of the pesticides analysed in atmospheric samples were not detected or observed very episodically at very low concentrations. For metolachlor, alachlor, trifluralin, atrazine and diflufenican, higher concentrations were observed, essentially during the application of these compounds. Moreover, some "spraying peaks" were observed for alachlor in the south rural site (near crops) at a level of 31 ng m -3 on 16-17 May 2003. These results show site and time dependence of atmospheric contamination by pesticides. A limited dispersal was also observed especially in the urban area during the application periods of pesticides.

  12. Agricultural chemicals in ground and surface water in a small watershed in Clayton County, Iowa, 1988-91

    USGS Publications Warehouse

    Kalkhoff, S.J.; Schaap, B.D.

    1995-01-01

    Nitrogen was present in all water samples from Deer Creek. Nitrate concentrations ranged from 0.70 to 17 mg/L. Alachlor was detected in 11 percent of the samples, atrazine in 69 percent, cyanazine in 19 percent, and metolachlor in 33 percent. Alachlor concentrations ranged from less than 0.10 to 0.53 ug/L, atrazine ranged from less than 0.10 to 55 ug/L, cyanazine ranged from less than 0.10 to 12 ug/L, and metolachlor ranged from less than 0.10 to 69 ug/L. Herbicide detections occurred most frequently in late spring and early summer during or just following chemical application. Overland flow is an important source of nitrogen and herbicides to Deer Creek. Substantial amounts of agricultural chemicals are transported from the watershed. As much as 4,700 pounds, or 6.7 pounds per acre, of nitrogen were estimated to be transported from the watershed in 1 year. Nitrogen loads transported from the Deer Creek watershed were less during dry years than during years with average or greater than average rainfall.

  13. Batch vs continuous-feeding operational mode for the removal of pesticides from agricultural run-off by microalgae systems: A laboratory scale study.

    PubMed

    Matamoros, Víctor; Rodríguez, Yolanda

    2016-05-15

    Microalgae-based water treatment technologies have been used in recent years to treat different water effluents, but their effectiveness for removing pesticides from agricultural run-off has not yet been addressed. This paper assesses the effect of microalgae in pesticide removal, as well as the influence of different operation strategies (continuous vs batch feeding). The following pesticides were studied: mecoprop, atrazine, simazine, diazinone, alachlor, chlorfenvinphos, lindane, malathion, pentachlorobenzene, chlorpyrifos, endosulfan and clofibric acid (tracer). 2L batch reactors and 5L continuous reactors were spiked to 10 μg L(-1) of each pesticide. Additionally, three different hydraulic retention times (HRTs) were assessed (2, 4 and 8 days) in the continuous feeding reactors. The batch-feeding experiments demonstrated that the presence of microalgae increased the efficiency of lindane, alachlor and chlorpyrifos by 50%. The continuous feeding reactors had higher removal efficiencies than the batch reactors for pentachlorobenzene, chlorpyrifos and lindane. Whilst longer HRTs increased the technology's effectiveness, a low HRT of 2 days was capable of removing malathion, pentachlorobenzene, chlorpyrifos, and endosulfan by up to 70%. This study suggests that microalgae-based treatment technologies can be an effective alternative for removing pesticides from agricultural run-off. PMID:26882523

  14. Occurrence of Atrazine and Related Compounds in Sediments of Upper Great Lakes.

    PubMed

    Guo, Jiehong; Li, Zhuona; Ranasinghe, Prabha; Bonina, Solidea; Hosseini, Soheil; Corcoran, Margaret B; Smalley, Colin; Kaliappan, Rajashankar; Wu, Yan; Chen, Da; Sandy, Andy L; Wang, Yawei; Rockne, Karl J; Sturchio, Neil C; Giesy, John P; Li, An

    2016-07-19

    Surface grab and core sediment samples were collected from Lakes Michigan, Superior, and Huron from 2010 to 2012, and concentrations of herbicides atrazine, simazine, and alachlor, as well as desethylatrazine (DEA), were determined. Concentrations of atrazine in surface grabs ranged from 0.01 to 1.7 ng/g dry weight and are significantly higher in the southern basin of Lake Michigan (latitude <44°) than other parts of the three lakes. The highest concentration of alachlor was found in sediments of Saginaw Bay in Lake Huron. The inventory and net fluxes of these herbicides were found to decline exponentially from the south to the north. The concentration ratio of DEA to atrazine (DEA/ATZ) increased with latitude, suggesting degradation of atrazine to DEA during atmospheric transport. DEA/ATZ also increased with sediment depth in the sediment cores. Diffusion of deposited herbicides from the upper sediment into deeper sediments has occurred, on the basis of the observed patterns of concentrations in dated sediment cores. Concentrations of atrazine in pore water were estimated and were higher than those reported for the bulk waters, suggesting the occurrence of solid-phase deposition of atrazine through the water column and that contaminated sediments act as a source releasing atrazine to the overlying water. PMID:27322944

  15. Estimating contributions of nitrate and herbicides from groundwater to headwater streams, northern Atlantic Coastal Plain, USA

    USGS Publications Warehouse

    Ator, Scott; Denver, Judith

    2012-01-01

    Groundwater transport often complicates understanding of surface-water contamination. We estimated the regional flux of nitrate and selected herbicides from groundwater to nontidal headwater streams of the Atlantic Coastal Plain (New Jersey through North Carolina) based on late-winter or spring base-flow samples from 174 streams. Sampled streams were selected randomly, and flux estimates are based on resulting population estimates rather than on empirical models, which have been used previously for similar estimates. Base-flow flux in the estimated 8,834 headwater streams of the study area are an estimated 21,200 kg/day of nitrate (as N) and 5.83, 0.565, and 20.7 kg/day of alachlor, atrazine, and metolachlor (and selected degradates), respectively. Base-flow flux of alachlor and metolachlor is <3% of the total base-flow flux of those compounds plus degradates. Base-flow flux of nitrate and herbicides as a percentage of applications is typically highest in well-drained areas and lowest in areas with abundant poor drainage and anoxic conditions. In Coastal Plain watersheds of Albemarle and Pamlico Sounds, <2% of applied nitrogen reaches headwater streams as base flow. On the Delmarva Peninsula part of the Chesapeake Bay watershed, however, more than 10% of such applications are transported through groundwater to streams, and base-flow nitrate flux represents 70% of total nitrogen flux in headwater streams.

  16. Degradates provide insight to spatial and temporal trends of herbicides in ground water

    USGS Publications Warehouse

    Kolpin, D.W.; Schnoebelen, D.J.; Thurman, E.M.

    2004-01-01

    During 2001, 86 municipal wells in Iowa were sampled and analyzed for 21 herbicide parent compounds and 24 herbicide degradates. The frequency of detection increased from 17% when only herbicide parent compounds were considered to 53% when both herbicide parents and degradates were considered. Thus, the transport of herbicide compounds to ground water is substantially underestimated when herbicide degradates are not considered. A significant difference in the results among the major aquifer types was apparent only when both herbicide parent compounds and their degradates were considered. In addition, including herbicide degradates greatly improved the statistical relation to the age of the water being sampled. When herbicide parent compounds are considered, only 40% of the wells lacking a herbicide detection could be explained by the age of the water predating herbicide use. However, when herbicide degradates were also considered, 80% of the ground water samples lacking a detection could be explained by the age of the water predating herbicide use. Finally, a temporal pattern in alachlor concentrations in ground water could only be identified when alachlor degradates were considered.

  17. Adsorption of pesticides from water by functionalized organobentonites.

    PubMed

    Cruz-Guzmán, Marta; Celis, Rafael; Hermosín, M Carmen; Koskinen, William C; Cornejo, Juan

    2005-09-21

    Replacement of natural inorganic cations of clay minerals with organic cations has been proposed as a strategy to improve the adsorptive capacity of clay minerals for organic compounds, including pesticides. The organic cations most commonly used for this purpose have been quaternary ammonium ions containing alkyl or aryl chains without specific functional groups. In this work, we evaluated the ability of two bentonites (SWy-2 and SAz-1) exchanged with four natural organic cations containing diverse functional groups (L-carnitine, L-cysteine ethyl ester, L-cystine dimethyl ester, and thiamine) as adsorbents of pesticides varying in their chemical structures (simazine, hexazinone, triadimefon, alachlor, carbaryl, and imazethapyr). For comparison purposes, the adsorptive properties of two "classical" organobentonites, hexadecyltrimethylammonium- and phenyltrimethylammonium-exchanged bentonites, were also determined. Most organobentonites displayed higher affinity for the pesticides than the untreated bentonites, but the improvement in adsorption capacity varied depending on the characteristics of the pesticide and the interlayer organic cation. Triadimefon, carbaryl, and imazethapyr displayed the highest affinity for carnitine (K(f) = 229-2377)-, thiamine (K(f) = 83-354)-, and cystine (K(f) = 96-100)-treated bentonites, respectively, whereas alachlor was adsorbed similarly by all organobentonites. In general, pesticide adsorption-desorption hysteresis was greater for adsorbents with the highest adsorption capacities. The results demonstrate that selective modification of smectitic clay minerals with natural organic cations containing appropriate functional groups can be a useful strategy to improve their performance for the removal of specific pesticides from the environment. PMID:16159179

  18. Pressurized fluid extraction for quantitative recovery of chloroacetanilide and nitrogen heterocyclic herbicides in soil.

    PubMed

    Zhu, Y; Yanagihara, K; Guo, F; Li, Q X

    2000-09-01

    Pressurized fluid extraction (PFE) is a new sample extraction method operated at elevated temperatures and pressures with liquid solvents. The use of PFE was investigated for the extraction of four Hawaiian clayey soils fortified with the selected chloroacetanilide and nitrogen heterocyclic herbicides Alachlor, Bromacil, Hexazinone, Metribuzin, and Tebuthiuron. The effects of operation temperature, pressure, flush volume, and static cycles on PFE performance were studied. Water was the most effective modifier of PFE for quantitative recoveries of the five herbicides in soils. The simple extraction method required pretreatment of the soil with 37.6% water and subsequent two-static-cycle extraction with a total of 32 mL of acetone at 1500 psi and 100 degrees C. Average recoveries of Alachlor, Bromacil, Hexazinone, Metribuzin, and Tebuthiuron ranged from 93 to 103% by the water-assisted PFE, compared with only 68-83% recoveries of the corresponding chemicals when no water was used. The extraction time and total organic solvent consumption were reduced from 18 h and 300 mL by Soxhlet to 22 min or less and 80 mL or less of organic solvent by PFE. PMID:10995321

  19. HYPOTHYROIDISM AND PESTICIDE USE AMONG MALE PRIVATE PESTICIDE APPLICATORS IN THE AGRICULTURAL HEALTH STUDY

    PubMed Central

    Goldner, Whitney S.; Sandler, Dale P.; Yu, Fang; Shostrom, Valerie; Hoppin, Jane A.; Kamel, Freya; LeVan, Tricia D.

    2013-01-01

    Objective Evaluate the association between thyroid disease and use of insecticides, herbicides, fumigants/fungicides in male applicators in the Agricultural Health Study. Methods We examined the association between use of 50 specific pesticides and self-reported hypothyroidism, hyperthyroidism, and ‘other’ thyroid disease among 22,246 male pesticide applicators. Results There was increased odds of hypothyroidism with ever-use of the herbicides 2,4-D, 2,4,5-T, 2,4,5-TP, alachlor, dicamba, and petroleum oil. Hypothyroidism was also associated with ever-use of eight insecticides: organochlorines chlordane, DDT, heptachlor, lindane, and toxaphene; organophosphates diazinon and malathion; and the carbamate carbofuran. Exposure-response analysis showed increasing odds with increasing level of exposure for the herbicides alachlor and 2,4-D, and the insecticides aldrin, chlordane, DDT, lindane, and parathion. Conclusions There is an association between hypothyroidism and specific herbicides and insecticides in male applicators, similar to previous results for spouses. PMID:24064777

  20. Sulphur flux through the sulphate assimilation pathway is differently controlled by adenosine 5′-phosphosulphate reductase under stress and in transgenic poplar plants overexpressing γ-ECS, SO, or APR

    PubMed Central

    Scheerer, Ursula; Haensch, Robert; Mendel, Ralf R.; Kopriva, Stanislav; Rennenberg, Heinz; Herschbach, Cornelia

    2010-01-01

    Sulphate assimilation provides reduced sulphur for the synthesis of cysteine, methionine, and numerous other essential metabolites and secondary compounds. The key step in the pathway is the reduction of activated sulphate, adenosine 5′-phosphosulphate (APS), to sulphite catalysed by APS reductase (APR). In the present study, [35S]sulphur flux from external sulphate into glutathione (GSH) and proteins was analysed to check whether APR controls the flux through the sulphate assimilation pathway in poplar roots under some stress conditions and in transgenic poplars. (i) O-Acetylserine (OAS) induced APR activity and the sulphur flux into GSH. (ii) The herbicide Acetochlor induced APR activity and results in a decline of GSH. Thereby the sulphur flux into GSH or protein remained unaffected. (iii) Cd treatment increased APR activity without any changes in sulphur flux but lowered sulphate uptake. Several transgenic poplar plants that were manipulated in sulphur metabolism were also analysed. (i) Transgenic poplar plants that overexpressed the γ-glutamylcysteine synthetase (γ-ECS) gene, the enzyme catalysing the key step in GSH formation, showed an increase in sulphur flux into GSH and sulphate uptake when γ-ECS was targeted to the cytosol, while no changes in sulphur flux were observed when γ-ECS was targeted to plastids. (ii) No effect on sulphur flux was observed when the sulphite oxidase (SO) gene from Arabidopsis thaliana, which catalyses the back reaction of APR, that is the reaction from sulphite to sulphate, was overexpressed. (iii) When Lemna minor APR was overexpressed in poplar, APR activity increased as expected, but no changes in sulphur flux were observed. For all of these experiments the flux control coefficient for APR was calculated. APR as a controlling step in sulphate assimilation seems obvious under OAS treatment, in γ-ECS and SO overexpressing poplars. A possible loss of control under certain conditions, that is Cd treatment, Acetochlor

  1. Sulphur flux through the sulphate assimilation pathway is differently controlled by adenosine 5'-phosphosulphate reductase under stress and in transgenic poplar plants overexpressing gamma-ECS, SO, or APR.

    PubMed

    Scheerer, Ursula; Haensch, Robert; Mendel, Ralf R; Kopriva, Stanislav; Rennenberg, Heinz; Herschbach, Cornelia

    2010-01-01

    Sulphate assimilation provides reduced sulphur for the synthesis of cysteine, methionine, and numerous other essential metabolites and secondary compounds. The key step in the pathway is the reduction of activated sulphate, adenosine 5'-phosphosulphate (APS), to sulphite catalysed by APS reductase (APR). In the present study, [(35)S]sulphur flux from external sulphate into glutathione (GSH) and proteins was analysed to check whether APR controls the flux through the sulphate assimilation pathway in poplar roots under some stress conditions and in transgenic poplars. (i) O-Acetylserine (OAS) induced APR activity and the sulphur flux into GSH. (ii) The herbicide Acetochlor induced APR activity and results in a decline of GSH. Thereby the sulphur flux into GSH or protein remained unaffected. (iii) Cd treatment increased APR activity without any changes in sulphur flux but lowered sulphate uptake. Several transgenic poplar plants that were manipulated in sulphur metabolism were also analysed. (i) Transgenic poplar plants that overexpressed the gamma-glutamylcysteine synthetase (gamma-ECS) gene, the enzyme catalysing the key step in GSH formation, showed an increase in sulphur flux into GSH and sulphate uptake when gamma-ECS was targeted to the cytosol, while no changes in sulphur flux were observed when gamma-ECS was targeted to plastids. (ii) No effect on sulphur flux was observed when the sulphite oxidase (SO) gene from Arabidopsis thaliana, which catalyses the back reaction of APR, that is the reaction from sulphite to sulphate, was overexpressed. (iii) When Lemna minor APR was overexpressed in poplar, APR activity increased as expected, but no changes in sulphur flux were observed. For all of these experiments the flux control coefficient for APR was calculated. APR as a controlling step in sulphate assimilation seems obvious under OAS treatment, in gamma-ECS and SO overexpressing poplars. A possible loss of control under certain conditions, that is Cd treatment

  2. [The Study on the Characteristics of Organic Pollution in Typical Herbicide Plant Wastewater].

    PubMed

    Chen, Yu-hui; Xi, Hong-bo; Yu, Dong; Zhou, Yue-xi; Chen, Xue-min; Fu, Xiao-yong

    2015-12-01

    Herbicide wastewater is one of tne industrial wastewater, it has high salt content, poor biodegradability, biodegradable characteristics. Nitrogen-containing organic compounds are dominated in dissolved organic matter and dissolved organic matter of wastewater, BOD: COD = 0.045, C:N:P = 692:426:1. Applying static headspace, purg and trap, solid-phase extraction, solid-phase microextraction and liquid-liquid extraction as pretreatment methods combined with gas chromatography/mass spectrometry (GC/MS), which qualitatively analyzed the organic components of the Atrazine, acetochlor herbicide production wastewater and researched the UV spectrum, three-dimensional fluorescence spectroscopy of the wastewater and its major pollutants. The study of GC/MS indicated that Wastewater contained chlorinated hydrocarbons, BTEX and triazines, amides herbicides etc. 38 kinds of volatile and semi-volatile organic compounds, atrazine and acetochlor herbicides accounted for 87. 99%. Affected monocyclic or heterocyclic substances, the ultraviolet absorption spectrum of the wastewater in 210-230 and 250-270 nm in that the amino group lead to the UV absorption red shift 20 nm. Wastewater generated 5 fluorescence peak in λ(ex)/λ(em) = 200-280/300-400 nm, such as a(225/305 nm), b(265/365 nm), c(275/305 nm), d(285/390 nm), e(320/375 nm). Based on three-dimensional fluorescence results of the different functional groups of the characteristics organic, fluorescent area of unsaturated bond is in λ(ex)/λ(em) = 215-230/290-340 nm, the main contribution of the fluorescent substance in the region were olefins, benzene, heterocyclic in the wastewater; fluorescent area of Phenolic hydroxyl and carbonyl is in λ(ex)/λ(em) = 270/300 nm, the main contribution of the fluorescent substance in the region were phenols, ketones. PMID:26964227

  3. Herbicides in ground water beneath Nebraska's Management Systems Evaluation Area.

    PubMed

    Spalding, Roy F; Exner, Mary E; Snow, Daniel D; Cassada, David A; Burbach, Mark E; Monson, Stephen J

    2003-01-01

    Profiles of ground water pesticide concentrations beneath the Nebraska Management Systems Evaluation Area (MSEA) describe the effect of 20 yr of pesticide usage on ground water in the central Platte Valley of Nebraska. During the 6-yr (1991-1996) study, 14 pesticides and their transformation products were detected in 7848 ground water samples from the unconfined water table aquifer. Triazine and acetamide herbicides applied on the site and their transformation products had the highest frequencies of detection. Atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4,-diamine] concentrations decreased with depth and ground water age determined with 3H/3He dating techniques. Assuming equivalent atrazine input during the past 20 yr, the measured average changes in concentration with depth (age) suggest an estimated half-life of >10 yr. Hydrolysis of atrazine and deethylatrazine (DEA; 2-chloro-4-amino-6-isopropylamino-s-triazine) to hydroxyatrazine [6-hydroxy-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine] appeared to be the major degradation route. Aqueous hydroxyatrazine concentrations are governed by sorption on the saturated sediments. Atrazine was detected in the confined Ogallala aquifer in ultra-trace concentrations (0.003 microg L(-1)); however, the possibility of introduction during reverse circulation drilling of these deep wells cannot be eliminated. In fall 1997 sampling, metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide] was detected in 57% of the 230 samples. Metolachlor oxanilic acid [(2-ethyl-6-methylphenyl)(2-methoxy-1-methylethyl) amino]oxo-acetic acid] was detected in most samples. In ground water profiles, concentrations of metolachlor ethane sulfonic acid [2-[(ethyl-6-methylphenyl)(2-methoxy-1-methylethyl)amino]-2-oxo-ethanesulfonic acid] exceeded those of deethylatrazine. Alachlor [2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)acetamide] was detected in <1% of the samples; however, alachlor

  4. Pesticides and their metabolites in wells of Suffolk County, New York, 1998

    USGS Publications Warehouse

    Phillips, Patrick J.; Eckhardt, D.A.; Terracciano, S.A.; Rosenmann, Larry

    1999-01-01

    Five insecticide residues and 20 herbicide residues were detected in water samples collected from 50 shallow wells screened in the surficial sand and gravel aquifer in Suffolk County, Long Island in areas with known or suspected residues. Laboratory analytical methods with extremely low detection limits - from 0.001 to 0.2 ?g/L (micrograms per liter) - were used to analyze the samples for 60 pesticide residues. Forty-four of the samples contained at least one pesticide residue, and some samples contained as many as 11 different pesticides or pesticide metabolites. Only four water- quality standards were exceeded in the samples collected in this study. Dieldrin exceeded the New York State Class GA standard (0.004 ?g/L) in samples from eight wells. The Federal and New York State Maximum Contaminant Level for simazine (4 ?g/L) was exceeded in samples from two wells, and the State Class GA standard for simazine (0.5 ?g/L) was exceeded in samples from six wells. Federal water-quality standards have not been established for many of the compounds detected in this study, including herbicide metabolites. Maximum concentrations of four herbicide metabolites -metolachlor ESA (ethanesulfonic acid), metolachlor OA (oxanilic acid), and the alachlor metabolites alachlor ESA and alachlor OA -exceeded 20 ?g/L. The maximum concentration of one herbicide (tebuthiuron) exceeded 10 ?g/L, and the maximum concentration of three herbicides (simazine, metolachlor, and atrazine) and one herbicide metabolite (deisopropylatrazine) ranged from 1 to 10 ?g/L. The herbicide metolachlor, which is used on potato fields in Suffolk County, and its metabolites (metolachlor ESA and metolachlor OA) were most frequently detected in samples from agricultural areas. The herbicides simazine and tebuthiuron, which were used in utility rights-of-way, and the simazine metabolite deisopropylatrazine were detected at concentrations greater than 0.05 ?g/L most frequently in samples from residential and mixed land

  5. Phytotoxicity of four herbicides on Ceratophyllum demersum, Vallisneria natans and Elodea nuttallii.

    PubMed

    Pan, Huiyun; Li, Xiaolu; Xu, Xiaohua; Gao, Shixiang

    2009-01-01

    The physiological effects of 4 herbicides (butachlor, quinclorac, bensulfuron-methyl and atrazine) on 3 submerged macrophytes (Ceratophyllum demersum, Vallisneria natans and Elodea nuttallii) were tested in laboratory. The variables of the relative growth rate and the photosynthetic pigment content showed that all of the tested herbicides affected the growth of the plants obviously, even at the lowest concentration (0.0001 mg/L). Except for the C. demersum treated with quinclorac at 0.005 and 0.01 mg/L, the relative growth rates of the plants were inhibited significantly (p < 0.01). Statistical analysis of chlorophyll a (Chl-a) contents was carried out with both the t-test and one-way ANOVA to determine the difference between the treatment and control. The results showed that Chl-a contents of the plants in all treatment groups were affected by herbicides significantly, except for the C. demersum treated with bensulfuron-methyl at 0.0005 mg/L. The decrease in Chl-a content was positively correlated to the dosage of the herbicides in most treatment groups. It was suggested that herbicides in water bodies might potentially affect the growth of aquatic macrophytes. Since the Chl-a content of submerged macrophytes responded to the stress of herbicides sensitively and directly, it could be used as a biomaker in environmental monitoring or in the ecological risk assessment of herbicide contamination. PMID:19634441

  6. Identification of pesticide varieties by testing microalgae using Visible/Near Infrared Hyperspectral Imaging technology.

    PubMed

    Shao, Yongni; Jiang, Linjun; Zhou, Hong; Pan, Jian; He, Yong

    2016-01-01

    In our study, the feasibility of using visible/near infrared hyperspectral imaging technology to detect the changes of the internal components of Chlorella pyrenoidosa so as to determine the varieties of pesticides (such as butachlor, atrazine and glyphosate) at three concentrations (0.6 mg/L, 3 mg/L, 15 mg/L) was investigated. Three models (partial least squares discriminant analysis combined with full wavelengths, FW-PLSDA; partial least squares discriminant analysis combined with competitive adaptive reweighted sampling algorithm, CARS-PLSDA; linear discrimination analysis combined with regression coefficients, RC-LDA) were built by the hyperspectral data of Chlorella pyrenoidosa to find which model can produce the most optimal result. The RC-LDA model, which achieved an average correct classification rate of 97.0% was more superior than FW-PLSDA (72.2%) and CARS-PLSDA (84.0%), and it proved that visible/near infrared hyperspectral imaging could be a rapid and reliable technique to identify pesticide varieties. It also proved that microalgae can be a very promising medium to indicate characteristics of pesticides. PMID:27071456

  7. Ecological risk assessment of herbicides in Japan: Integrating spatiotemporal variation in exposure and effects using a multimedia model and algal density dynamics models.

    PubMed

    Hayashi, Takehiko I; Imaizumi, Yoshitaka; Yokomizo, Hiroyuki; Tatarazako, Norihisa; Suzuki, Noriyuki

    2016-01-01

    Application of herbicides to paddy fields in Japan has strong seasonality, and their environmental concentrations exhibit clear spatiotemporal variation. The authors developed an approach that combines a multimedia environmental exposure model (Grid-Catchment Integrated Modeling System) and density dynamics models for algae. This approach enabled assessment of ecological risk when the exposure concentration shows spatiotemporal variation. First, risk maps of 5 herbicides (pretilachlor, butachlor, simetryn, mefenacet, and esprocarb) were created from the spatial predictions of environmental concentrations and 50% inhibitory concentrations of the herbicides. Simulations of algal density dynamics at high-risk sites were then conducted by incorporating the predicted temporal dynamics of the environmental concentration of each herbicide at the sites. The results suggested that the risk of pretilachlor was clearly the highest of the 5 herbicides, in terms of both the spatial distributions and the temporal durations. The present study highlights the importance of integrating exposure models and effect models to clarify spatial and temporal risk and to develop management plans for chemical exposure that shows high spatiotemporal variation. PMID:26183805

  8. Ternary toxicological interactions of insecticides, herbicides, and a heavy metal on the earthworm Eisenia fetida.

    PubMed

    Wang, Yanhua; Chen, Chen; Qian, Yongzhong; Zhao, Xueping; Wang, Qiang

    2015-03-01

    The combined toxicities of five insecticides (chlorpyrifos, avermectin, imidacloprid, λ-cyhalothrin, and phoxim), two herbicides (atrazine and butachlor), and a heavy metal (cadmium) have been examined using the acute toxicity test on the earthworm. With a concentration of 2.75 mg/kg being lethal for 50% of the organisms, imidacloprid exhibited the highest acute toxicity toward the earthworm Eisenia fetida. Toxicological interactions of these chemicals in ternary mixtures were studied using the combination-index (CI) equation method. Twenty-one ternary mixtures exhibited various interactive effects, in which 11 combinations showed synergistic effects, four led to dual synergistic/additive behaviors, one exhibited an additive effect, and five showed increasing antagonism within the entire range of effects. The CI method was compared with the classical models of concentration addition and independent action, and it was found that the CI method could accurately predict combined toxicity of the chemicals studied. The predicted synergism in the majority of the mixtures, especially at low-effect levels, might have implications in the real terrestrial environment. PMID:25463238

  9. The synergistic toxicity of the multiple chemical mixtures: implications for risk assessment in the terrestrial environment.

    PubMed

    Chen, Chen; Wang, Yanhua; Qian, Yongzhong; Zhao, Xueping; Wang, Qiang

    2015-04-01

    The combined toxicity of five insecticides (chlorpyrifos, avermectin, imidacloprid, λ-cyhalothrin, and phoxim), two herbicides (atrazine and butachlor) and a heavy metal (cadmium) has been examined with the earthworm acute toxicity test. Toxicological interactions of these chemicals in four, five, six, seven, and eight-component mixtures were studied using the combination-index (CI) equation method. In four-component and five-component mixtures, the synergistic effects predominated at lower effect levels, while the patterns of interactions found in six, seven, and eight-component mixtures displayed synergism. The λ-CY+IMI+BUT+ATR+CPF+PHO combination displayed the most strongly synergistic interaction, with CI values ranging from 0.09 to 0.15. The nature of the interaction changes with the effect level and the relevance of synergistic effects increase with the complexity of the mixture. The CI method was compared with the classical models of concentration addition (CA) and independent action (IA) and we found that the CI method could accurately predict the combined toxicity. The predicted synergism resulted from co-existence of the pesticides and the heavy metal especially at low effect levels may have important implications in risk assessment for the real terrestrial environment. PMID:25667058

  10. Identification of pesticide varieties by testing microalgae using Visible/Near Infrared Hyperspectral Imaging technology

    PubMed Central

    Shao, Yongni; Jiang, Linjun; Zhou, Hong; Pan, Jian; He, Yong

    2016-01-01

    In our study, the feasibility of using visible/near infrared hyperspectral imaging technology to detect the changes of the internal components of Chlorella pyrenoidosa so as to determine the varieties of pesticides (such as butachlor, atrazine and glyphosate) at three concentrations (0.6 mg/L, 3 mg/L, 15 mg/L) was investigated. Three models (partial least squares discriminant analysis combined with full wavelengths, FW-PLSDA; partial least squares discriminant analysis combined with competitive adaptive reweighted sampling algorithm, CARS-PLSDA; linear discrimination analysis combined with regression coefficients, RC-LDA) were built by the hyperspectral data of Chlorella pyrenoidosa to find which model can produce the most optimal result. The RC-LDA model, which achieved an average correct classification rate of 97.0% was more superior than FW-PLSDA (72.2%) and CARS-PLSDA (84.0%), and it proved that visible/near infrared hyperspectral imaging could be a rapid and reliable technique to identify pesticide varieties. It also proved that microalgae can be a very promising medium to indicate characteristics of pesticides. PMID:27071456

  11. Identification of pesticide varieties by testing microalgae using Visible/Near Infrared Hyperspectral Imaging technology

    NASA Astrophysics Data System (ADS)

    Shao, Yongni; Jiang, Linjun; Zhou, Hong; Pan, Jian; He, Yong

    2016-04-01

    In our study, the feasibility of using visible/near infrared hyperspectral imaging technology to detect the changes of the internal components of Chlorella pyrenoidosa so as to determine the varieties of pesticides (such as butachlor, atrazine and glyphosate) at three concentrations (0.6 mg/L, 3 mg/L, 15 mg/L) was investigated. Three models (partial least squares discriminant analysis combined with full wavelengths, FW-PLSDA; partial least squares discriminant analysis combined with competitive adaptive reweighted sampling algorithm, CARS-PLSDA; linear discrimination analysis combined with regression coefficients, RC-LDA) were built by the hyperspectral data of Chlorella pyrenoidosa to find which model can produce the most optimal result. The RC-LDA model, which achieved an average correct classification rate of 97.0% was more superior than FW-PLSDA (72.2%) and CARS-PLSDA (84.0%), and it proved that visible/near infrared hyperspectral imaging could be a rapid and reliable technique to identify pesticide varieties. It also proved that microalgae can be a very promising medium to indicate characteristics of pesticides.

  12. Effects of sampling strategies on estimates of annual mean herbicide concentrations in midwestern rivers

    USGS Publications Warehouse

    Battaglin, W.A.; Hay, L.E.

    1996-01-01

    The effects of 10 sampling strategies on estimates of annual mean concentrations of the herbicides atrazine, alachlor, and cyanazine in selected midwestern rivers were tested. The accuracy of the strategies was computed by comparing time-weighted annual mean herbicide concentrations calculated from water samples collected from 17 locations on midwestern rivers, with simulated annual mean concentrations calculated for each sampling strategy, using Monte Carlo simulations. Monthly sampling was the most accurate strategy tested. The U.S. Environmental Protection Agency requires quarterly sampling for municipalities using surface water as a source of drinking water. Due to the seasonality of herbicide occurrence and transport, quarterly sampling underestimates annual mean herbicide concentrations in over 40% of the simulations. Three of the strategies tested showed that, relative to quarterly sampling, a more accurate representation of annual mean concentrations could be obtained by sampling more frequently during spring and early summer runoff and assuming zero herbicide concentration during late summer and winter months.

  13. Are Streams in Agricultural and Urban Areas Contaminated by Pesticides?

    USGS Publications Warehouse

    Kimbrough, R.A.

    1995-01-01

    To answer this question, a study of pesticides in streams in a small agricultural area and a small urban area in Colorado was conducted in 1993 by the U.S. Geological Survey (USGS) as part of the National Water-Quality Assessment (NAWQA) program. The results indicate that pesticides are present in streams, and both agricultural and urban areas are probable sources of the contamination. In the agricultural area, 30 pesticides were detected and in the urban area, 26 pesticides were detected at least once during the thirteen month study. In the agricultural area, the herbicides alachlor (two samples) and cyanazine (four samples) and the insecticide diazinon (one sample) were the only pesticides that exceeded the U.S. Environmental Protection Agency's maximum contaminant levels (MCLs) or health advisory levels (HALs) for drinking water. No pesticides exceeded MCLs or HALs in the urban area.

  14. Organomineral Interactions and Herbicide Sorption in Brazilian Tropical and Subtropical Oxisols under No-Tillage.

    PubMed

    Bonfleur, Eloana J; Kookana, Rai S; Tornisielo, Valdemar L; Regitano, Jussara B

    2016-05-25

    We evaluated the effects of the soil organic matter (SOM) composition, distribution between soil aggregates size, and their interactions with the mineral phase on herbicide sorption (alachlor, bentazon, and imazethapyr) in tropical and subtropical Oxisols under no-till systems (NT). Using soil physical fractionation approach, sorption experiments were performed on whole soils and their aggregates. SOM chemistry was assessed by CP/MAS (13)C NMR. The lower sorption observed in tropical soils was attributed to the greater blockage of SOM sorption sites than in subtropical soils. When these sites were exposed upon physical fractionation, sorption of the three herbicides in tropical soils increased, especially for imazethapyr. High amounts of poorly crystallized sesquioxides in these soils may have contributed to masking of sorption sites, indicating that organomineral interactions may lead to blockage of sorption sites on SOM in tropical soils. PMID:26666375

  15. Photocatalytic oxidation of pesticides by solar-irradiated TiO[sub 2] systems

    SciTech Connect

    Sullivan, J.M.; Grinstead, J.H. Jr.

    1992-01-01

    Research at the Tennessee Valley Authority's National Fertilizer and Environmental Research Center has been directed toward the development of passive basin type solar evaporators as a simple means of reducing the volume of fertilizer and pesticide contaminated rinsewater generated at fertilizer and agrichemical dealerships. In conjunction with this work, investigations are also devoted to TiO[sub 2] catalyzed solar photooxidation as a potential procedure for destroying pesticides in dilute aqueous systems. Initial tests in which dilute samples of the herbicides; Bicep (atrazine and metolachlor), Lasso (alachlor), and Sencor (metribuzin); were recirculated continuously over TiO[sub 2] impregnated fiberglass gauze, under solar irradiation, gave promising results. In the case of metribuzin, solar irradiation induced oxidation appeared effective at concentrations as high as 600 ppM. Catalytic efficiency did not appear greatly affected by using tap water rather than distilled water to dilute the pesticides. Two solar reactor designs will be discussed.

  16. Photocatalytic oxidation of pesticides by solar-irradiated TiO{sub 2} systems

    SciTech Connect

    Sullivan, J.M.; Grinstead, J.H. Jr.

    1992-12-01

    Research at the Tennessee Valley Authority`s National Fertilizer and Environmental Research Center has been directed toward the development of passive basin type solar evaporators as a simple means of reducing the volume of fertilizer and pesticide contaminated rinsewater generated at fertilizer and agrichemical dealerships. In conjunction with this work, investigations are also devoted to TiO{sub 2} catalyzed solar photooxidation as a potential procedure for destroying pesticides in dilute aqueous systems. Initial tests in which dilute samples of the herbicides; Bicep (atrazine and metolachlor), Lasso (alachlor), and Sencor (metribuzin); were recirculated continuously over TiO{sub 2} impregnated fiberglass gauze, under solar irradiation, gave promising results. In the case of metribuzin, solar irradiation induced oxidation appeared effective at concentrations as high as 600 ppM. Catalytic efficiency did not appear greatly affected by using tap water rather than distilled water to dilute the pesticides. Two solar reactor designs will be discussed.

  17. Movement of pesticides and nutrients into tile drainage water. Final report, 22 September 1985-22 September 1988

    SciTech Connect

    Van Scoyoc, G.E.; Kladivko, E.J.

    1989-01-01

    Concern about contamination of surface and ground water by agricultural chemicals has increased in the last five years. The objectives of this study were to determine field-scale pesticide and nutrient losses to tile drains over a 3-year period on a low-organic-matter, poorly structured silt loam soil under typical agricultural management practices. A tile-drainage spacing study was instrumented to measure water outflow rates and to continuously collect tile outflow samples on a flow-proportional basis. Two replicates of 3 tile spacings (5, 10, and 20 m) were included in the study. Water samples were analyzed for all applied pesticides (atrazine, cyanazine, alachlor, carbofuran, terbufos, and chlorpyrifos) as well as major nutrients (N,P,K) and sediment.

  18. Distribution of major herbicides in ground water of the United States

    USGS Publications Warehouse

    Barbash, Jack E.; Thelin, Gail P.; Kolpin, Dana W.; Gilliom, Robert J.

    1999-01-01

    Frequencies of detection at or above 0.01 microgram per liter in shallow ground water beneath agricultural areas during the NAWQA study were significantly correlated with agricultural use in those areas for atrazine, cyanazine, alachlor, and metolachlor (P<0.05; Spearman rank correlations), but not for simazine (P>0.05). In urban areas, overall frequencies of detection of these five herbicides in shallow ground water were positively correlated with their total nonagricultural use nationwide (P=0.026; simple linear correlation). Multivariate statistical analysis indicated that frequencies of detection in shallow ground water beneath agricultural areas were positively correlated with half-lives for transformation in aerobic soil and agricultural use of the comp

  19. Pesticide distributions in surface water: The distribution of pesticide concentrations at two study sites points to herbicides that may affect management of public water supplies

    USGS Publications Warehouse

    Stamer, J.K.; Wieczorek, M.E.

    1996-01-01

    Distributions of concentrations of 46 pesticides were documented from May 1992 through March 1994 for Maple Creek near Nickerson, Neb., and Platte River at Louisville, Neb. As their source of public water supplies, Lincoln and the western part of Omaha withdraw groundwater from the adjacent alluvium near the Platte River site, which is hydraulically connected to the Platte River. Organonitrogen herbicides dominated the pesticide distributions at each site. Variations in the distributions of pesticides at the two sites partly reflect differences in land use and land management practices. Diazinon, an insecticide used in urban areas, was commonly detected at the Platte River site but not at the Maple Creek site. Of the 46 pesticides analyzed at the Platte River site, the herbicides atrazine and alachlor were more likely to exceed their respective maximum contaminant levels of 3.0 and 2.0 pg/L; cyanazine was more likely to exceed the health advisory level of 1.0 ??g/L.

  20. Occurrence of active and inactive herbicide ingredients at selected sites in Iowa

    USGS Publications Warehouse

    Wang, W.; Liszewski, M.; Buchmiller, R.; Cherryholmes, K.

    1995-01-01

    Herbicides were detected in 50% of water samples, ranging from 78% of water samples from the Ames site to 25% from the Walnut Creek site. Among herbicides detected, listed in decreasing order of frequency, were atrazine > alachlor > cyanazine > metolachlor > metribuzin. Volatile organic compounds were detected in 11% of water samples. Among the compounds detected, listed in decreasing order of frequency, were xylene > toluene > acetone. One sample contained a detectable amount of aliphatic compound(s), with the empirical formula of C8H18. Results from the Deer Creek site showed that herbicides were detected primarily in the top layer (1.2 m), whereas xylene and other alkylbenzenes were detected at 2.1 m or deeper. Apparently, physico-chemical and other factors are separating herbicides and volatile organic compounds in the shallow unsaturated zone.

  1. Performance of different work clothing types for reducing skin exposure to pesticides during open field treatment.

    PubMed

    Protano, Carmela; Guidotti, Maurizio; Vitali, Matteo

    2009-07-01

    The aim of this study was to estimate the performance of different work clothing types for reducing skin exposure to five pesticides (azinphos-methyl, terbutylazine, alachlor, dimethoate, and dicamba) in field distribution by tractor equipped with boom sprayer. Performance was assessed by measuring the penetration factors of different types of work clothing. The results show that the protection offered by personal protective equipment (PPE) was always >97%, whereas the performance of cotton garments ranged from 84.1% to 92.5%. The different cotton garments differed significantly in their permeability, and the upper part of the body was the anatomical region showing the greatest values of the penetration factors. These results confirm the necessity of using PPE properly to minimise dermal exposure to pesticides. PMID:19424648

  2. Hydrologic data for the Big Spring basin, Clayton County, Iowa, water year 1991

    USGS Publications Warehouse

    Kalkhoff, S.J.; Kuzniar, R.L.

    1994-01-01

    Stream discharge, specific conductance, pH, and water temperature were monitored continuously, and monthly water-quality samples were collected at a site on Roberts Creek and at Big Spring. Nitrite plus nitrate as nitrogen concentrations in 27 samples from Roberts Creek at the point where it leaves the study area ranged from 1.8 to 22 mg/L. Herbicide concentrations in 26 samples from the Roberts Creek site ranged from less than 0.10 μg/L (micrograms per liter) to 43 μg/L. Alachlor was detected in 42 percent of the samples; atrazine in 92 percent; and cyanazine and metolachlor in 35 percent of the samples. The total suspended-sediment load discharged in Roberts Creek was about 160,000 tons. At Big Spring, the ground-water discharge point, the daily mean specific conductance ranged from 414 to 788 microsiemens per centimeter at 25 degrees Celsius, the daily median pH ranged from 6.7 to 7.1, and the daily mean water temperature ranged from 8.5 to 13.0 degrees Celsius. Concentrations of nitrite plus nitrate as nitrogen in 23 samples ranged from 4.2 to 17 mg/L. The total measured suspended-sediment discharged from Big Spring was about 17,000 tons. Alachlor was detected in 26 percent; atrazine in 100 percent; cyanazine in 26 percent, and metolachlor in 9 percent of the samples. The maximum atrazine concentration was 16 μg/L.

  3. Estimating the Regional Flux of Nitrate and Agricultural Herbicide Compounds from Groundwater to Headwater Streams of the Northern Atlantic Coastal Plain, USA

    NASA Astrophysics Data System (ADS)

    Ator, S.; Denver, J. M.

    2011-12-01

    Agriculture is common in the Northern Atlantic Coastal Plain (NACP, including New Jersey through North Carolina), and groundwater discharge provides nitrogen (primarily in the form of nitrate) and herbicide compounds from agricultural sources along with the majority of flow to NACP streams. Poor water quality has contributed to ecological degradation of tidal streams and estuaries along much of the adjacent mid-Atlantic coast. Although statistical models have provided estimates of total instream nutrient flux in the Coastal Plain, the regional flux of nitrogen and herbicides during base flow is less well understood. We estimated the regional flux of nitrate and selected commonly used herbicide compounds from groundwater to non-tidal headwater streams of the NACP on the basis of late-winter or spring base-flow samples from 174 such streams. Sampled streams were selected using an unequal-probability random approach, and flux estimates are based on resulting population estimates rather than empirical models, which are commonly used for such estimates. Base-flow flux in the estimated 8,834 NACP non-tidal headwater streams are an estimated 21,200 kilograms per day of nitrate (as N) and 5.83, 0.565, and 20.7 kilograms per day of alachlor, atrazine, and metolachlor (including selected degradates), respectively. Base-flow flux of alachlor and metolachlor is dominated by degradates; flux of parent compounds is less than 3 percent of the total flux of parent plus degradates. Base-flow flux of nitrate and herbicides as a percentage of applications generally varies predictably with regional variations in hydrogeology. Abundant nonpoint (primarily agricultural) sources and hydrogeologic conditions, for example, contribute to particularly large base-flow flux from the Delmarva Peninsula to Chesapeake Bay. In the Delmarva Peninsula part of the Chesapeake Watershed, more than 10 percent of total nonpoint nitrogen applications is transported through groundwater to stream base flow

  4. Ascorbic acid/Fe@Fe2O3: A highly efficient combined Fenton reagent to remove organic contaminants.

    PubMed

    Hou, Xiaojing; Huang, Xiaopeng; Ai, Zhihui; Zhao, Jincai; Zhang, Lizhi

    2016-06-01

    In this study, we demonstrate that the combination of ascorbic acid and Fe@Fe2O3 core-shell nanowires (AA/Fe@Fe2O3) offers a highly efficient Fenton reagent. This combined Fenton reagent exhibited extremely high activity on the decomposition of H2O2 to produce OH for the degradation of various organic contaminants, including rhodamine B, methylene blue, alachlor, atrazine, siduron, lincomycin, and chloroamphenicol. The contaminant degradation constants in the AA/Fe@Fe2O3/H2O2 Fenton systems were 38-53 times higher than those in the conventional homogeneous Fenton system (Fe(II)/H2O2) at pH 3.8. Moreover, the OH generation rate constant in the AA/Fe@Fe2O3/H2O2 Fenton system was 1-3 orders of magnitudes greater than those of heterogeneous Fenton systems developed with other iron-containing materials (α-FeOOH, α-Fe2O3, FeOCl, and so on). The high activity of AA/Fe@Fe2O3 was attributed to the effective Fe(III)/Fe(II) cycle and the iron-ascorbate complex formation to stabilize ferrous ions with desirable and steady concentrations. During the AA/Fe@Fe2O3/H2O2 Fenton process, ascorbic acid served as a reducing and complexing reagent, enabling the reuse of Fe@Fe2O3 nanowires. We systematically investigated the alachlor and ascorbic acid degradation and found that they could be effectively degraded in the AA/Fe@Fe2O3/H2O2 system, accompanying with 100% of dechlorination and 92% of denitrification. This study sheds light on the importance of Fe(III)/Fe(II) cycle for the design of high efficient Fenton system and provides an alternative pathway for the organic contaminants removal. PMID:26921510

  5. Amidase activity in soils. IV. Effects of trace elements and pesticides

    SciTech Connect

    Frankenberger, W.T., Jr.; Tabatabai, M.A.

    1981-11-01

    Amidase was recently detected in soils, and this study was carried out to assess the effects of 21 trace elements, 12 herbicides, 2 fungicides, and 2 insecticides on the activity of this enzyme. Results showed that most of the trace elements and pesticides studied inhibited amidase activity in soils. The degree of inhibition varied among the soils used. When the trace elements were compared by using 5 ..mu..mol/g of soil, the average inhibition of amidase in three soils showed that Ag(I), Hg(I), As(III), and Se(IV) were the most effective inhibitors, but only Ag(I) and As(III) showed average inhibition > 50%. The least effective inhibitors (average inhibition < 3%) included Cu(I), Ba(II), Cu(II), Fe(II), Ni(II), Al(III), Fe(III), Ti(IV), V(IV), As(V), Mo(VI), and W(VI). Other elements that inhibited amidase activity in soils were Cd(II), Co(II), Mn(II), Pb(II), Sn(II), Zn(II), B(III), and Cr(III). Enzyme kinetic studies showed that As(III) was a competitive inhibitor of amidase, whereas Ag(I), Hg(II), and Se(IV) were noncompetitive inhibitors. When the pesticides studied were compared by using 10 ..mu..g of active ingredient per gram of soil, the average inhibition of amidase in three soils ranged from 2% with dinitroamine, EPTC plus R-25788, and captan to 10% with butylate. Other pesticides that inhibited amidase activity in soils were atrazine, naptalam, chloramben, dicamba, cyanazine, 2,4-D, alachlor, paraquat, trifluralin, maneb, diazinon, and malathion. The inhibition of amidase by diazinon, alachlor, and butylate followed noncompetitive kinetics.

  6. Compilation of atrazine and selected herbicide data from previous surface-water-quality investigations within the Big Blue River basin, Nebraska, 1983-92

    USGS Publications Warehouse

    Frankforter, J.D.

    1994-01-01

    Atrazine has been detected in the surface water of the Big Blue River Basin during every month of the year. Recent data (1983-92) documenting the occurrence of atrazine and related herbicides in the surface water of the basin are compiled in this report. In samples analyzed during these studies, atrazine was the herbicide detected most frequently within the basin. Of the 385 samples analyzed, 369 contained atrazine in detectable concentrations with detection levels varying from 0 to 0.1 micrograms per liter. The concentrations of atrazine within the samples varied from 0.5 to 166 micrograms per liter, with a median concentration of 2.7 micrograms per liter. Other herbicides frequently detected in the Big Blue River Basin were alachlor, cyanazine, metolachlor, and simazine, and two metabolites of atrazine, desethylatrazine and deisopropylatrazine. In the 226 samples which alachlor was detected, the concentrations of the herbicide ranged from 0.05 to 56 micrograms per liter, and the median concen- tration was 1.1 micrograms per liter. Cyanazine was detected in 210 of 365 samples collected with con- centrations that ranged from 0.05 to 8.6 micrograms per liter with a median concentration of 0.4 microgram per liter. The maximum concentrations of metolachlor and simazine were 26 and 35 micrograms per liter, respectively. The median concentrations of these herbicides were 1.0 and 0.1 micrograms per liter, respectively. The maximum concentration of desethylatrazine, was 3.7 micrograms per liter, with a median concentration of 1.0 microgram per liter. Deisopropylatrazine, was detected in 152 samples with maximum and median concentrations of 2.6 and 0.6 micrograms per liter, respectively.

  7. Comparative sensitivity of Selenastrum capricornutum and Lemna minor to sixteen herbicides

    USGS Publications Warehouse

    Fairchild, J.F.; Ruessler, D.S.; Haverland, P.S.; Carlson, A.R.

    1997-01-01

    Aquatic plant toxicity tests are frequently conducted in environmental risk assessments to determine the potential impacts of contaminants on primary producers. An examination of published plant toxicity data demonstrates that wide differences in sensitivity can occur across phylogenetic groups of plants. Yet relatively few studies have been conducted with the specific intent to compare the relative sensitivity of various aquatic plant species to contaminants. We compared the relative sensitivity of the algae Selenestrum capricornutum and the floating vascular plant Lemna minor to 16 herbicides (atrazine, metribuzin, simazine, cyanazine, alachlor, metolachlor, chlorsulfuron, metsulfuron, triallate, EPTC, trifluralin, diquat, paraquat, dicamba, bromoxynil, and 2,4-D). The herbicides studied represented nine chemical classes and several modes of action and were chosen to represent major current uses in the United States. Both plant species were generally sensitive to the triazines (atrazine, metribuzin, simazine, and cyanazine), sulfonureas (metsulfuron and chlorsulfuron), pyridines (diquat and paraquat), dinitroaniline (trifluralin), and acetanilide (alachlor and metolachlor) herbicides. Neither plant species was uniformly more sensitive than the other across the broad range of herbicides tested. Lemna was more sensitive to the sulfonureas (metsulfuron and chlorsulfuron) and the pyridines (diquat and parequat) than Selenastrum. However Selenastrum was more sensitive than Lemna to one of two thiocarbamates (triallate) and one of the triazines (cyanazine). Neither species was sensitive to selective broadleaf herbicides including bromoxynil, EPTC, dicamba, or 2,4-D. Results were not always predictable in spite of obvious differences in herbicide modes of action and plant phylogeny. Major departures in sensitivity of Selenastrum occurred between chemicals within individual classes of the triazine, acetanilide, and thiocarbamate herbicides. Results indicate that neither

  8. Pesticide Use and Relative Leukocyte Telomere Length in the Agricultural Health Study.

    PubMed

    Andreotti, Gabriella; Hoppin, Jane A; Hou, Lifang; Koutros, Stella; Gadalla, Shahinaz M; Savage, Sharon A; Lubin, Jay; Blair, Aaron; Hoxha, Mirjam; Baccarelli, Andrea; Sandler, Dale; Alavanja, Michael; Beane Freeman, Laura E

    2015-01-01

    Some studies suggest that telomere length (TL) may be influenced by environmental exposures, including pesticides. We examined associations between occupational pesticide use reported at three time points and relative telomere length (RTL) in the Agricultural Health Study (AHS), a prospective cohort study of pesticide applicators in Iowa and North Carolina. RTL was measured by qPCR using leukocyte DNA from 568 cancer-free male AHS participants aged 31-94 years with blood samples collected between 2006 and 2008. Self-reported information, including pesticide use, was collected at three time points: enrollment (1993-1997) and two follow-up questionnaires (1998-2003, 2005-2008). For each pesticide, we evaluated cumulative use (using data from all three questionnaires), and more recent use (using data from the last follow-up questionnaire). Multivariable linear regression was used to examine the associations between pesticide use (ever, lifetime days, intensity-weighted lifetime days (lifetime days*intensity score)) and RTL, adjusting for age at blood draw and use of other pesticides. Of the 57 pesticides evaluated with cumulative use, increasing lifetime days of 2,4-D (p-trend=0.001), diazinon (p-trend=0.002), and butylate (p-trend=0.01) were significantly associated with shorter RTL, while increasing lifetime days of alachlor was significantly associated with longer RTL (p-trend=0.03). Only the association with 2,4-D was significant after adjustment for multiple comparisons. Of the 40 pesticides evaluated for recent use, malathion was associated with shorter RTL (p=0.03), and alachlor with longer RTL (p=0.03). Our findings suggest that leukocyte TL may be impacted by cumulative use and recent use of certain pesticides. PMID:26196902

  9. Pesticide Use and Relative Leukocyte Telomere Length in the Agricultural Health Study

    PubMed Central

    Andreotti, Gabriella; Hoppin, Jane A.; Hou, Lifang; Koutros, Stella; Gadalla, Shahinaz M.; Savage, Sharon A.; Lubin, Jay; Blair, Aaron; Hoxha, Mirjam; Baccarelli, Andrea; Sandler, Dale; Alavanja, Michael; Beane Freeman, Laura E.

    2015-01-01

    Some studies suggest that telomere length (TL) may be influenced by environmental exposures, including pesticides. We examined associations between occupational pesticide use reported at three time points and relative telomere length (RTL) in the Agricultural Health Study (AHS), a prospective cohort study of pesticide applicators in Iowa and North Carolina. RTL was measured by qPCR using leukocyte DNA from 568 cancer-free male AHS participants aged 31-94 years with blood samples collected between 2006 and 2008. Self-reported information, including pesticide use, was collected at three time points: enrollment (1993-1997) and two follow-up questionnaires (1998-2003, 2005-2008). For each pesticide, we evaluated cumulative use (using data from all three questionnaires), and more recent use (using data from the last follow-up questionnaire). Multivariable linear regression was used to examine the associations between pesticide use (ever, lifetime days, intensity-weighted lifetime days (lifetime days*intensity score)) and RTL, adjusting for age at blood draw and use of other pesticides. Of the 57 pesticides evaluated with cumulative use, increasing lifetime days of 2,4-D (p-trend=0.001), diazinon (p-trend=0.002), and butylate (p-trend=0.01) were significantly associated with shorter RTL, while increasing lifetime days of alachlor was significantly associated with longer RTL (p-trend=0.03). Only the association with 2,4-D was significant after adjustment for multiple comparisons. Of the 40 pesticides evaluated for recent use, malathion was associated with shorter RTL (p=0.03), and alachlor with longer RTL (p=0.03). Our findings suggest that leukocyte TL may be impacted by cumulative use and recent use of certain pesticides. PMID:26196902

  10. Agricultural chemicals in alluvial aquifers in Missouri after the 1993 flood

    USGS Publications Warehouse

    Heimann, D.C.; Richards, J.M.; Wilkison, D.H.

    1997-01-01

    Intense rains produced flooding during the spring and summer of 1993 over much of the midwestern USA including many agricultural areas of Missouri. Because of potential contamination from floodwater, an investigation was conducted to determine the changes in concentrations of agricultural chemicals in water samples from alluvial wells in Missouri after the flood. Water samples from 80 alluvial wells with historical data were collected in March, July, and November 1994, and analyzed for dissolved herbicides, herbicide metabolites, and nitrate (NO3). There were no statistically significant differences in the distribution of alachlor ((2,chloro-2'-6'-diethyl-N-[methoxymethyl]acetanilide), atrazine (2-chloro- 4-ethylamino-6-isopropylamino-1, 3, 5 triazine), and nitrate concentrations between pre- and postflood samples (?? = 0.05). The detection frequency of alachlor and atrazine in postflood samples was generally lower than the frequency in preflood samples. Analyses of agricultural chemicals in water samples from an intensely sampled well field indicate significant differences between the distribution of dissolved P concentrations in pre- and postflood samples (?? = 0.05). However, no significant differences were detected between the pre- and postflood distributions of NO3 or ammonia concentrations. Because of the numerous sources of temporal variability and the relatively short record of water-quality data for the study wells, a cause-and-effect relation between changes in agricultural chemical concentrations and a single factor of the 1993 flood is difficult to determine. Based on the results of this study, the 1993 flood did not cause widespread or long-term significant changes in concentrations of agricultural chemicals in water from alluvial aquifers in Missouri.

  11. Impact of grassed waterways and compost filter socks on the quality of surface runoff from corn fields.

    PubMed

    Shipitalo, Martin J; Bonta, James V; Dayton, Elizabeth A; Owens, Lloyd B

    2010-01-01

    Surface runoff from cropland frequently has high concentrations of nutrients and herbicides, particularly in the first few events after application. Grassed waterways can control erosion while transmitting this runoff offsite, but are generally ineffective in removing dissolved agrochemicals. In this study, we routed runoff from one tilled (0.67 ha) and one no-till watershed (0.79 ha) planted to corn (Zea mays L.) into parallel, 30-m-long grassed waterways. Two 46-cm-diam. filter socks filled with composted bark and wood chips were placed 7.5 m apart in the upper half of one waterway and in the lower half of the other waterway to determine if they decreased concentrations of sediment and dissolved chemicals. Automated samplers were used to obtain samples above and below the treated segments of the waterways for two crop years. The filter socks had no significant effect (P alachlor [2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)acetamide] (18%) concentrations for the tilled watersheds, but this was insufficient to reduce alachlor concentrations to acceptable levels. PMID:20400596

  12. Sources and transport of contaminants of emerging concern: A two-year study of occurrence and spatiotemporal variation in a mixed land use watershed.

    PubMed

    Fairbairn, David J; Karpuzcu, M Ekrem; Arnold, William A; Barber, Brian L; Kaufenberg, Elizabeth F; Koskinen, William C; Novak, Paige J; Rice, Pamela J; Swackhamer, Deborah L

    2016-05-01

    The occurrence and spatiotemporal variation of 26 contaminants of emerging concern (CECs) were evaluated in 68 water samples in 2011-2012 in the Zumbro River watershed, Minnesota, U.S.A. Samples were collected across a range of seasonal/hydrological conditions from four stream sites that varied in associated land use and presence of an upstream wastewater treatment plant (WWTP). Selected CECs included human/veterinary pharmaceuticals, personal care products, pesticides, phytoestrogens, and commercial/industrial compounds. Detection frequencies and concentrations varied, with atrazine, metolachlor, acetaminophen, caffeine, DEET, and trimethoprim detected in more than 70% of samples, acetochlor, mecoprop, carbamazepine, and daidzein detected in 30%-50% of samples, and 4-nonylphenol, cotinine, sulfamethoxazole, erythromycin, tylosin, and carbaryl detected in 10%-30% of samples. The remaining target CECs were not detected in water samples. Three land use-associated trends were observed for the detected CECs. Carbamazepine, 4-nonylphenol, erythromycin, sulfamethoxazole, tylosin, and carbaryl profiles were WWTP-dominated, as demonstrated by more consistent loading and significantly greater concentrations downstream of the WWTP and during low-flow seasons. In contrast, acetaminophen, trimethoprim, DEET, caffeine, cotinine, and mecoprop patterns demonstrated both seasonally-variable non-WWTP-associated and continual WWTP-associated influences. Surface water studies of CECs often target areas near WWTPs. This study suggests that several CECs often characterized as effluent-associated have additional important sources such as septic systems or land-applied biosolids. Finally, agricultural herbicide (atrazine, acetochlor, and metolachlor) profiles were strongly influenced by agricultural land use and seasonal application-runoff, evident by significantly greater concentrations and loadings at upstream sites and in early summer when application and precipitation rates are

  13. Pesticide management and their residues in sediments and surface and drinking water in the Mekong Delta, Vietnam.

    PubMed

    Toan, Pham Van; Sebesvari, Zita; Bläsing, Melanie; Rosendahl, Ingrid; Renaud, Fabrice G

    2013-05-01

    Public concern in Vietnam is increasing with respect to pesticide pollution of the environment and of drinking water resources. While established monitoring programs in the Mekong Delta (MD) focus on the analysis of organochlorines and some organophosphates, the environmental concentrations of more recently used pesticides such as carbamates, pyrethroides, and triazoles are not monitored. In the present study, household level pesticide use and management was therefore surveyed and combined with a one year environmental monitoring program of thirteen relevant pesticides (buprofezin, butachlor, cypermethrin, α-endosulfan, β-endosulfan, endosulfan-sulfate, fenobucarb, fipronil, isoprothiolane, pretilachlor, profenofos, propanil, and propiconazole) in surface water, soil, and sediment samples. The surveys showed that household level pesticide management remains suboptimal in the Mekong Delta. As a consequence, a wide range of pesticide residues were present in water, soil, and sediments throughout the monitoring period. Maximum concentrations recorded were up to 11.24 μg l(-1) in water for isoprothiolane and up to 521 μg kg(-1) dm in sediment for buprofezin. Annual average concentrations ranged up to 3.34 μg l(-1) in water and up to 135 μg kg(-1) dm in sediment, both for isoprothiolane. Occurrence of pesticides in the environment throughout the year and co-occurrence of several pesticides in the samples indicate a considerable chronic exposure of biota and humans to pesticides. This has a high relevance in the delta as water for drinking is often extracted from canals and rivers by rural households (GSO, 2005, and own surveys). The treatment used by the households for preparing surface water prior to consumption (flocculation followed by boiling) is insufficient for the removal of the studied pesticides and boiling can actually increase the concentration of non-volatile pollutants. PMID:23500396

  14. Chemical and toxicologic assessment of organic contaminants in surface water using passive samplers

    USGS Publications Warehouse

    Alvarez, D.A.; Cranor, W.L.; Perkins, S.D.; Clark, R.C.; Smith, S.B.

    2008-01-01

    Passive sampling methodologies were used to conduct a chemical and toxicologic assessment of organic contaminants in the surface waters of three geographically distinct agricultural watersheds. A selection of current-use agrochemicals and persistent organic pollutants, including polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and organochlorine pesticides, were targeted using the polar organic chemical integrative sampler (POCIS) and the semipermeable membrane device passive samplers. In addition to the chemical analysis, the Microtox assay for acute toxicity and the yeast estrogen screen (YES) were conducted as potential assessment tools in combination with the passive samplers. During the spring of 2004, the passive samplers were deployed for 29 to 65 d at Leary Weber Ditch, IN; Morgan Creek, MD; and DR2 Drain, WA. Chemical analysis of the sampler extracts identified the agrochemicals predominantly used in those areas, including atrazine, simazine, acetochlor, and metolachlor. Other chemicals identified included deethylatrazine and deisopropylatrazine, trifluralin, fluoranthene, pyrene, cis- and trans-nonachlor, and pentachloroanisole. Screening using Microtox resulted in no acutely toxic samples. POCIS samples screened by the YES assay failed to elicit a positive estrogenic response. Copyright ?? 2008 by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. All rights reserved.

  15. Agricultural herbicide transport in a first-order intermittent stream, Nebraska, USA

    USGS Publications Warehouse

    Vogel, J.R.; Linard, J.I.

    2011-01-01

    The behavior of herbicides in surface waters is a function of many variables, including scale of the watershed, physical and chemical properties of the herbicide, physical and chemical properties of the soil, rainfall intensity, and time of year. In this study, the transport of 6 herbicides and 12 herbicide degradates was examined during the 2004 growing season in an intermediate-scale agricultural watershed (146 ha) that is drained by a first-order intermittent stream, and the mass load for each herbicide in the stream was estimated. The herbicide load during the first week of storm events after application ranged from 17% of annual load for trifluralin to 84% of annual load for acetochlor. The maximum weekly herbicide load in the stream was generally within the first 3 weeks after application for those compounds that were applied within the watershed during 2004, and later for herbicides not applied within the watershed during 2004 but still detected in the stream. The apparent dominant mode of herbicide transport in the stream-determined by analysis amongst herbicide and conservative ion concentrations at different points in the hydrograph and in base flow samples-was either overland runoff or shallow subsurface flow, depending on the elapsed time after application and type of herbicide. The load as a percentage of use (LAPU) for the parent compounds in this study was similar to literature values for those compounds applied by the farmer within the watershed, but smaller for those herbicides that had rainfall as their only source within the watershed.

  16. Occurrence of currently used pesticides in ambient air of Centre Region (France)

    NASA Astrophysics Data System (ADS)

    Coscollà, Clara; Colin, Patrice; Yahyaoui, Abderrazak; Petrique, Olivier; Yusà, Vicent; Mellouki, Abdelwahid; Pastor, Agustin

    2010-10-01

    Ambient air samples were collected, from 2006 to 2008 at three rural and two urban sites in Centre Region (France) and analyzed for 56 currently used pesticides (CUPs), of which 41 were detected. The four CUPs most frequently detected were the herbicides trifluralin, acetochlor and pendimethalin and the fungicide chlorothalonil, which were found with frequencies ranging between 52 and 78%, and with average concentrations of 1.93, 1.32, 1.84 and 12.15 ng m -3, respectively. Among the detected pesticides, concentrations of eight fungicides (spiroxamine, fenpropimorph, cyprodinil, tolyfluanid, epoxiconazole, vinchlozolin, fluazinam, fludioxinil), two insecticides (propargite, ethoprophos), and one herbicide (oxyfluorfen) are, to our knowledge, reported for the first time in the literature. The majority of the CUPs showed a seasonal trend, with most of the detections and the highest concentrations occurring during the spring and early summer. The most important pesticides detected were related to arable crops and fruit orchards, the main cultures in this region, highlighting the fact that the main sources come from local applications. Minor differences were found in the profiles of pesticides within rural areas and between rural and urban areas.

  17. Application of the KeratinoSens™ assay for assessing the skin sensitization potential of agrochemical active ingredients and formulations.

    PubMed

    Settivari, Raja S; Gehen, Sean C; Amado, Ricardo Acosta; Visconti, Nicolo R; Boverhof, Darrell R; Carney, Edward W

    2015-07-01

    Assessment of skin sensitization potential is an important component of the safety evaluation process for agrochemical products. Recently, non-animal approaches including the KeratinoSens™ assay have been developed for predicting skin sensitization potential. Assessing the utility of the KeratinoSens™ assay for use with multi-component mixtures such as agrochemical formulations has not been previously evaluated and is a significant need. This study was undertaken to evaluate the KeratinoSens™ assay prediction potential for agrochemical formulations. The assay was conducted for 8 agrochemical active ingredients (AIs) including 3 sensitizers (acetochlor, meptyldinocap, triclopyr), 5 non-sensitizers (aminopyralid, clopyralid, florasulam, methoxyfenozide, oxyfluorfen) and 10 formulations for which in vivo sensitization data were available. The KeratinoSens™ correctly predicted the sensitization potential of all the AIs. For agrochemical formulations it was necessary to modify the standard assay procedure whereby the formulation was assumed to have a common molecular weight. The resultant approach correctly predicted the sensitization potential for 3 of 4 sensitizing formulations and all 6 non-sensitizing formulations when compared to in vivo data. Only the meptyldinocap-containing formulation was misclassified, as a result of high cytotoxicity. These results demonstrate the promising utility of the KeratinoSens™ assay for evaluating the skin sensitization potential of agrochemical AIs and formulations. PMID:25981449

  18. Sorption of four hydrophobic organic contaminants by biochars derived from maize straw, wood dust and swine manure at different pyrolytic temperatures.

    PubMed

    Wang, Ziying; Han, Lanfang; Sun, Ke; Jin, Jie; Ro, Kyoung S; Libra, Judy A; Liu, Xitao; Xing, Baoshan

    2016-02-01

    Sorption behavior of acetochlor (ACE), dibutyl phthalate (DBP), 17α-Ethynyl estradiol (EE2) and phenanthrene (PHE) with biochars produced from three feedstocks (maize straw (MABs), pine wood dust (WDBs) and swine manure (SWBs)) at seven heat treatment temperatures (HTTs) was evaluated. The bulk polarity of these biochars declined with increasing HTT while the aromaticity and CO2-surface area (CO2-SA) rose. The surface OC contents of biochars were generally higher than bulk OC contents. The organic carbon (OC)-normalized CO2-SA (CO2-SA/OC) of biochars significantly correlated with the sorption coefficients (n and logK(oc)), suggesting that pore filling could dominate the sorption of tested sorbates. SWBs had higher logK(oc) values compared to MABs and WDBs, due to their higher ash contents. Additionally, the logK(oc) values for MABs was relatively greater than that for WDBs at low HTTs (≤400 °C), probably resulting from the higher CO2-SA/OC, ash contents and aromaticity of MABs. Surface polarity and the aliphatic C may dominate the sorption of WDBs obtained at relatively low HTTs (≤400 °C), while aromatic C affects the sorption of biochars at high HTTs. Results of this work aid to deepen our understanding of the sorption mechanisms, which is pivotal to wise utilization of biochars as sorbents for hazardous organic compounds. PMID:26364218

  19. Nitrate-induced photolysis in natural waters: Controls on concentrations of hydroxyl radical photo-intermediates by natural scavenging agents

    SciTech Connect

    Brezonik, P.L.; Fulkerson-Brekken, J.

    1998-10-01

    The importance of the principal natural scavenging agents for hydroxyl radicals ({sup {sm_bullet}}OH) was evaluated, and a general framework was developed to predict the significance of nitrate-induced, {sup {sm_bullet}}OH-mediated degradation of aquatic contaminants. Rate constants for *OH scavenging by dissolved organic matter (DOM) from five surface water sources were in a narrow range which is similar to previously reported values and suggests that the importance of DOM as a {sup {sm_bullet}}OH sink can be estimated simply from the dissolved organic carbon (DOC) concentration of a water. Scavenging of {sup {sm_bullet}}*OH by carbonate and bicarbonate is generally less important, but these ions can be the major cause of *OH scavenging in low DOC, high alkalinity waters. Use of the framework is illustrated by predicting levels of {sup {sm_bullet}}OH and half-lives of the corn herbicide acetochlor in waters ranging from pristine to highly influenced by agricultural activities.

  20. Synthesis and Biological Activity Evaluation of Novel α-Amino Phosphonate Derivatives Containing a Pyrimidinyl Moiety as Potential Herbicidal Agents.

    PubMed

    Chen, Jin-Long; Tang, Wu; Che, Jian-Yi; Chen, Kai; Yan, Gang; Gu, Yu-Cheng; Shi, De-Qing

    2015-08-19

    To find novel high-activity and low-toxicity herbicide lead compounds with novel herbicidal mode of action, series of novel α-amino phosphonate derivatives containing a pyrimidinyl moiety, I, II, III, and IV, were designed and synthesized by Lewis acid (magnesium perchlorate) catalyzed Mannich-type reaction of aldehydes, amines, and phosphites. Their structures were clearly identified by spectroscopy data (IR, (1)H NMR, (31)P NMR, EI-MS) and elemental analyses. The bioassay [in vitro, in vivo (GH1 and GH2)] showed that most compounds I exhibited good herbicidal activities; for example, the activities of compounds Ib, Ic, Ig, Ii, Ik, and Im were as good as the positive control herbicides (acetochlor, atrazine, mesotrione, and glyphosate). However, their structural isomers II and III and analogues IV did not display any herbicidal activities in vivo, although some of them possessed selective inhibitory activity against Arabidopsis thaliana in vitro. Interestingly, it was found that compounds IVs, IVt, and IVl showed selective insecticidal activities against Aphis species or Plutella xylostella, respectively. Their preliminary herbicidal mode of action and structure-activity relationships were also studied. PMID:26222653

  1. Assessment of the effects of farming and conservation programs on pesticide deposition in high plains wetlands.

    PubMed

    Belden, Jason B; Hanson, Brittany Rae; McMurry, Scott T; Smith, Loren M; Haukos, David A

    2012-03-20

    We examined pesticide contamination in sediments from depressional playa wetlands embedded in the three dominant land-use types in the western High Plains and Rainwater Basin of the United States including cropland, perennial grassland enrolled in conservation programs (e.g., Conservation Reserve Program [CRP]), and native grassland or reference condition. Two hundred and sixty four playas, selected from the three land-use types, were sampled from Nebraska and Colorado in the north to Texas and New Mexico in the south. Sediments were examined for most of the commonly used agricultural pesticides. Atrazine, acetochlor, metolachlor, and trifluralin were the most commonly detected pesticides in the northern High Plains and Rainwater Basin. Atrazine, metolachlor, trifluralin, and pendimethalin were the most commonly detected pesticides in the southern High Plains. The top 5-10% of playas contained herbicide concentrations that are high enough to pose a hazard for plants. However, insecticides and fungicides were rarely detected. Pesticide occurrence and concentrations were higher in wetlands surrounded by cropland as compared to native grassland and CRP perennial grasses. The CRP, which is the largest conservation program in the U.S., was protective and had lower pesticide concentrations compared to cropland. PMID:22356096

  2. Utilizing toxicogenomic data to understand chemical mechanism of action in risk assessment

    SciTech Connect

    Wilson, Vickie S.; Keshava, Nagalakshmi; Hester, Susan; Segal, Deborah; Chiu, Weihsueh; Thompson, Chad M.; Euling, Susan Y.

    2013-09-15

    The predominant role of toxicogenomic data in risk assessment, thus far, has been one of augmentation of more traditional in vitro and in vivo toxicology data. This article focuses on the current available examples of instances where toxicogenomic data has been evaluated in human health risk assessment (e.g., acetochlor and arsenicals) which have been limited to the application of toxicogenomic data to inform mechanism of action. This article reviews the regulatory policy backdrop and highlights important efforts to ultimately achieve regulatory acceptance. A number of research efforts on specific chemicals that were designed for risk assessment purposes have employed mechanism or mode of action hypothesis testing and generating strategies. The strides made by large scale efforts to utilize toxicogenomic data in screening, testing, and risk assessment are also discussed. These efforts include both the refinement of methodologies for performing toxicogenomics studies and analysis of the resultant data sets. The current issues limiting the application of toxicogenomics to define mode or mechanism of action in risk assessment are discussed together with interrelated research needs. In summary, as chemical risk assessment moves away from a single mechanism of action approach toward a toxicity pathway-based paradigm, we envision that toxicogenomic data from multiple technologies (e.g., proteomics, metabolomics, transcriptomics, supportive RT-PCR studies) can be used in conjunction with one another to understand the complexities of multiple, and possibly interacting, pathways affected by chemicals which will impact human health risk assessment.

  3. Nonpoint-source pollutant discharges of the three major tributaries to Reelfoot Lake, west Tennessee, October 1987-September 1989

    USGS Publications Warehouse

    Lewis, Michael E.; Garrett, Jerry W.; Hoos, Anne B.

    1992-01-01

    runof/ Significant diflerences in the mean concentrations of nutrients in runoff were defined between the active agricultural months (April through September) and the inactive months (October through March). Storm-runofS samples were analyzed for II selected triazine herbicides. Alachlor and atrazine were the most commonly detected herbicides. Thirty-two percent of the samples contained detectable levels of alachlor and 93 percent of the samples contained detectable levels of atrazine. Ninety percent of the samples collected during the active agricultural months contained detectable leveki of alachlor and all 29 samples contained detectable levels of atrazine. Sixteen samples exceeded lifetime health-advisory levels for atrazine in drinking water (3 micrograms per liter); two samples collected from the April IS, 1988, storm at North Reelfoot Creek and South Reelfoot Creek contained 42 and 57 micrograms per liter of atrazine, respectively. Concentrations of the other nine triazine herbicides were generally less than the level of detection (0.1 microgram per liter).

  4. Factors affecting herbicide yields in the Chesapeake Bay watershed, June 1994

    USGS Publications Warehouse

    Hainly, R.A.; Kahn, J.M.

    1996-01-01

    Median concentrations and instantaneous yields of alachlor, metolachlor, atrazine, cyanazine, and simazine were generally highest at sites in the Lower Susquehanna River Basin and in agricultural subbasins. Instantaneous herbicide yields are related to land use, hydrogeologic setting, streamflow yield, and agricultural row cropping practices. The significance of these relations may be affected by the interdependence of the factors. The percentage of basin area planted in corn is the most influential factor in the prediction of herbicide yield. Instantaneous yields of all five herbicides measured in June 1994 related poorly to averaged 199094 herbicide use. Annually averaged herbicide-use data are too general to use as a predictor for short-term herbicide yields. An evaluation of factors affecting herbicide yields could be refined with more-current land use and land cover information and a more accurate estimate of the percentage of basin area planted in corn. Factors related to herbicide yields can be used to predict herbicide yields in other basins within the Chesapeake Bay watershed and to develop an estimate of herbicide loads to Chesapeake Bay.Median concentrations and instantaneous yields of alachlor, metolachlor, atrazine, cyanazine, and simazine were generally highest at sites in the Lower Susquehanna River Basin and in agricultural subbasins. Instantaneous herbicide yields are related to land use, hydrogeologic setting, streamflow yield, and agricultural row cropping practices. The significance of these relations may be affected by the interdependence of the factors. The percentage of basin area planted in corn is the most influential factor in the prediction of herbicide yield. Instantaneous yields of all five herbicides measured in June 1994 related poorly to averaged 1990-94 herbicide use. Annually averaged herbicide-use data are too general to use as a predictor for short-term herbicide yields. An evaluation of factors affecting herbicide yields could

  5. Herbicide concentrations in and loads transported by the Conestoga River and Pequea Creek, Lancaster County, Pennsylvania, 1992-95

    USGS Publications Warehouse

    Reed, Lloyd A.; Koerkle, Edward H.; Takita, Charles S.

    1997-01-01

    Water samples were collected from four streams in Lancaster County from 1992 through 1995 and analyzed for selected herbicides. Samples were collected from the Little Conestoga Creek near Churchtown, Mill Creek (a tributary to the Conestoga River) at Elshelman Mill Road near Lyndon, the Conestoga River at Conestoga, and Pequea Creek at Martic Forge. Most samples were collected from stormflow that occurred during the growing season. Samples were analyzed for alachlor, aldrin, atrazine, chlordane, cyanazine, dieldrin, malathion, metolachlor, propazine, simazine, and toxaphene. Most samples had detectable concentrations of alachlor, atrazine, metolachlor, and simazine, and the loads of these constituents that were transported during each of the 4 years were computed. Of the samples collected from each of the streams?Little Conestoga Creek, Mill Creek, Conestoga River, and Pequea Creek?10, 12, 15, and 18 percent, respectively, had atrazine concentrations greater than 3.0 micrograms per liter, the U.S. Environmental Protection Agency maximum contaminant level. Loads of atrazine, metolochlor, and simazine were greater than loads of any other herbicides. The largest loads were transported during 1994. Loads of atrazine transported by the four streams during periods of storm- flow from May to September 1994 totaled 3.46, 28.3, 263, and 46.8 pounds, respectively. The total loads of atrazine transported by the four streams?Little Conestoga Creek, Mill Creek, Conestoga River, and Pequea Creek?during calendar year 1994 were 6.48, 54.1, 498, and 102 pounds, respectively. A little less than half the atrazine load transported by each stream?45, 39, 42, and 42 percent, respectively?was transported during storms that occurred from May through September. Average annual yields of atrazine for the period 1992-95 were 0.59, 0.64, 0.68, and 0.51 pounds per square mile from the Little Conestoga Creek, Mill Creek, Conestoga River, and Pequea Creek, respectively. Average annual yields of

  6. Assessment of herbicide leaching risk in two tropical soils of Reunion Island (France).

    PubMed

    Bernard, H; Chabalier, P F; Chopart, J L; Legube, B; Vauclin, M

    2005-01-01

    Application of organic chemicals to a newly irrigated sugarcane (Saccharum officinarum L.) area located in the semiarid western part of Reunion Island has prompted local regulatory agencies to determine their potential to contaminate ground water resources. For that purpose, simple indices known as the ground water ubiquity score (Gustafson index, GUS), the retardation factor (RF), the attenuation factor (AF), and the log-transformed attenuation factor (AFT) were employed to assess the potential leaching of five herbicides in two soil types. The herbicides were alachlor [2-chloro-2',6'-diethyl-N-(methoxy-methy) acetanilide], atrazine [2-chloro-4-(ethylamino)-6-(isopropylamino)-1,3,5-triazine], diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea], 2,4-D [(2,4-dichlorophenoxy) acetic-acid], and triclopyr [((3,5,6-trichloro-2-pyridyl)oxy) acetic-acid]. The soil types were Vertic (BV) and Andepts (BA) Inceptisols, which are present throughout the Saint-Gilles study area on Reunion Island. To calculate the indices, herbicide sorption (K(oc)) and dissipation (half-life, DT50) properties were determined from controlled batch experiments. Water fluxes below the root zone were estimated by a capacity-based model driven by a rainfall frequency analysis performed on a 13-yr data series. The results show a lower risk of herbicide leaching than in temperate regions due to the tropical conditions of the study area. Higher temperatures and the presence of highly adsorbent soils may explain smaller DT50 and higher K(oc) values than those reported in literature concerning temperate environments. Based on the RF values, only 2,4-D and triclopyr appear mobile in the BV soil, with all the other herbicides being classified from moderately to very immobile in both soils. The AFT values indicate that the potential leaching of the five herbicides can be considered as unlikely, except during the cyclonic period (about 40 d/yr) when there is a 2.5% probability of recharge rates equal to or

  7. Airborne pesticide residues along the Mississippi River

    USGS Publications Warehouse

    Majewski, M.S.; Foreman, W.T.; Goolsbys, D.A.; Nakagaki, N.

    1998-01-01

    The occurrence, concentration, and geographical distribution of agricultural pesticides were determined in air over the Mississippi River from New Orleans, LA, to St. Paul, MN, during the first 10 days of June 1994. Air samples were collected from a research vessel by pulling air through polyurethane foam plugs at about 100 L/min for up to 24 h. Each sample was analyzed for 42 pesticides and 3 pesticide transformation products. Twenty- five compounds-15 herbicides, 7 insecticides, and 3 pesticide transformation products-were detected in one or more samples with concentrations ranging from 0.05 to 80 ng/m3. Alachlor, chlorpyrifos, diazinon, fonofos, malathion, methyl parathion, metolachlor, metribuzin, pendimethalin, and trifluralin were detected in 80% or more of the samples. The highest concentrations for chlorpyrifos (1.6 ng/m3), diazinon (0.36 ng/m3), and malathion (4.6 ng/m3) all occurred near major metropolitan areas. These samples represent a 'snapshot in time', a spatial and temporal integration of which pesticides were present in the air during each sampling period. The occurrence and atmospheric concentrations of the observed pesticides were most closely related to their use on cropland within 40 km of the river.The occurrence, concentration, and geographical distribution of agricultural pesticides were determined in air over the Mississippi River from New Orleans, LA, to St. Paul, MN, during the first 10 days of June 1994. Air samples were collected from a research vessel by pulling air through polyurethane foam plugs at about 100 L/min for up to 24 h. Each sample was analyzed for 42 pesticides and 3 pesticide transformation products. Twenty-five compounds-15 herbicides, 7 insecticides, and 3 pesticide transformation products-were detected in one or more samples with concentrations ranging from 0.05 to 80 ng/m3. Alachlor, chlorpyrifos, diazinon, fonofos, malathion, methyl parathion, metolachlor, metribuzin, pendimethalin, and trifluralin were detected in

  8. Interaction of environmental chemicals with the estrogen and progesterone receptors from the oviduct of the American alligator.

    PubMed Central

    Vonier, P M; Crain, D A; McLachlan, J A; Guillette, L J; Arnold, S F

    1996-01-01

    Reports of reproductive abnormalities in the American alligator from Lake Apopka, Florida, have been linked to a spill of DDT and other pesticides suspected of having hormonelike activity. To determine whether environmental chemicals had the potential to function as exogenous hormones in the American alligator, we examined the ability of chemicals to bind the estrogen receptor (aER) and progesterone receptor (aPR) in a protein extract prepared from the oviduct of the alligator. In competition binding assays with [3H]17 beta-estradiol, some DDT metabolites showed inhibition of [3H]17 beta-estradiol binding to aER. A combination of DDTs demonstrated an additive decrease in [3H]17 beta-estradiol binding to aER. Modern-use chemicals such as alachlor, trans-nonachlor, endosulfan, and atrazine also competed with [3H]17 beta-estradiol for binding to the aER. To test the effect of chemicals identified in alligator eggs from Lake Apopka on [3H]17 beta-estradiol binding, we mixed these chemicals at concentrations measured in eggs in the competition binding assay. 2,2-bis(4-chlorophenyl)-N-(methoxymethyl)acetamide (p,p'-DDD) and trans-nonachlor, both found in Lake Apopka, interacted with aER, whereas others such as chlordane and toxaphene did not. Surprisingly, combinations of these chemicals decreased [3H]17 beta-estradiol binding in a greater than additive manner. To assess the ability of chemicals to interact with aPR, we performed commpetition binding assays with the synthetic progestin [3H]R5020. Most of the chemicals tested did not reduce [3H]R5020 binding to aPR, whereas endosulfan, alachlor, and kepone inhibited binding. These results provide the first evidence that environmental chemicals bind the aER and aPR from the American alligator, supporting the hypothesis that the reported reproductive abnormalities may be related to the modulation of endocrine-related responses. The findings that combinations of chemicals demonstrated a greater than additive interaction with

  9. Phosphatidylcholine Specific PLC-Induced Dysregulation of Gap Junctions, a Robust Cellular Response to Environmental Toxicants, and Prevention by Resveratrol in a Rat Liver Cell Model

    PubMed Central

    Sovadinova, Iva; Babica, Pavel; Böke, Hatice; Kumar, Esha; Wilke, Andrew; Park, Joon-Suk; Trosko, James E.; Upham, Brad L.

    2015-01-01

    Dysregulation of gap junctional intercellular communication (GJIC) has been associated with different pathologies, including cancer; however, molecular mechanisms regulating GJIC are not fully understood. Mitogen Activated Protein Kinase (MAPK)-dependent mechanisms of GJIC-dysregulation have been well-established, however recent discoveries have implicated phosphatidylcholine-specific phospholipase C (PC-PLC) in the regulation of GJIC. What is not known is how prevalent these two signaling mechanisms are in toxicant/toxin-induced dysregulation of GJIC, and do toxicants/toxins work through either signaling mechanisms or both, or through alternative signaling mechanisms. Different chemical toxicants were used to assess whether they dysregulate GJIC via MEK or PC-PLC, or both Mek and PC-PLC, or through other signaling pathways, using a pluripotent rat liver epithelial oval-cell line, WB-F344. Epidermal growth factor, 12-O-tetradecanoylphorbol-13-acetate, thrombin receptor activating peptide-6 and lindane regulated GJIC through a MEK1/2-dependent mechanism that was independent of PC-PLC; whereas PAHs, DDT, PCB 153, dicumylperoxide and perfluorodecanoic acid inhibited GJIC through PC-PLC independent of Mek. Dysregulation of GJIC by perfluorooctanoic acid and R59022 required both MEK1/2 and PC-PLC; while benzoylperoxide, arachidonic acid, 18β-glycyrrhetinic acid, perfluorooctane sulfonic acid, 1-monolaurin, pentachlorophenol and alachlor required neither MEK1/2 nor PC-PLC. Resveratrol prevented dysregulation of GJIC by toxicants that acted either through MEK1/2 or PC-PLC. Except for alachlor, resveratrol did not prevent dysregulation of GJIC by toxicants that worked through PC-PLC-independent and MEK1/2-independent pathways, which indicated at least two other, yet unidentified, pathways that are involved in the regulation of GJIC. In conclusion: the dysregulation of GJIC is a contributing factor to the cancer process; however the underlying mechanisms by which gap

  10. Coupling solid-phase extraction and enzyme-linked immunosorbent assay for ultratrace determination of herbicides in pristine water

    USGS Publications Warehouse

    Aga, D.S.; Thurman, E.M.

    1993-01-01

    Solid-phase extraction (SPE) and enzyme-linked immunosorbent assay (ELISA) were coupled for automated trace analysis of pristine water samples containing 2-chloro-4-ethylamino-6-isopropylamine-s-triazine (atrazine) and 2-chloro-2???,6???-diethyl-N-(methoxymethyl)acetanilide (alachlor). The isolation of the two herbicides on a C18-resin involved the selection of an elution solvent that both removes interfering substances and is compatible with ELISA. Ethyl acetate was selected as the elution solvent followed by a solvent exchange with methanol/water (20/80, % v/v). The SPE-ELISA method has a detection limit of 5.0 ng/L (5 ppt), >90% recovery, and a relative standard deviation of ??10%. The performance of a microtiter plate-based ELISA and a magnetic particle-based ELISA coupled to SPE was also evaluated. Although the sensitivity of the two ELISA methods was comparable, the precision using magnetic particles was improved considerably (??10% versus ??20%) because of the faster reaction kinetics provided by the magnetic particles. Finally, SPE-ELISA and isotope dilution gas chromatography/ mass spectrometry correlated well (correlation coefficient of 0.96) for lake-water samples. The SPE-ELISA method is simple and may have broader applications for the inexpensive automated analysis of other contaminants in water at trace levels.

  11. Determination of trace levels of herbicides and their degradation products in surface and ground waters by gas chromatography/ion-trap mass spectrometry

    USGS Publications Warehouse

    Pereira, W.E.; Rostad, C.E.; Leiker, T.J.

    1990-01-01

    A rapid, specific and highly sensitive method is described for the determination of several commonly used herbicides and their degradation products in surface and ground waters by using gas chromatography/ion-trap mass spectrometry. The compounds included atrazine, and its degradation products desethylatrazine and desisopropylatrazine; Simazine; Cyanazine; Metolachlor; and alachlor and its degradation products, 2-chloro-2', 6'-diethylacetanilide, 2-hydroxy-2', 6'-diethylacetanilide and 2,6-diethylaniline. The method was applied to surface-water samples collected from 16 different stations along the lower Mississippi River and its major tributaries, and ground-water samples beneath a cornfield in central Nebraska. Average recovery of a surrogate herbicide, terbuthylazine, was greater than 99%. Recoveries of the compounds of interest from river water spiked at environmental levels are also presented. Full-scan mass spectra of these compounds were obtained on 1 ng or less of analyte. Data were collected in the full-scan acquisition mode. Quantitation was based on a single characteristic ion for each compound. The detection limit was 60 pg with a signal-to-noise ratio of greater than 10:1.

  12. Plan of study to determine the effect of changes in herbicide use on herbicide concentrations in Midwestern streams, 1989-94

    USGS Publications Warehouse

    Goolsby, Donald A.; Boyer, Laurie L.; Battaglin, William A.

    1994-01-01

    An approach was developed to determine if recent changes in the use of herbicides has affected herbicide concentrations in Midwestern streams. This approach also provides a plan to determine if the abnormally high rainfall and flooding in 1993 has an effect on nitrate concentrations in 1994 in streams that flooded in 1993. The approach involves sampling 53 stream sites, 50 of which were sampled in 1989 and 1990 as part of a reconnaissance to determine the geographic and seasonal distribution of herbicides in 10 Midwestern States. Sites will be sampled twice, once prior to application of herbicides, in March or early April, and once during the first runoff event after application of herbicides. Samples will be analyzed for 11 herbicide and 2 atrazine metabolites by gas chromatography/mass spectrometry. Samples will also be analyzed for ESA (an alachlor metabolite), two cyanazine metabolites, and nutrients. Changes to the manufacturers' label have decreased the maximum recommended application rate for atrazine on com and sorghum by about 50 percent since the 1989-90 study. Conversely, the use of other herbicides, such as cyanazine, has increased by more than 25 percent since 1989. Statistical procedures such as Wilcoxon signed rank tests for paired samples will be used to determine if the distributions of herbicide and nitrate concentrations in 1994 are different from those measured in 1989 and 1990.

  13. The impact of agricultural practices on shallow groundwater in the Bluegrass Region of Kentucky

    SciTech Connect

    Hampson, S.K.; Sendlein, L.V.A. . Dept. of Geological Sciences)

    1993-03-01

    To study the effects of agricultural practices on the groundwater quality of the Inner Bluegrass Region of Kentucky, a large representative row crop and livestock production operation was chosen. Located in southeastern Bourbon County, the study area encompasses a 1,400 acre watershed underlain by limestones and shales of the Ordovician age Lexington Limestone Formation. Sampling and testing of surface water, ephemeral, and perennial spring waters began in the area in October, 1989. At crop and pasture micro-sites within the study area, nests containing porous-cup lysimeters and monitoring wells were installed prior to the 1992 growing season. Samples from the nest locations were analyzed for Nitrate-N, triazines, metolochlor, carbofuran, alachlor, and 2,4-D. While only ten per cent of the total samples from the study area showed triazine or Nitrate-N concentrations in excess of EPA limits, greater than 80 per cent of the samples showed concentrations of triazines above detection limits, and greater than 70 per cent of the samples contained concentrations of Nitrate-N above detection limits. Occurrences of detectable concentrations of triazines and Nitrate-N were more frequent at crop-site nests, than at pasture-site nests. Nests at both the crop and pasture sites indicated dilution of Nitrate-N and triazine concentrations with depth.

  14. Net photosynthesis and respiration of sago pondweed (Potamogeton pectinatus) exposed to herbicides

    USGS Publications Warehouse

    Fleming, W.J.; Ailstock, M.S.; Momot, J.J.

    1995-01-01

    We determined net photosynthesis and respiration rates for sago pondweed (potamogeton pectinatus) exposed to various concentrations of 11 herbicides widely used in Maryland during the past decade. Net photosynthesis and respiration were determined by measuring changes in the. oxygen content of solutions containing dilutions of technical grade herbicides. At 20-22? C and 58 umol/m2/sec of photosynthetically active radiation (PAR), oxygen production of undosed plants averaged 0.72-2.03 mg/g fresh wt/h. Respiration rates of undosed plants averaged 0.46-0.60 mg O2/g fresh wt/h. Nominal herbicide concentrations (ng/L) that reduced net photosynthesis by 5O percent (IC5O) were: metribuzin, 8; atrazine, 29; cyanazine, 32; linuron, 70; simazine, 164; and paraquat, 240. IC5O values for 2,4-D, acifluorfen, glyphosate and metolachlor exceeded the maximum test concentration of 10,000 ng/L. The IC5O value for alachlor was estimated to be between 1,000 and 10,000 ng/L. None of the herbicides tested had a significant effect on dark respiration.

  15. Multiresidue method for the quantitation of 20 pesticides in aquatic products.

    PubMed

    Cho, Ha Ra; Park, Jun Seo; Kim, Junghyun; Han, Sang Beom; Choi, Yong Seok

    2015-12-01

    As the consumption of aquatic products increased, the need for regulation of pesticide residues in aquatic products also emerged. Thus, in this study, a scheduled multiple reaction monitoring (sMRM) method employing a novel extraction and purification step based on QuEChERS with EDTA was developed for the simultaneous quantitation of 20 pesticides (alachlor, aldicarb, carbofuran, diazinon, dimethoate, dimethomorph, ethoprophos, ferimzone, fluridone, hexaconazole, iprobenfos, malathion, methidathion, methiocarb, phenthoate, phosalone, phosmet, phosphamidon, pirimicarb, and simazine) in aquatic products. Additionally, the present method was validated in the aspects of specificity, linearity (r ≥ 0.980), sensitivity (the limit of quantitation (LOQ) ≤ 5 ng/g), relative standard deviation, RSD (1.0% ≤ RSD ≤ 19.4%), and recovery (60.1% ≤ recovery ≤ 117.9%). Finally, the validated method was applied for the determination of the 20 pesticide residues in eel and shrimp purchased from local food markets. In the present study, QuEChERS with EDTA was successfully expanded to residual pesticide analysis for the first time. The present method could contribute to the rapid and successful establishment of the positive list system in South Korea. PMID:26466578

  16. A multi-residue method for determination of 70 organic micropollutants in surface waters by solid-phase extraction followed by gas chromatography coupled to tandem mass spectrometry.

    PubMed

    Terzopoulou, Evangelia; Voutsa, Dimitra; Kaklamanos, George

    2015-01-01

    A multi-residue method, based on gas chromatography coupled to tandem mass spectrometry (GC-MS/MS), has been developed for the determination of 70 organic micropollutants from various chemical classes (organochlorinated, organophosphorous, triazines, carbamate and urea, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, pharmaceuticals, phenols, etc.) in surface waters. A single-step SPE extraction using OASIS HLB cartridges was employed for the recovery of target micropollutants. The method has been validated according to monitoring performance criteria of the Water Framework Directive, taking into account the approved guidelines on quality assurance and quality control. The recoveries ranged from 60 to 110 %, the coefficient of variation from 0.84 to 27.4 %, and the uncertainty from 6 to 37 %. The LOD varied from 6.0 to 40 ng/L. The limits of quantification for the priority pollutants anthracene, alachlor, atrazine, benzo(a)pyrene, chlorfenvinphos, diuron, isoproturon, nonylphenol, simazine, and terbutryn fulfill the criterion of <30 % of the relevant environmental standards. The method was employed to investigate the water quality in the basin of a transboundary river, Strymonas, in NE Greece during three sampling campaigns conducted in the year 2013. Thirty-nine compounds were detected in the river water. Metolachlor, diuron, isoproturon, salicylic acid, chlorfenvinphos, 1,2-benzanthracene, pyrene, diflubenzuron, and carbaryl exhibited the highest detection frequencies. PMID:25109470

  17. Water: pesticides in ground water beneath irrigated farmland in Nebraska, August 1978

    SciTech Connect

    Spalding, R.F.; Junk, G.A.; Richard, J.J.

    1980-09-01

    During the 1978 irrigation season, 14 ground water samples were collected in the Central Platte region of Nebraska, an area known to have high nitrate-nitrogen (NO-N) levels, and analyzed for the presence of 13 pesticide residues. Atrazine levels ranged from 0.06 ..mu..g/liter to 3.12 ..mu..g/liter and were correlated to NO/sub 3/-N concentrations with a coefficient of r = +0.55. Nitrate-nitrogen concentrations were measured as indicators of deep percolation from irrigated lands and ranged from 17.1 mg/liter to 34.3 mg/liter. Alachlor levels ranged from <0.01 ..mu..g/liter to 0.71 ..mu..g/liter. The amounts of 2,4-D were indeterminate because of experimental problems. Levels of the herbicides silvex and EPTC were below the limits of detectability. Levels of the oragnochlorine insecticides endrin, ..gamma..-BHC (lindane), dieldrin, DDT and its primary metabolite DDE, heptachlor and its primary derivative heptachlor epoxide, and methoxychlor were all below the detectable limits of 0.005 and 0.010 ..mu..g/liter.

  18. Investigation of factors affecting terrestrial passive sampling device performance and uptake rates in laboratory chambers

    SciTech Connect

    Johnson, K.A.; Weisskopf, C.P.

    1995-12-31

    A rapid sampling method using passive sampling devices (PSDS) for soil contaminant characterization shows extreme promise. The use of PSDs increases ease and speed of analysis, decreases solvent usage and cost, and minimizes the transport of contaminated soils. Time and cost savings allow a high sampling frequency, providing a more thorough site characterization than traditional methods. The authors have conducted both laboratory and field studies with terrestrial PSDS. Laboratory studies demonstrated the concentration and moisture dependence of sampler uptake and provided an estimate of the optimal field sampling time for soils contaminated with polychlorinated biphenyls (PCBs). These PSDs were also used to accurately estimate PCB concentrations at hazardous waste site where concentrations ranged from 0.01 to 200 ug PCB/g soil. However, PSDs in the field had sampling rates approximately three times greater than in the laboratory. As a result several factors affecting PSD sampling rates and/or performance in laboratory chambers were evaluated. The parameters investigated were soil bulk density or compactness, chamber size and air flow. The chemicals used in these studies included two PCB congeners (52 and 153), three organochlorine pesticides (DDT, dieldrin and methoxychlor), three organophosphate pesticides (chlorpyrifos, diazinon and terbufos) and three herbicides (alachlor, atrazine and metolachlor).

  19. Contribution of subsoil and aquifer microorganisms to ground-water quality. Technical report, 1 July 1988-30 June 1989. (Final)

    SciTech Connect

    Turco, R.F.; Konopka, A.E.

    1989-06-01

    Little information about the microbiology of the subsurface environment is available. The study was conducted to better understand the microbiology and microbial processes that occur in the subsurface under a typical midwestern agricultural soil. A 26-meter bore was installed in November of 1988. Sterile collections of soils were made at 17 different depths. A physical as well as biological investigation of the subsurface materials was conducted. Among the measured parameters were particle-size analysis, carbon, carbonates, nitrogen, phosphorus, potassium, and water-holding capacity. The level of three pesticides, atrazine, metolachlor, and alachlor, was determined. Microbial biomass was assessed using direct counts, phospholipid content, and plate counts. The ability of microbial populations resident in the strata to use glucose, phenol, aniline, (14)C-ring labeled 2-methyl-6-ethyl-aniline, (14)C-ring labeled metolachlor, (14)C-carbonyl labeled metolachlor, and atrazine was assessed. Physical analysis indicated that the site contained up to 17 different strata. The site materials were primarily glacial tills with high carbonate content. Microbial numbers and activity in the tills was much lower than either in the surface materials or the aquifer located at 25 m.

  20. Pesticides in ground water beneath irrigated farmland in Nebraska, August 1978

    SciTech Connect

    Spalding, R.F.; Junk, G.A.; Richard, J.J.

    1980-09-01

    During the 1978 irrigation season, 14 ground water samples were collected in the Central Platte region of Nebraska, an area known to have high nitrate-nitrogen (NO/sub 3/--N) levels, and analyzed for the presence of 13 pesticide residues. Atrazine levels ranged from 0.06 microgram/liter to 3.12 microgram/liter and were correlated to NO/sub 3/--N concentrations with a coefficient of r . +0.55. Nitrate-nitrogen concentrations were measured as indicators of deep percolation from irrigated lands and ranged from 17.1 mg/liter to 34.3 mg/liter. Alachlor levels ranged from less than 0.01 microgram/liter to 0.71 microgram/liter. The amounts of 2,4-D were indeterminate because of experimental problems. Levels of the herbicides silvex and EPTC were below the limits of detectability. Levels of the organochlorine insecticides endrin, gamma-BHC (lindane), dieldrin, DDT and its primary metabolite DDE, heptachlor and its primary derivative heptachlor epoxide, and methoxychlor were all below the detectable limits of 0.005-0.010 microgram/liter.

  1. BOREAS TGB-7 Dry Deposition Herbicide and Organochlorine Flux Data

    NASA Technical Reports Server (NTRS)

    Waite, Don; Conrad, Sara K. (Editor); Hall, Forrest G. (Editor)

    2000-01-01

    The BOREAS TGB-7 team measured the concentration and flux of several agricultural pesticides in air, rainwater, and dry deposition samples in order to determine the associated yearly deposition rates. This data set contains information on the dry deposition flux of seven herbicides [2,4- dichlorophenoxyacidic_acid (2,4-D), bromoxynil, dicamb, 2-methyl-4-chlorophenoxyacetic acid (MCPA), triallate, trifluralin, and diclop-methyl] known to appear in the atmosphere of the Canadian prairies. Also, the concentration of three herbicides (atrazine, alachlor, and metolachlor), two groups of insecticides (lindane and breakdown products and dichloro-diphenyl-trichloroethane (DDT) and breakdown products), and several polychlorinated biphenyls commonly used in the central United States was measured. All of these chemicals are reported, in the literature, to be transported in the atmosphere. Many have been reported to occur in boreal and arctic food chains. The sampling was carried out from 16-Jun to 13-Aug-1993 and 04-May to 20-Jul-1994 at the BOREAS site in the Prince Albert National Park (Waskesiu). The data are stored in tabular ASCII files.

  2. BOREAS TGB-7 Ambient Air Herbicide and Organochlorine Concentration Data

    NASA Technical Reports Server (NTRS)

    Waite, Don; Hall, Forrest G. (Editor); Conrad, Sara K. (Editor)

    2000-01-01

    The BOReal Ecosystem-Atmosphere Study Trace Gas Biogeochemistry (BOREAS TGB)-7 team measured the concentration and flux of several agricultural pesticides in air, rainwater, and dry deposition samples in order to determine the associated yearly deposition rates. This data set contains information on the ambient air concentration of seven herbicides [2,4- dichlorophenoxyacidic_acid (2,4-D), bromoxynil, dicamb, 2-methyl-4-chlorophenoxyacetic acid (MCPA), triallate, trifluralin, and diclop-methyl] known to appear in the atmosphere of the Canadian prairies. Also, the concentration of three herbicides (atrazine, alachlor, and metolachlor), two groups of insecticides (lindane and breakdown products and dichloro-diphenyl-trichloroethane (DDT) and breakdown products), and several polychlorinated biphenyls commonly used in the central United States was measured. All of these chemicals are reported, in the literature, to be transported in the atmosphere. Many have been reported to occur in boreal and arctic food chains. The sampling was carried out from 16-Jun to 13-Aug-1993 and 04-May to 20-Jul-1994 at the BOREAS site in the Prince Albert National Park (Waskesiu). The data are stored in tabular ASCII files. The data files are available on a CD-ROM (see document number 20010000884).

  3. BOREAS TGB-7 Rainwater Herbicide and Organochlorine Concentration Data

    NASA Technical Reports Server (NTRS)

    Waite, Don; Conrad, Sara K. (Editor); Hall, Forrest G. (Editor)

    2000-01-01

    The BOREAS TGB-7 team measured the concentration and flux of several agricultural pesticides in air and rainwater samples in order to determine the associated yearly deposition rates. This data set contains information on the rainwater concentration of seven herbicides [2,4- dichlorophenoxyacidic_acid (2,4-D), bromoxynil, dicamb, 2-methyl-4-chlorophenoxyacetic acid (MCPA), triallate, trifluralin, and diclop-methyl] known to appear in the atmosphere of the Canadian prairies. Also, the concentration of three herbicides (atrazine, alachlor, and metolachlor), two groups of insecticides (lindane and breakdown products and dichloro-diphenyl-trichloroethane (DDT) and breakdown products), and several polychlorinated biphenyls commonly used in the central United States was measured. All of these chemicals are reported, in the literature, to be transported in the atmosphere. Many have been reported to occur in boreal and arctic food chains. The sampling was carried out from 16-Jun to 13-Aug-1993 and 04-May to 20-Jul-1994 at the BOREAS site in the Prince Albert National Park (Waskesiu). The data are stored in tabular ASCII files.

  4. Simultaneous determination of herbicide residues in tobacco using ultraperformance convergence chromatography coupled with solid-phase extraction.

    PubMed

    Guo, Weiyun; Bian, Zhaoyang; Zhang, Daohong; Tang, Gangling; Liu, Wei; Wang, Jianlong; Li, Zhonghao; Yang, Fei

    2015-03-01

    A time-saving and organic solvent efficient method to simultaneously determine six kinds of herbicide residues in tobacco using solid-phase extraction for sample clean-up and preconcentration and the highly sensitive ultraperformance convergence chromatography method was developed. Parameters for ultraperformance convergence chromatography, including the choice of stationary phase and modifiers, autobackpressure regulator pressure, column temperature, and the flow rate of mobile solvents, were optimized. The herbicide residues of napropamide, alachlor, quizalofop-ethyl, diphenamid, metolachlor, and clomazone in tobacco samples were successfully separated and detected at levels as low as 0.0043-0.0086 mg/kg within 5 min using a nonpolar high strength silica C18 selectivity for bases column and methanol as the cosolvent of the mobile phase of carbon dioxide (75-99.9%, v/v). Analysis of tobacco samples had recoveries of 69.8-95.0%, limit of quantitation of 0.0127-0.0245 mg/kg, limit of detection of 0.0043-0.0086 mg/kg, and correlation coefficient of >0.9990. Results support this method as an efficient alternative to current methodologies for the determination of herbicide residues in tobacco. PMID:25546570

  5. Quality of surface water before implementation of a flood-control project in Chaska, Minnesota

    USGS Publications Warehouse

    Tornes, L.H.

    1981-01-01

    Samples were collected for 1 year from East Creek, Chaska Creek, and Courthouse Lake in Chaska, Minnesota, to determine the water quality before implementation of a flood-control project proposed by the U.S. Army Corps of Engineers. The creeks had similar water-quality characteristics. Data indicate that ground water may be the primary source of dissolved solids, sulfate, chloride, and chromium in the creeks. The pesticides alachlor, atrazine, simazine, and 2,4-D were found in water samples from both creeks but were well below the lethal concentrations for fish. Courthouse Lake, a 57-foot-deep stream-trout lake, had a mean summer trophic-state index of 35. Phytoplankton populations varied seasonally, and blue-green algae were predominant only in late summer. The algal-pollution index was highest in late summer, but did not provide evidence of high organic pollution. The apparently successful recovery of Courthouse Lake from past inundations by Minnesota River floodwaters having total phosphorus concentrations as high as 0.66 milligram per liter suggests that the lake, in time, will also recover from the added runoff expected as a result of implementing the flood-control project. The runoff could temporarily raise the total phosphorus concentration in the lake from 0.03 to 0.12 milligram per liter and raise the spring trophic-state index from 49 to 69.

  6. Extraction of pesticides from contaminated soil using supercritical carbon dioxide

    SciTech Connect

    Hunter, G.B.

    1991-01-01

    The demand for processes to clean up contaminated soils without generating additional contaminants, such as hazardous solvents, is increasing. One approach to minimizing this problem is to use supercritical fluids like light hydrocarbons and CO[sub 2] to extract contaminants from soils. Gases exhibit unique properties under supercritical conditions. They retain the ability to diffuse through the interstitial spaces of solid materials, plus they have the solvating power of liquids. Some examples of extractions using SCFs are caffeine from coffee, cholesterol from eggs, drugs from plants, and nicotine from tobacco. Supercritical CO[sub 2] is an attractive, alternative extraction medium for removal of pesticides from soils. Carbon dioxide is readily available, relatively inexpensive, and if recycled, nonpolluting. Contaminants may be easily recovered by evaporating the CO[sub 2] into an expansion vessel. Supercritical fluid extraction technology is discussed and results are given for the extraction of atrazine, bentazon, alachlor, and permethrin from contaminated soil prepared in the laboratory. Initial studies show >95% removal for these pesticides.

  7. Extraction of pesticides from contaminated soil using supercritical carbon dioxide

    SciTech Connect

    Hunter, G.B.

    1991-12-31

    The demand for processes to clean up contaminated soils without generating additional contaminants, such as hazardous solvents, is increasing. One approach to minimizing this problem is to use supercritical fluids like light hydrocarbons and CO{sub 2} to extract contaminants from soils. Gases exhibit unique properties under supercritical conditions. They retain the ability to diffuse through the interstitial spaces of solid materials, plus they have the solvating power of liquids. Some examples of extractions using SCFs are caffeine from coffee, cholesterol from eggs, drugs from plants, and nicotine from tobacco. Supercritical CO{sub 2} is an attractive, alternative extraction medium for removal of pesticides from soils. Carbon dioxide is readily available, relatively inexpensive, and if recycled, nonpolluting. Contaminants may be easily recovered by evaporating the CO{sub 2} into an expansion vessel. Supercritical fluid extraction technology is discussed and results are given for the extraction of atrazine, bentazon, alachlor, and permethrin from contaminated soil prepared in the laboratory. Initial studies show >95% removal for these pesticides.

  8. Integrated use of biomarkers and bioaccumulation data in Zebra mussel (Dreissena polymorpha) for site-specific quality assessment.

    PubMed

    Binelli, A; Ricciardi, F; Riva, C; Provini, A

    2006-01-01

    One of the useful biological tools for environmental management is the measurement of biomarkers whose changes are related to the exposure to chemicals or environmental stress. Since these responses might vary with different contaminants or depending on the pollutant concentration reached in the organism, the support of bioaccumulation data is needed to prevent false conclusions. In this study, several persistent organic pollutants -- 23 polychlorinated biphenyl (PCB) congeners, 11 polycyclic aromatic hydrocarbons (PAHs), six dichlorodiphenyltricholroethane (DDT) relatives, hexachlorobenzene (HCB), chlorpyrifos and its oxidized metabolite -- and some herbicides (lindane and the isomers alpha, beta, delta; terbutilazine; alachlor; metolachlor) were measured in the soft tissues of the freshwater mollusc Zebra mussel (Dreissena polymorpha) from 25 sampling sites in the Italian portions of the sub-alpine great lakes along with the measure of ethoxyresorufin dealkylation (EROD) and acetylcholinesterase (AChE) activity. The linkage between bioaccumulation and biomarker data allowed us to create site-specific environmental quality indexes towards man-made chemicals. This classification highlighted three different degrees of xenobiotic contamination of the Italian sub-alpine great lakes: a high water quality in Lake Lugano with negligible pollutant levels and no effects on enzyme activities, an homogeneous poor quality for Lakes Garda, Iseo and Como, and the presence of some xenobiotic point-sources in Lake Maggiore, whose ecological status could be jeopardized, also due to the heavy DDT contamination revealed since 1996. PMID:16966160

  9. Distribution of agrochemicals in the lower Mississippi River and its tributaries

    USGS Publications Warehouse

    Pereira, W.E.; Rostad, C.E.; Leiker, T.J.

    1990-01-01

    The Mississippi River and its tributaries drain extensive agricultural regions of the Mid-Continental United States. Millions of pounds of herbicides are applied annually in these areas to improve crop yields. Many of these compounds are transported into the river from point and nonpoint sources, and eventually are discharged into the Gulf of Mexico. Studies being conducted by the U.S. Geological Survey along the lower Mississippi River and its major tributaries, representing a 2000 km river reach, have confirmed that several triazine and acetanilide herbicides and their degradation products are ubiquitous in this riverine system. These compounds include atrazine and its degradation products desethyl and desisopropylatrazine, cyanazine, simazine, metolachlor, and alachlor and its degradation products 2-chloro-2',6'-diethylacetanilide, 2-hydroxy-2',6-diethylacetanilide and 2,6-diethylaniline. Loads of these compounds were determined at 16 different sampling stations. Stream-load calculations provided information concerning (a) conservative or nonconservative behavior of herbicides; (b) point sources or nonpoint sources; (c) validation of sampling techniques; and (d) transport past each sampling station.

  10. Comparison of two screening bioassays, based on the frog sciatic nerve and yeast cells, for the assessment of herbicide toxicity.

    PubMed

    Papaefthimiou, Chrisovalantis; Cabral, Maria de Guadalupe; Mixailidou, Christina; Viegas, Cristina A; Sá-Correia, Isabel; Theophilidis, George

    2004-05-01

    Two different test systems, one based on the isolated sciatic nerve of an amphibian and the other on a microbial eukaryote, were used for the assessment of herbicide toxicity. More specifically, we determined the deleterious effects of increasing concentrations of herbicides of different chemical classes (phenoxyacetic acids, triazines, and acetamides), and of 2,4-dichlorophenol (2,4-DCP), a degradation product of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D), on electrophysiological parameters and the vitality of the axons of the isolated sciatic nerve of the frog (Rana ridibunda) and on the growth curve of the yeast Saccharomyces cerevisiae based on microtiter plate susceptibility assays. The no-observed-effect-concentration (NOEC), defined as the maximum concentration of the tested compound that has no effect on these biological parameters, was estimated. In spite of the different methodological approaches and biological systems compared, the NOEC values were identical and correlated with the lipophilicity of the tested compounds. The relative toxicity established here, 2,4-DCP > alachlor, metolachlor > metribuzin > 2,4-D, 2-methyl-4-chlorophenoxyacetic acid (MCPA), correlates with the toxicity indexes reported in the literature for freshwater organisms. Based on these results, we suggest that the relatively simple, rapid, and low-cost test systems examined here may be of interest as alternative or complementary tests for toxicological assessment of herbicides. PMID:15180372

  11. Herbicide transport in rivers: Importance of hydrology and geochemistry in nonpoint-source contamination

    USGS Publications Warehouse

    Squillace, P.J.; Thurman, E.M.

    1992-01-01

    Alachlor, atrazine, cyanazine, metolachlor, and metribuzin were measured at six sites during 1984 and 1985 in large subbasins within the Cedar River, IA. A computer model separated the Cedar River discharge hydrograph into groundwater and overland-flow components. The concentration of herbicides in the river when groundwater was the major flow component was less than 1.0 μg/L and averaged 0.2 μg/L. The maximum concentrations of herbicides occurred when overland flow was the major component of river discharge, exceeding 50 pg/L for total herbicides. About 6% of the annual river load of atrazine was transported with the groundwater component, while 94% was transported with overland flow. From 1.5 to 5% of the atrazine applied during the year was transported from the basin. Atrazine concentrations in the river in- creased according to the discharge divided by the drainage area. This correlation indicates that rivers with large normalized 2-year peak flows have the potential to transport large concentrations of herbicides. A diagrammatic model of nonpoint-source transport of herbicides was developed that suggests that sorbed transport from fields occurs during episodes of overland flow with rapid dissolution of herbicides downstream. 

  12. Assessing the quality of freshwaters in a protected area within the Tagus River basin district (central Portugal).

    PubMed

    Silva, Emília; Pereira, Ana Carina; Estalagem, Soraia Patrícia; Moreira-Santos, Matilde; Ribeiro, Rui; Cerejeira, Maria José

    2012-01-01

    Water-sediment quality was assessed in an agricultural zone of a protected area within the Tagus River basin district (central Portugal) combining chemical analysis to 12 pesticide compounds and whole toxicity testing using the bacterium , the algae , the crustacean , and the midge . The herbicides alachlor, atrazine ethofumesate, metolachlor, terbuthylazine, the insecticides chlorfenvinphos and chlorpyrifos, and the metabolite 3,4-dichloroaniline were detected in surface water samples at four sites and in groundwater samples from six wells, during four sampling occasions. Measured concentrations were compared with parametric values for human consumption, groundwater quality standards, and environmental quality standards applicable to surface water established in European Union legislation. Most severe adverse effects were noted on the growth of and lethality of in nondiluted water samples. Taking into account the values calculated by the method of toxic unit summation for pesticide mixtures, it was not possible to link the pesticides found to the toxicity detected in the water samples. Conducting this study with chemical analyses and biotests provided a more comprehensive quality assessment and realistic picture of the environmental samples analyzed, although additional studies are needed to evaluate the performance of mixture models for predicting mixture toxicity. This study underlines the importance of chemical analysis and whole toxicity testing as tools for assessing the impact of human activity on the status of water, mainly in protected zones. PMID:23099932

  13. Factors affecting leaching in agricultural areas and an assessment of agricultural chemicals in the ground water of Kansas

    USGS Publications Warehouse

    Perry, C.A.; Robbins, F.V.; Barnes, P.L.

    1988-01-01

    As assessment of hydrologic factors and agricultural practices that may affect the leaching of agricultural chemicals to groundwater was conducted to evaluate the extent and severity of chemical contamination of groundwater resources in Kansas. The climate of a particular area determines the length of the growing season and the availability of water, at the surface and in the ground, for the growth of plants. Climate, together with surficial geology, soil, and principal aquifers, determines the types of crops to be planted,types of tillage, conservation and irrigation practices, and affects the quantity and method of application of agricultural chemicals. Examination of groundwater nitrate-nitrogen data collected from 766 wells throughout Kansas during 1976-81 indicated that 13 of 14 geohydrologic regions had wells producing samples that exceeded the 10-mg/L drinking water standard determined by the U.S. Environmental Protection Agency. One or more herbicides were detected in water samples from 11 of 56 wells during 1985-86 located in areas susceptible to agricultural leaching. Atrazine was the most common herbicide that was detected; it was detected in water at 9 of 11 wells. Cyanazine was detected in water at three wells; metolachlor at two wells; and metribuzin, alachlor, simazine, and propazine were detected at one well each. (USGS)

  14. Massive immuno multiresidue screening of water pollutants.

    PubMed

    Dobosz, Paulina; Morais, Sergi; Bonet, Emilio; Puchades, Rosa; Maquieira, Ángel

    2015-10-01

    An immuno multiresidue screening assay in microarray format for the determination of complex chemical mixtures at the microgram per liter level, using antibody-functionalized gold nanoparticles, is presented. The analytical method relies on the use of a cocktail of nanogold-labeled specific antibodies, acting as recognition and detection species. The concept of multireside screening is proved by developing a multiplex assay on a compact disk support for the determination of 2-(2,4,5-trichlorophenoxy)propionic acid, 3-phenoxybenozic acid, 4-nitrophenol, alachlor, atrazine, azoxystrobin, chlorpyrifos, diazinon, diuron, endosulfan, fenthion, forchlorfenuron, imidacloprid, malathion, pentachlorophenol, pyraclostrobin, sulfasalazine, and triclosan, achieving detection limits of 0.07, 0.24, 10.9, 0.21, 0.14, 0.11, 0.11, 102, 0.36, 1.8, 1.7, 0.06, 0.08, 5.8, 1.0, 0.39, 0.003, and 12 μg/L, respectively. Due to the selectivity of the antibody-functionalized nanoparticles, the developed screening methodology allows the simultaneous determination of mixtures of water pollutants in a 10-plex configuration. The analytical performances were compared with those of reference chromatographic methods by the analysis of spiked water samples, the sensitivity and recovery results being in good agreement. The presented screening approach directly quantifies the concentration of complex chemical mixtures without sample treatment or preconcentration steps in a total time of 35 min. PMID:26390221

  15. Response of sago pondweed, a submerged aquatic macrophyte, to herbicides in three laboratory culture systems

    USGS Publications Warehouse

    Fleming, W.J.; Ailstock, M.S.; Momot, J.J.; Norman, C.M.

    1991-01-01

    The phytotoxicity of atrazine, paraquat, glyphosate, and alachlor to sago pondweed (Potamogeton pectinatus), a submerged aquatic macrophyte, was tested under three types of laboratory culture conditions. In each case, tests were conducted in static systems, the test period was four weeks, and herbicide exposure was chronic, resulting from a single addition of herbicide to the test vessels at the beginning of the test period. The three sets of test conditions employed were(1) axenic cultures in 125-mL flasks containing a nutrient media and sucrose; (2) a microcosm system employing 18.9-L buckets containing a sand, shell, and peat substrate; and (3) an algae-free system employing O.95-L jars containing reconstituted freshwater and a nutrient agar substrate. The primary variable measured was biomass production. Plants grew well in all three test systems, with biomass of untreated plants increasing by a factor of about 5 to 6.5 during the four-week test period. Biomass production in response to herbicide exposure differed significantly among culture systems, which demonstrates the need for a standardized testing protocol for evaluating the effects of toxics on submerged aquatic plants.

  16. Trends in pesticide concentrations and use for major rivers of the United States.

    PubMed

    Ryberg, Karen R; Gilliom, Robert J

    2015-12-15

    Trends in pesticide concentrations in 38 major rivers of the United States were evaluated in relation to use trends for 11 commonly occurring pesticide compounds. Pesticides monitored in water were analyzed for trends in concentration in three overlapping periods, 1992-2001, 1997-2006, and 2001-2010 to facilitate comparisons among sites with variable sample distributions over time and among pesticides with changes in use during different periods and durations. Concentration trends were analyzed using the SEAWAVE-Q model, which incorporates intra-annual variability in concentration and measures of long-term, mid-term, and short-term streamflow variability. Trends in agricultural use within each of the river basins were determined using interval-censored regression with high and low estimates of use. Pesticides strongly dominated by agricultural use (cyanazine, alachlor, atrazine and its degradate deethylatrazine, metolachlor, and carbofuran) had widespread agreement between concentration trends and use trends. Pesticides with substantial use in both agricultural and nonagricultural applications (simazine, chlorpyrifos, malathion, diazinon, and carbaryl) had concentration trends that were mostly explained by a combination of agricultural-use trends, regulatory changes, and urban use changes inferred from concentration trends in urban streams. When there were differences, concentration trends usually were greater than use trends (increased more or decreased less). These differences may occur because of such factors as unaccounted pesticide uses, delayed transport to the river through groundwater, greater uncertainty in the use data, or unquantified land use and management practice changes. PMID:26318227

  17. Liposome-enhanced immunomigration strips for field screening of toxic chemicals

    SciTech Connect

    Roberts, M.A.; Reeves, S.G.; Siebert, S.T.; Durst, R.A. |

    1995-12-31

    The use of liposomes containing encapsulated dye to provide instantaneous enhancement of signals generated in competitive immunoassays is described for two model analytes of environmental concern, alachlor and PCBs. The application of this strategy to field assays is demonstrated utilizing two complementary assay designs based on immunomigration along a nitrocellulose test strip. The liposome immunocompetition (LIC) assay involves immobilizing antibodies onto a strip and allowing the sample and analyte-tagged, dye-containing liposomes to migrate through this zone. Liposomes passing through without binding, as a result of competition from the sample analyte, are totally bound in an upper collection region, and the degree of color in this region is proportional to the analyte concentration. The liposome immunoaggregation (LIA) assay detects antibody-liposome association in a homogeneous incubation solution into which a test strip is subsequently placed. Antibody-bound aggregates of liposomes are trapped on the porous nitrocellulose test strip at the level of the meniscus, due to mechanisms that will be discussed. However, sample analyte competitively inhibits antibody-liposome association and, therefore, a proportional amount of unbound liposomes will escape entrapment on the nitrocellulose and can then be collected and quantitated in a measurement zone. This latter technique shows enhanced sensitivity, but involves an extra incubation step. Therefore these two techniques may be used interchangeably depending on the sensitivity and time requirements of a particular project. Prototype assay designs are demonstrated here and emerging detection strategies are discussed.

  18. Water quality survey of Mississippi's Upper Pearl River.

    PubMed

    Tagert, Mary Love M; Massey, Joseph H; Shaw, David R

    2014-05-15

    Surface water samples were collected from May 2002 through May 2003 at seven locations within the Upper Pearl River Basin (UPRB) in east-central Mississippi to assess levels of pesticide impairment in the watershed. Depth-integrated samples were collected at three sites from September 2001 through January 2003 for total dissolved solid (TDS) analysis. Samples were extracted via Solid Phase Extraction (SPE) and analyzed for fifteen pesticides: triclopyr, 2,4-D, tebuthiuron, simazine, atrazine, metribuzin, alachlor, metolachlor, cyanazine, norflurazon, hexazinone, pendimethalin, diuron, fluometuron, and the dichlorodiphenyltrichloroethane (DDT) degradation product p,p'-DDE. Of the analyzed compounds, hexazinone was detected in 94% of the samples, followed by metolachlor (76%), tebuthiuron (48%), and atrazine (47%). Metribuzin was detected in 6% of the samples and was the least detected compound of those analyzed. Sediment concentrations ranged from 20.64 mg/L at Burnside to 42.20mg/L at Carthage, which also had the highest cumulative total sediment concentration at 4,009 mg/L. PMID:24631619

  19. Analysis of selected herbicide metabolites in surface and ground water of the United States

    USGS Publications Warehouse

    Scribner, E.A.; Thurman, E.M.; Zimmerman, L.R.

    2000-01-01

    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 - triazine, chloroacetanilide and phenyl-urea - have been developed. Methods for triazine metabolite detection cover nine compounds: six compounds are detected by gas chromatography/mass spectrometry; one is detected by high-performance liquid chromatography with diode-array detection; and eight are detected by liquid chromatography/mass spectrometry. Two metabolites of the chloroacetanilide herbicides - ethane sulfonic acid and oxanilic acid - are detected by high-performance liquid chromatography with diode-array detection and liquid chromatography/mass 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 chromatography/mass spectrometry; four of the six metabolites also are detected by gas chromatography/mass 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. Copyright (C) 2000 Elsevier Science B.V.

  20. Aquatic risk assessment of priority and other river basin specific pesticides in surface waters of Mediterranean river basins.

    PubMed

    Silva, Emília; Daam, Michiel A; Cerejeira, Maria José

    2015-09-01

    To meet good chemical and ecological status, Member States are required to monitor priority substances and chemicals identified as substances of concern at European Union and local/river-basin/national level, respectively, in surface water bodies, and to report exceedances of the environmental quality standards (EQSs). Therefore, standards have to be set at national level for river basin specific pollutants. Pesticides used in dominant crops of several agricultural areas within the catchment of Mediterranean river basins ('Mondego', 'Sado' and 'Tejo', Portugal) were selected for monitoring, in addition to the pesticides included in priority lists defined in Europe. From the 29 pesticides and metabolites selected for the study, 20 were detected in surface waters of the river basins, seven of which were priority substances: alachlor, atrazine, chlorfenvinphos, chlorpyrifos, endosulfan, simazine and terbutryn, all of which exceeded their respective EQS values. QSs for other specific pollutants were calculated using different extrapolation techniques (i.e. deterministic or probabilistic) largely based on the method described in view of the Water Framework Directive. Non-acceptable aquatic risks were revealed for molinate, oxadiazon, pendimethalin, propanil, terbuthylazine, and the metabolite desethylatrazine. Implications of these findings for the classification of the ecological status of surface water bodies in Portugal and at the European level are discussed. PMID:26002046

  1. Regression models for estimating herbicide concentrations in U.S. streams from watershed characteristics

    USGS Publications Warehouse

    Larson, S.J.; Gilliom, R.J.

    2001-01-01

    Regression models were developed for estimating stream concentrations of the herbicides alachlor, atrazine, cyanazine, metolachlor, and trifluralin from use-intensity data and watershed characteristics. Concentrations were determined from samples collected from 45 streams throughout the United States during 1993 to 1995 as part of the U.S. Geological Survey's National Water-Quality Assessment (NAWQA). Separate regression models were developed for each of six percentiles (10th, 25th, 50th, 75th, 90th, 95th) of the annual distribution of stream concentrations and for the annual time-weighted mean concentration. Estimates for the individual percentiles can be combined to provide an estimate of the annual distribution of concentrations for a given stream. Agricultural use of the herbicide in the watershed was a significant predictor in nearly all of the models. Several hydrologic and soil parameters also were useful in explaining the variability in concentrations of herbicides among the streams. Most of the regression models developed for estimation of concentration percentiles and annual mean concentrations accounted for 50 percent to 90 percent of the variability among streams. Predicted concentrations were nearly always within an order of magnitude of the measured concentrations for the model-development streams, and predicted concentration distributions reasonably matched the actual distributions in most cases. Results from application of the models to streams not included in the model development data set are encouraging, but further validation of the regression approach described in this paper is needed.

  2. Pesticides, polycyclic aromatic hydrocarbons, and polychlorinated biphenyls in transport in two Atlantic coastal plain tributaries and loadings to Chesapeake Bay

    USGS Publications Warehouse

    Foster, G.D.; Miller, C.V.; Huff, T.B.; Roberts, E., Jr.

    2003-01-01

    Concentrations of current-use pesticides, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and organochlorine (OC) insecticides were determined above the reach of tide in the Chesterville Branch and Nanticoke River on the eastern shore of Chesapeake Bay during base-flow and storm-flow hydrologic regimes to evaluate mass transport to Chesapeake Bay. The two rivers monitored showed relatively high concentrations of atrazine, simazine, alachlor, and metolachlor in comparison to previously investigated western shore tributaries, and reflected the predominant agricultural land use in the eastern shore watersheds. The four current use pesticides showed the greatest seasonal contribution to annual loadings to tidal waters of Chesapeake Bay from the two rivers, and the relative order of annual loadings for the other contaminant classes was PAHs > PCBs > OC insecticides. Annual loadings normalized to the landscape areas of selected Chesapeake Bay watersheds showed correlations to identifiable source areas, with the highest pesticide yields (g/km2/yr) occurring in eastern shore agricultural landscapes, and the highest PAH yields derived from urban regions.

  3. Comparison of Gas Chromatography-Mass Spectrometry and Gas Chromatography-Tandem Mass Spectrometry with Electron Ionization and Negative-Ion Chemical Ionization for Analyses of Pesticides at Trace Levels in Atmospheric Samples

    PubMed Central

    Raina, Renata; Hall, Patricia

    2008-01-01

    A comparison of detection limits of gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring (SIM) with gas chromatography-tandem mass spectrometry (GC-MS/MS) in selected reaction monitoring (SRM) mode with both electron ionization (EI) and negative-ion chemical ionization (NCI) are presented for over 50 pesticides ranging from organochlorines (OCs), organophosphorus pesticides (OPs) and pre-emergent herbicides used in the Canadian prairies (triallate, trifluralin, ethalfluralin). The developed GC-EI/SIM, GC-NCI/SIM, and GC-NCI/SRM are suitable for the determination of pesticides in air sample extracts at concentrations <100 pg μL−1 (<100 pg m−3 in air). No one method could be used to analyze the range of pre-emergent herbicides, OPs, and OCs investigated. In general GC-NCI/SIM provided the lowest method detection limits (MDLs commonly 2.5–10 pg μL−1) along with best confirmation (<25% RSD of ion ratio), while GC-NCI/SRM is recommended for use where added selectivity or confirmation is required (such as parathion-ethyl, tokuthion, carbofenothion). GC-EI/SRM at concentration <100 pg μL−1 was not suitable for most pesticides. GC-EI/SIM was more prone to interference issues than NCI methods, but gave good sensitivity (MDLs 1–10 pg μL−1) for pesticides with poor NCI response (OPs: sulfotep, phorate, aspon, ethion, and OCs: alachlor, aldrin, perthane, and DDE, DDD, DDT). PMID:19609395

  4. Pesticides removal in the process of drinking water production.

    PubMed

    Ormad, M P; Miguel, N; Claver, A; Matesanz, J M; Ovelleiro, J L

    2008-03-01

    The aim of this research work was to study the effectiveness of the treatments commonly used in drinking water plants in Spain to degrade 44 pesticides systematically detected in the Ebro River Basin. The pesticides studied are: alachlor, aldrin, ametryn, atrazine, chlorfenvinfos, chlorpyrifos, pp'-DDD, op'-DDE, op'-DDT, pp'-DDT, desethylatrazine, 3,4-dichloroaniline, 4,4'-dichlorobenzophenone, dicofol, dieldrin, dimethoate, diuron, alpha-endosulphan, endosulphan-sulphate, endrin, alpha-HCH, beta-HCH, gamma-HCH, delta-HCH, heptachlor, heptachlor epoxide A, heptachlor epoxide B, hexachlorobenzene, isodrin, 4-isopropylaniline, isoproturon, metholachlor, methoxychlor, molinate, parathion methyl, parathion ethyl, prometon, prometryn, propazine, simazine, terbuthylazine, terbutryn, tetradifon and trifluralin. The techniques applied are: preoxidation by chlorine or ozone, chemical precipitation with aluminium sulphate and activated carbon adsorption. Oxidation by chlorine removes 60% of the studied pesticides, although combining this technique with a coagulation-flocculation-decantation process is more effective. The disadvantage of this treatment is the formation of trihalomethanes. Oxidation by ozone removes 70% of the studied pesticides. Although combination with a subsequent coagulation-flocculation-decantation process does not improve the efficiency of the process, combination with an activated-carbon absorption process gives rise to 90% removal of the studied pesticides. This technique was found to be the most efficient among the techniques studied for degrading the majority of the studied pesticides. PMID:18023468

  5. Chemical stress sensitive luminescent human cells: Molecular biology approach using inducible Drosophila melanogaster hsp22 promoter

    SciTech Connect

    Mandon, C.A.; Diaz, C.; Arrigo, A.-P.; Blum, L.J. . E-mail: Loic.Blum@univ-lyon1.fr

    2005-09-23

    A whole-cell bioassay has been developed for the total toxicity testing of liquid samples. The method is based on the induction of the bioluminescent activity of genetically manipulated mammalian cells. For that purpose, transfection was used to introduce, in HeLa cells, a DNA sensing element that responds to chemical stress agents (heavy metals, genotoxic agents, and endocrine-disrupting chemicals). Such element was designed to direct the expression of a reporting gene (firefly luciferase) through the activation of Drosophila melanogaster hsp22 promoter. A molecular approach was conducted to optimize hsp22 promoter element in order to decrease the background expression level of the reporting gene and to increase the sensitivity of the bioassay for testing endocrine disruptors. As a result, in the presence of 20-100 {mu}M cadmium chloride, a 6-fold increase in luciferase expression was obtained using a specially designed truncated hsp22 promoter construction. The following chemicals known to be found in the polluted samples were tested: CdCl{sub 2}, Cd(NO{sub 3}){sub 2}, NaAsO{sub 2}, alachlore, fentine acetate, thiram, and maneb. The stressing effect of each of them was sensitively detected by the present bioassay in the 0.05-50 {mu}M concentration range.

  6. Light-sensitized decontamination of ground-water hazardous chemicals. Technical report (Final)

    SciTech Connect

    Larson, R.A.; Schlauch, M.B.; Ellis, D.D.; Marley, K.A.; Ju, H.L.

    1988-01-01

    The use of sunlight, oxygen, and dissolved organic compounds active as 'photosensitizers' (substances capable of absorbing sunlight and transforming it into chemically useful forms) is a promising treatment for contaminated waters. Light is absorbed by the sensitizing substance, raising it to a higher energy excited state. Reaction with the excited state substance converts molecular oxygen to a form much more reactive with dissolved compounds. Riboflavin (Vitamin B2), a naturally occurring compound and a known photosensitizer, was investigated for use in this process. A series of kinetic experiments explored its ability to photodegrade several aromatic compounds, phenols and anilines, that are related to some herbicides (such as carbaryl, 2, 4-D, alachlor, atrazine, and trifluralin) commonly found in polluted waters. It was found that riboflavin when added to solutions of phenols or anilines greatly accelerated the rate of their loss in the presence of light. The sensitized photolysis rates increased in the absence of oxygen, suggesting a mechanism involving direct energy or electron transfer between flavin excited states and acceptor molecules. In addition, it was found that some iron salts were very significant promoters of photodestruction of the triazine herbicide, atrazine.

  7. Propachlor degradation by a soil bacterial community.

    PubMed Central

    Villarreal, D T; Turco, R F; Konopka, A

    1991-01-01

    Soil from a pesticide disposal site was used to enrich for microorganisms that degraded the acylanilide herbicide propachlor (2-chloro-N-isopropylacetanilide). After seven transfers of the enrichment, the culture contained about six strains. The highest yield of microbial biomass occurred if just two of these isolates, strains DAK3 and MAB2, were inoculated into a mineral salts medium containing propachlor. When only strain DAK3 was grown on propachlor, a metabolite (2-chloro-N-isopropylacetamide) was released into the medium. Strain MAB2 could grow on this metabolite. The results of morphological and physiological tests suggest that strains DAK3 and MAB2 most closely resemble species belonging to the genera Moraxella and Xanthobacter, respectively. Strain DAK3 can respire and grow on N-substituted acylanilides containing methyl, ethyl, or isopropyl substitutions, but is incapable of respiration or growth on acetanilide, aniline, or the acylanilide herbicides alachlor and metolachlor. Strain DAK3 appears to use the aromatic C atoms of propachlor for growth, as suggested by the growth yield on propachlor and the induction of catechol 2,3-oxygenase activity in acylanilide-grown cells. PMID:1768085

  8. Propachlor degradation by a soil bacterial community.

    PubMed

    Villarreal, D T; Turco, R F; Konopka, A

    1991-08-01

    Soil from a pesticide disposal site was used to enrich for microorganisms that degraded the acylanilide herbicide propachlor (2-chloro-N-isopropylacetanilide). After seven transfers of the enrichment, the culture contained about six strains. The highest yield of microbial biomass occurred if just two of these isolates, strains DAK3 and MAB2, were inoculated into a mineral salts medium containing propachlor. When only strain DAK3 was grown on propachlor, a metabolite (2-chloro-N-isopropylacetamide) was released into the medium. Strain MAB2 could grow on this metabolite. The results of morphological and physiological tests suggest that strains DAK3 and MAB2 most closely resemble species belonging to the genera Moraxella and Xanthobacter, respectively. Strain DAK3 can respire and grow on N-substituted acylanilides containing methyl, ethyl, or isopropyl substitutions, but is incapable of respiration or growth on acetanilide, aniline, or the acylanilide herbicides alachlor and metolachlor. Strain DAK3 appears to use the aromatic C atoms of propachlor for growth, as suggested by the growth yield on propachlor and the induction of catechol 2,3-oxygenase activity in acylanilide-grown cells. PMID:1768085

  9. Direct surface analysis of pesticides on soil, leaves, grass, and stainless steel by static secondary ion mass spectrometry

    SciTech Connect

    Ingram, J.C.; Groenewold, G.S.; Appelhans, A.D.; Delmore, J.E.; Olson, J.E.; Miller, D.L.

    1997-02-01

    Direct surface analyses by static secondary ion mass spectrometry (SIMS) were performed for the following pesticides adsorbed on dandelion leaves, grass, soil, and stainless steel samples: alachlor, atrazine, captan, carbofuran, chlorpyrifos, chlorosulfuron, chlorthal-dimethyl, cypermethrin, 2,4-D, diuron, glyphosate, malathion, methomyl, methyl arsonic acid, mocap, norflurazon, oxyfluorfen, paraquat, temik, and trifluralin. The purpose of this study was to evaluate static SIMS as a tool for pesticide analysis, principally for use in screening samples for pesticides. The advantage of direct surface analysis compared with conventional pesticide analysis methods is the elimination of sample pretreatment including extraction, which streamlines the analysis substantially; total analysis time for SIMS analysis was ca. 10 min/sample. Detection of 16 of the 20 pesticides on all four substrates was achieved. Of the remaining four pesticides, only one (trifluralin) was not detected on any of the samples. The minimum detectable quantity was determined for paraquat on soil in order to evaluate the efficacy of using SIMS as a screening tool. Paraquat was detected at 3 pg/mm{sup 2} (c.a. 0.005 monolayers). The results of these studies suggest that SIMS is capable of direct surface detection of a range of pesticides, with low volatility, polar pesticides being the most easily detected. 25 refs., 2 figs., 2 tabs.

  10. Concentrations of nutrients, pesticides, and suspended sediment in the karst terrane of the Sinking Creek basin, Kentucky, 2004

    USGS Publications Warehouse

    Crain, Angela S.

    2006-01-01

    Water samples were collected in streams and springs in the karst terrane of the Sinking Creek Basin in 2004 as part of study in cooperation with the Kentucky Department of Agriculture. A total of 48 water samples were collected at 7 sites (4 springs, 2 streams, and 1 karst window) from April through November 2004. The karst terrane of the Sinking Creek Basin (also known as Boiling Spring Basin) encompasses about 125 square miles in Breckinridge County and portions of Meade and Hardin Counties in Kentucky. Fourteen pesticides were detected of the 52 pesticides analyzed in the stream and spring samples. Of the 14 detected pesticides, 12 were herbicides and 2 were insecticides. The most commonly detected pesticides?atrazine, simazine, metolachlor, and acetochlor?were those most heavily used on crops during the study. Atrazine was detected in 100 percent of all samples; simazine, metolachlor, and acetochlor were detected in more than 35 percent of all samples. The pesticide-transformation compound, deethylatrazine, was detected in 98 percent of the samples. Only one nonagricultural herbicide, prometon, was detected in more than 30 percent of the samples. Malathion, the most commonly detected insecticide, was found in 4 percent of the samples, which was followed by carbofuran (2 percent). Most of the pesticides were present in low concentrations; however, atrazine was found in springs exceeding the U.S. Environmental Protection Agency?s (USEPA) standards for drinking water. Atrazine exceeded the USEPA?s maximum contaminant level 2 times in 48 detections. Concentrations of nitrate greater than 10 milligrams per liter (mg/L) were not found in water samples from any of the sites. Concentrations of nitrite plus nitrate ranged from 0.21 to 3.9 mg/L at the seven sites. The median concentration of nitrite plus nitrate for all sites sampled was 1.5 mg/L. Concentrations of nitrite plus nitrate generally were higher in the springs than in the main stem of Sinking Creek. Forty

  11. Pesticide pollution of multiple drinking water sources in the Mekong Delta, Vietnam: evidence from two provinces.

    PubMed

    Chau, N D G; Sebesvari, Z; Amelung, W; Renaud, F G

    2015-06-01

    Pollution of drinking water sources with agrochemicals is often a major threat to human and ecosystem health in some river deltas, where agricultural production must meet the requirements of national food security or export aspirations. This study was performed to survey the use of different drinking water sources and their pollution with pesticides in order to inform on potential exposure sources to pesticides in rural areas of the Mekong River delta, Vietnam. The field work comprised both household surveys and monitoring of 15 frequently used pesticide active ingredients in different water sources used for drinking (surface water, groundwater, water at public pumping stations, surface water chemically treated at household level, harvested rainwater, and bottled water). Our research also considered the surrounding land use systems as well as the cropping seasons. Improper pesticide storage and waste disposal as well as inadequate personal protection during pesticide handling and application were widespread amongst the interviewed households, with little overall risk awareness for human and environmental health. The results show that despite the local differences in the amount and frequency of pesticides applied, pesticide pollution was ubiquitous. Isoprothiolane (max. concentration 8.49 μg L(-1)), fenobucarb (max. 2.32 μg L(-1)), and fipronil (max. 0.41 μg L(-1)) were detected in almost all analyzed water samples (98 % of all surface samples contained isoprothiolane, for instance). Other pesticides quantified comprised butachlor, pretilachlor, propiconazole, hexaconazole, difenoconazole, cypermethrin, fenoxapro-p-ethyl, tebuconazole, trifloxystrobin, azoxystrobin, quinalphos, and thiamethoxam. Among the studied water sources, concentrations were highest in canal waters. Pesticide concentrations varied with cropping season but did not diminish through the year. Even in harvested rainwater or purchased bottled water, up to 12 different pesticides were detected at

  12. Coupling passive sampling and time of flight mass spectrometry for a better estimation of polar pesticide freshwater contamination: Simultaneous target quantification and screening analysis.

    PubMed

    Guibal, Robin; Lissalde, Sophie; Charriau, Adeline; Poulier, Gaëlle; Mazzella, Nicolas; Guibaud, Gilles

    2015-03-27

    The aim of this study was first to develop and validate an analytical method for the quantification of 35 polar pesticides and 9 metabolites by ultra-high-performance-liquid chromatography combined with a high resolution time-of-flight mass spectrometer detector (UHPLC-(Q)-TOF). Various analytical conditions were investigated (eluent composition and mass parameters) to optimize analyte responses. Analytical performance (linearity, limit of quantification, and accuracy) was then evaluated and interference in the extract of a passive sampler exposed in freshwater (POCIS: Polar Organic Chemical Integrative Sampler) was studied. The proposed quantification method was validated for 43 compounds with variation of calibration slopes below 10% in environmental matrix. For the unvalidated compound DIA (atrazine-desisopropyl: an atrazine metabolite), interference increased the error of concentration determination (50%). The limits of quantification obtained by combining POCIS and UHPLC-(Q)-TOF for 43 target compounds were between 0.1 (terbuthylazine) and 10.7 ng/L (acetochlor). Secondly, the method was successfully applied during a 14-day POCIS river exposure, and gave concentration values similar to a more commonly used triple quadrupole detector regarding concentration, but allowed for the detection of more compounds. Additionally with the targeted compound quantification, the (Q)-TOF mass spectrometer was also used for screening non-target compounds (other pesticides and pharmaceuticals) in POCIS extracts. Moreover, the acquisition of full scan MS data allowed the identification of the polyethylene glycol (PEG) compounds which gave unresolvable interference to DIA, and thus questions the ability of DIA to be used as performance reference compound (PRC) to determine sampling rates in situ. This study therefore illustrates the potential, and proposes a pathway, of UHPLC-(Q)-TOF combined with POCIS in situ pre-concentration for both quantitative and screening analyses of

  13. Gene Expression and Microscopic Analysis of Arabidopsis Exposed to Chloroacetanilide Herbicides and Explosive Compounds. A Phytoremediation Approach1

    PubMed Central

    Mezzari, Melissa P.; Walters, Katherine; Jelínkova, Marcela; Shih, Ming-Che; Just, Craig L.; Schnoor, Jerald L.

    2005-01-01

    Understanding the function of detoxifying enzymes in plants toward xenobiotics is of major importance for phytoremediation applications. In this work, Arabidopsis (Arabidopsis thaliana; ecotype Columbia) seedlings were exposed to 0.6 mm acetochlor (AOC), 2 mm metolachlor (MOC), 0.6 mm 2,4,6-trinitrotoluene (TNT), and 0.3 mm hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). In vivo glutathione (GSH) conjugation reactions of AOC, MOC, RDX, and TNT were studied in root cells using a multiphoton microscope. In situ labeling with monochlorobimane, used as a competitive compound for conjugation reactions with GSH, confirmed that AOC and MOC are conjugated in Arabidopsis cells. Reverse transcription-PCR established the expression profile of glutathione S-transferases (GSTs) and nitroreductases enzymes. Genes selected for this study were AtGSTF2, AtGSTU1, AtGSTU24, and two isoforms of 12-oxophytodienoate reductase (OPR1 and OPR2). The five transcripts tested were induced by all treatments, but RDX resulted in low induction. The mRNA level of AtGSTU24 showed substantial increase for all chemicals (23-fold induction for AOC, 18-fold for MOC, 5-fold for RDX, and 40-fold for TNT). It appears that GSTs are also involved in the conjugation reactions with metabolites of TNT, and to a lesser extent with RDX. Results indicate that OPR2 is involved in plant metabolism of TNT (11-fold induction), and in oxidative stress when exposed to AOC (7-fold), MOC (9-fold), and RDX (2-fold). This study comprises gene expression analysis of Arabidopsis exposed to RDX and AOC, which are considered significant environmental contaminants, and demonstrates the importance of microscopy methods for phytoremediation investigations. PMID:15923336

  14. Concentration of Selected Sulfonylurea, Sulfonamide, and Imidazolinone Herbicides, Other Pesticides, and Nutrients in 71 Streams, 5 Reservoir Outflows, and 25 Wells in the Midwestern United States, 1998

    USGS Publications Warehouse

    Battaglin, William A.; Furlong, Edward T.; Burkhardt, Mark R.

    2001-01-01

    Sulfonylurea (SU), sulfonamide (SA), and imidazolinone (IMI) herbicides are recently developed herbicides that function by inhibiting the action of a key plant enzyme, stopping plant growth, and eventually killing the plant. These compounds generally have low mammalian toxicity, but crop and non-crop plants demonstrate a wide range in sensitivity to SUs, SAs, and IMIs, with over a 10,000-fold difference in observed toxicity levels for some compounds. SUs, SAs, and IMIs are applied either pre- or post-emergence to crops commonly at 1/50th or less of the rate of other herbicides. Little is known about their occurrence, fate, or transport in surface water or ground water in the United States. To obtain information on the occurrence of SU, SA, and IMI herbicides in the Midwestern United States, 214 water samples were collected from 76 surface-water and 25 ground-water sites in 1998. These samples were analyzed for 16 SU, SA, and IMI herbicides by using highperformance liquid chromatography/mass spectrometry. Samples also were analyzed for 46 pesticides and pesticide degradation products and 13 herbicides and 10 herbicide degradates. At least 1 of the 16 SUs, SAs, or IMIs was detected at or above the method reporting limit of 0.010 microgram per liter (ug/L) in 83 percent of 133 stream samples. Imazethapyr was detected most frequently (69 percent of samples), followed by flumetsulam (65 percent of samples) and nicosulfuron (53 percent of samples). At least one SU, SA, or IMI herbicide was detected at or above the method reporting limit in 6 of 8 reservoir samples and 5 of 25 ground-water samples. SU, SA, and IMI herbicides occurred less frequently and at a fraction (often 1/50th or less) of the concentrations of other herbicides such as atrazine. Acetochlor, atrazine, cyanazine, and metolachlor were all detected in 95 percent or more of 136 stream samples.

  15. Influence of the organic complex concentration on adsorption of herbicide in organic modified montmorillonite

    NASA Astrophysics Data System (ADS)

    Kaludjerovic, Lazar; Tomic, Zorica; Djurovic, Rada; Milosevic, Maja

    2016-04-01

    Pesticides are recognized as an important source of potential pollution to soil and water due to their mobility and degradation in soils. Results presented in this paper show impact of the organic complex concentration on the adsorption of herbicides (acetochlor) at the surface of the organic modified montmorillonite. In this work, natural montmorillonite from Bogovina, located near Boljevac municipality, was used for organic modification. Cation-exchange capacity of this montmorillonite was determined by extraction with ammonium acetate (86 mmol/100g of clay). Montmorillonite have been modified first with NaCl and than with two organic complexes, hexadecyltrimethylammonium bromide (HDTMA) and phenyltrimethylammonium chloride (PTMA). For both organic complexes, three saturation concentrations were selected for monitoring of the herbicide adsorption (43 mmol/100g of clay (0.5 CEC), 86 mmol/100g of clay (1 CEC) and 129 mmol/100g of clay (1.5 CEC)). Changes in the properties of the inorganic and organic bentonite have been examined using the X-ray powder diffraction (XRPD) and batch equilibrium method. Increase in basal spacing (d) of montmorillonites saturated with 1.5 CEC of organic cation indicate that sorption of PTMA and HDTMA can exceed the saturation of 1 CEC. Both organic montmorillonites have shown higher uptake of the herbicide, compared to the inorganic montmorillonite. Comparing the values Freundlich coefficients in batch equilibrium method, (presented in the form of log Kf and 1/n), it can be seen that the sorption decreases in the series: 0.5CEC> 1CEC> 1.5CEC> NaM, for both organic montmorillonites.

  16. Effects of Pesticide Mixtures on Host-Pathogen Dynamics of the Amphibian Chytrid Fungus

    PubMed Central

    Buck, Julia C.; Hua, Jessica; Brogan, William R.; Dang, Trang D.; Urbina, Jenny; Bendis, Randall J.; Stoler, Aaron B.; Blaustein, Andrew R.; Relyea, Rick A.

    2015-01-01

    Anthropogenic and natural stressors often interact to affect organisms. Amphibian populations are undergoing unprecedented declines and extinctions with pesticides and emerging infectious diseases implicated as causal factors. Although these factors often co-occur, their effects on amphibians are usually examined in isolation. We hypothesized that exposure of larval and metamorphic amphibians to ecologically relevant concentrations of pesticide mixtures would increase their post-metamorphic susceptibility to the fungus Batrachochytrium dendrobatidis (Bd), a pathogen that has contributed to amphibian population declines worldwide. We exposed five anuran species (Pacific treefrog, Pseudacris regilla; spring peeper, Pseudacris crucifer; Cascades frog, Rana cascadae; northern leopard frog, Lithobates pipiens; and western toad, Anaxyrus boreas) from three families to mixtures of four common insecticides (chlorpyrifos, carbaryl, permethrin, and endosulfan) or herbicides (glyphosate, acetochlor, atrazine, and 2,4-D) or a control treatment, either as tadpoles or as newly metamorphic individuals (metamorphs). Subsequently, we exposed animals to Bd or a control inoculate after metamorphosis and compared survival and Bd load. Bd exposure significantly increased mortality in Pacific treefrogs, spring peepers, and western toads, but not in Cascades frogs or northern leopard frogs. However, the effects of pesticide exposure on mortality were negligible, regardless of the timing of exposure. Bd load varied considerably across species; Pacific treefrogs, spring peepers, and western toads had the highest loads, whereas Cascades frogs and northern leopard frogs had the lowest loads. The influence of pesticide exposure on Bd load depended on the amphibian species, timing of pesticide exposure, and the particular pesticide treatment. Our results suggest that exposure to realistic pesticide concentrations has minimal effects on Bd-induced mortality, but can alter Bd load. This result

  17. A rapid, physiologic protocol for testing transcriptional effects of thyroid-disrupting agents in premetamorphic Xenopus tadpoles.

    PubMed

    Turque, Nathalie; Palmier, Karima; Le Mével, Sébastien; Alliot, Caroline; Demeneix, Barbara A

    2005-11-01

    Increasing numbers of substances present in the environment are postulated to have endocrine-disrupting effects on vertebrate populations. However, data on disruption of thyroid signaling are fragmentary, particularly at the molecular level. Thyroid hormone (TH; triiodothyronine, T3) acts principally by modulating transcription from target genes; thus, thyroid signaling is particularly amenable to analysis with a transcriptional assay. Also, T3 orchestrates amphibian metamorphosis, thereby providing an exceptional model for identifying thyroid-disrupting chemicals. We combined these two advantages to develop a method for following and quantifying the transcriptional action of T3 in Xenopus laevis tadpoles. This technology provides a means of assessing thyroid activity at the molecular level in a physiologically relevant situation. Moreover, translucent tadpoles are amenable to "on-line" imaging with fluorescent reporter constructs that facilitate in vivo measurement of transcriptional activity. We adapted transgenesis with TH-responsive elements coupled to either luciferase or green fluorescent protein to follow T3-dependent transcription in vivo. To reduce time of exposure and to synchronize responses, we optimized a physiologic pretreatment protocol that induced competence to respond to T3 and thus to assess T3 effects and T3 disruption within 48 hr. This pretreatment protocol was based on a short (24 hr), weak (10(-12) M) pulse of T3 that induced TH receptors, facilitating and synchronizing the transcriptional responses. This protocol was successfully applied to somatic and germinal transgenesis with both reporter systems. Finally, we show that the transcriptional assay allows detection of the thyroid-disrupting activity of environmentally relevant concentrations (10(-8) M) of acetochlor, a persistent herbicide. PMID:16263516

  18. Assessment of heavy metal and pesticide levels in soil and plant products from agricultural area of Belgrade, Serbia.

    PubMed

    Marković, Mirjana; Cupać, Svjetlana; Durović, Rada; Milinović, Jelena; Kljajić, Petar

    2010-02-01

    This study was aimed to assess the levels of selected heavy metals and pesticides in soil and plant products from an agricultural area of Belgrade, Serbia and to indicate possible sources and risks of contamination. Soil, vegetable, and fruit samples from the most important agricultural city areas were collected from July to November of 2006. Metal contents were determined by atomic absorption spectrometry, whereas pesticide residues were analyzed by gas chromatography-mass spectrometry after extraction performed using solid-phase microextraction technique. Soil characterization based on the determination of selected physical and chemical properties revealed heterogeneous soils belonging to different soil groups. The concentrations of lead, cadmium, copper, and zinc in soil samples do not exceed the limits established by national and international regulations. Residues of the herbicide atrazine were detected in three soil samples, with levels lower than the relevant limit. The presence of other herbicides, namely prometryn, chloridazon, acetochlor, flurochloridone, and napropamide, was registered in some soil samples as well. Among the insecticides investigated in the soil, fenitrothion and chlorpyrifos were the only ones detected. In most of the investigated vegetable samples from the Obrenovac area, Pb and Cd contents are higher in comparison with the maximum levels, indicating the emission of coal combustion products from local thermal power plants as a possible source of contamination. Residue levels of some herbicides and insecticides (metribuzin, trifluralin, pendimethalin, bifenthrin, chlorpyrifos, and cypermethrin) determined in tomato, pepper, potato, and onion samples from Slanci, Ovca, and Obrenovac areas are even several times higher than the maximum residue levels. Inappropriate use of these plant protection products is considered to be the most probable reason of contamination. Because increased levels of heavy metals and pesticide residues found in

  19. Herbicides and herbicide degradates in shallow groundwater and the Cedar River near a municipal well field, Cedar Rapids, Iowa

    USGS Publications Warehouse

    Boyd, R.A.

    2000-01-01

    Water samples were collected near a Cedar Rapids, Iowa municipal well field from June 1998 to August 1998 and analyzed for selected triazine and acetanilide herbicides and degradates. The purpose of the study was to evaluate the occurrence of herbicides and herbicide degradates in the well field during a period following springtime application of herbicides to upstream cropland. The well field is in an alluvial aquifer adjacent to the Cedar River. Parent herbicide concentrations generally were greatest in June, and decreased in July and August. Atrazine was most frequently detected and occurred at the greatest concentrations; acetochlor, cyanazine and metolachlor also were detected, but at lesser concentrations than atrazine. Triazine degradate concentrations were relatively small (<0.50 ??g/l) and generally decreased from June to August. Although the rate of groundwater movement is relatively fast (approx. 1 m per day) in the alluvial aquifer near the Cedar River, deethylatrazine (DEA) to atrazine ratios in groundwater samples collected near the Cedar River indicate that atrazine and DEA probably are gradually transported into the alluvial aquifer from the Cedar River. Deisopropylatrazine (DIA) to DEA ratios in water samples indicate most DIA in the Cedar River and alluvial aquifer is produced by atrazine degradation, although some could be from cyanazine degradation. Acetanilide degradates were detected more frequently and at greater concentrations than their corresponding parent herbicides. Ethanesulfonic-acid (ESA) degradates comprised at least 80% of the total acetanilide-degradate concentrations in samples collected from the Cedar River and alluvial aquifer in June, July and August; oxanilic acid degradates comprised less than 20% of the total concentrations. ESA-degradate concentrations generally were smallest in June and greater in July and August. Acetanilide degradate concentrations in groundwater adjacent to the Cedar River indicate acetanilide

  20. Metabolic pathway involved in 2-methyl-6-ethylaniline degradation by Sphingobium sp. strain MEA3-1 and cloning of the novel flavin-dependent monooxygenase system meaBA.

    PubMed

    Dong, Weiliang; Chen, Qiongzhen; Hou, Ying; Li, Shuhuan; Zhuang, Kai; Huang, Fei; Zhou, Jie; Li, Zhoukun; Wang, Jue; Fu, Lei; Zhang, Zhengguang; Huang, Yan; Wang, Fei; Cui, Zhongli

    2015-12-01

    2-Methyl-6-ethylaniline (MEA) is the main microbial degradation intermediate of the chloroacetanilide herbicides acetochlor and metolachlor. Sphingobium sp. strain MEA3-1 can utilize MEA and various alkyl-substituted aniline and phenol compounds as sole carbon and energy sources for growth. We isolated the mutant strain MEA3-1Mut, which converts MEA only to 2-methyl-6-ethyl-hydroquinone (MEHQ) and 2-methyl-6-ethyl-benzoquinone (MEBQ). MEA may be oxidized by the P450 monooxygenase system to 4-hydroxy-2-methyl-6-ethylaniline (4-OH-MEA), which can be hydrolytically spontaneously deaminated to MEBQ or MEHQ. The MEA microbial metabolic pathway was reconstituted based on the substrate spectra and identification of the intermediate metabolites in both the wild-type and mutant strains. Plasmidome sequencing indicated that both strains harbored 7 plasmids with sizes ranging from 6,108 bp to 287,745 bp. Among the 7 plasmids, 6 were identical, and pMEA02' in strain MEA3-1Mut lost a 37,000-bp fragment compared to pMEA02 in strain MEA3-1. Two-dimensional electrophoresis (2-DE) and protein mass fingerprinting (PMF) showed that MEA3-1Mut lost the two-component flavin-dependent monooxygenase (TC-FDM) MeaBA, which was encoded by a gene in the lost fragment of pMEA02. MeaA shared 22% to 25% amino acid sequence identity with oxygenase components of some TC-FDMs, whereas MeaB showed no sequence identity with the reductase components of those TC-FDMs. Complementation with meaBA in MEA3-1Mut and heterologous expression in Pseudomonas putida strain KT2440 resulted in the production of an active MEHQ monooxygenase. PMID:26386060

  1. Exposure to Atrazine and Selected Non-Persistent Pesticides among Corn Farmers during a Growing Season

    PubMed Central

    Bakke, Berit; De Roos, Anneclaire J.; Barr, Dana B.; Stewart, Patricia A.; Blair, Aaron; Freeman, Laura Beane; Lynch, Charles F.; Allen, Ruth H.; Alavanja, Michael C.R.; Vermeulen, Roel

    2011-01-01

    Objectives The aim was to develop quantitative estimates of farmers’ pesticide exposure to atrazine and to provide an overview of background levels of selected non-persistent pesticides among corn farmers in a longitudinal molecular epidemiologic study. Methods The study population consisted of 30 Agricultural Health Study farmers from Iowa and 10 nonfarming controls. Farmers completed daily and weekly diaries from March to November in 2002 and 2003 on pesticide use and other exposure determinants. Urine samples were collected at 10 timepoints relative to atrazine application and other farming activities. Pesticide exposure was assessed using urinary metabolites and diaries. Results The analytical limit of detection (LOD) ranged between 0.1–0.2 μg/l for all pesticide analytes except for isazaphos (1.5 μg/l) and diazinon (0.7 μg/l). Farmers had higher geometric mean urinary atrazine mercapturate (AZM) values than controls during planting (1.1 vs. acetochlor (92% vs. 47%, p<0.0001 and 45% vs. 4%, p<0.0001, respectively). Conclusion Urinary AZM levels in farmers were largely driven by recent application of atrazine. Therefore, the amount of atrazine applied is likely to provide valid surrogates of atrazine exposure in epidemiologic studies. Elevated background levels of non-persistent pesticides, especially 2,4-D, indicate importance in epidemiologic studies of capturing pesticide exposures that might not be directly related to the actual application. PMID:19052531

  2. Effect of herbicide combinations on Bt-maize rhizobacterial diversity.

    PubMed

    Valverde, José R; Marín, Silvia; Mellado, Rafael P

    2014-11-28

    Reports of herbicide resistance events are proliferating worldwide, leading to new cultivation strategies using combinations of pre-emergence and post-emergence herbicides. We analyzed the impact during a one-year cultivation cycle of several herbicide combinations on the rhizobacterial community of glyphosate-tolerant Bt-maize and compared them to those of the untreated or glyphosate-treated soils. Samples were analyzed using pyrosequencing of the V6 hypervariable region of the 16S rRNA gene. The sequences obtained were subjected to taxonomic, taxonomy-independent, and phylogeny-based diversity studies, followed by a statistical analysis using principal components analysis and hierarchical clustering with jackknife statistical validation. The resilience of the microbial communities was analyzed by comparing their relative composition at the end of the cultivation cycle. The bacterial communites from soil subjected to a combined treatment with mesotrione plus s-metolachlor followed by glyphosate were not statistically different from those treated with glyphosate or the untreated ones. The use of acetochlor plus terbuthylazine followed by glyphosate, and the use of aclonifen plus isoxaflutole followed by mesotrione clearly affected the resilience of their corresponding bacterial communities. The treatment with pethoxamid followed by glyphosate resulted in an intermediate effect. The use of glyphosate alone seems to be the less aggressive one for bacterial communities. Should a combined treatment be needed, the combination of mesotrione and s-metolachlor shows the next best final resilience. Our results show the relevance of comparative rhizobacterial community studies when novel combined herbicide treatments are deemed necessary to control weed growth.. PMID:25394507

  3. Metabolic Pathway Involved in 2-Methyl-6-Ethylaniline Degradation by Sphingobium sp. Strain MEA3-1 and Cloning of the Novel Flavin-Dependent Monooxygenase System meaBA

    PubMed Central

    Dong, Weiliang; Chen, Qiongzhen; Hou, Ying; Li, Shuhuan; Zhuang, Kai; Huang, Fei; Zhou, Jie; Li, Zhoukun; Wang, Jue; Fu, Lei; Zhang, Zhengguang; Huang, Yan; Wang, Fei

    2015-01-01

    2-Methyl-6-ethylaniline (MEA) is the main microbial degradation intermediate of the chloroacetanilide herbicides acetochlor and metolachlor. Sphingobium sp. strain MEA3-1 can utilize MEA and various alkyl-substituted aniline and phenol compounds as sole carbon and energy sources for growth. We isolated the mutant strain MEA3-1Mut, which converts MEA only to 2-methyl-6-ethyl-hydroquinone (MEHQ) and 2-methyl-6-ethyl-benzoquinone (MEBQ). MEA may be oxidized by the P450 monooxygenase system to 4-hydroxy-2-methyl-6-ethylaniline (4-OH-MEA), which can be hydrolytically spontaneously deaminated to MEBQ or MEHQ. The MEA microbial metabolic pathway was reconstituted based on the substrate spectra and identification of the intermediate metabolites in both the wild-type and mutant strains. Plasmidome sequencing indicated that both strains harbored 7 plasmids with sizes ranging from 6,108 bp to 287,745 bp. Among the 7 plasmids, 6 were identical, and pMEA02′ in strain MEA3-1Mut lost a 37,000-bp fragment compared to pMEA02 in strain MEA3-1. Two-dimensional electrophoresis (2-DE) and protein mass fingerprinting (PMF) showed that MEA3-1Mut lost the two-component flavin-dependent monooxygenase (TC-FDM) MeaBA, which was encoded by a gene in the lost fragment of pMEA02. MeaA shared 22% to 25% amino acid sequence identity with oxygenase components of some TC-FDMs, whereas MeaB showed no sequence identity with the reductase components of those TC-FDMs. Complementation with meaBA in MEA3-1Mut and heterologous expression in Pseudomonas putida strain KT2440 resulted in the production of an active MEHQ monooxygenase. PMID:26386060

  4. A cocktail of contaminants: how mixtures of pesticides at low concentrations affect aquatic communities.

    PubMed

    Relyea, Rick A

    2009-03-01

    The ubiquity of anthropogenic chemicals in nature poses a challenge to understanding how ecological communities are impacted by them. While we are rapidly gaining an understanding of how individual contaminants affect communities, communities are exposed to suites of contaminants yet investigations of the effects of diverse contaminant mixtures in aquatic communities are rare. I examined how a single application of five insecticides (malathion, carbaryl, chlorpyrifos, diazinon, and endosulfan) and five herbicides (glyphosate, atrazine, acetochlor, metolachlor, and 2,4-D) at low concentrations (2-16 p.p.b.) affected aquatic communities composed of zooplankton, phytoplankton, periphyton, and larval amphibians (gray tree frogs, Hyla versicolor, and leopard frogs, Rana pipiens). Using outdoor mesocosms, I examined each pesticide alone, a mix of insecticides, a mix of herbicides, and a mix of all ten pesticides. Individual pesticides had a wide range of direct and indirect effects on all trophic groups. For some taxa (i.e., zooplankton and algae), the impact of pesticide mixtures could largely be predicted from the impacts of individual pesticides; for other taxa (i.e., amphibians) it could not. For amphibians, there was an apparent direct toxic effect of endosulfan that caused 84% mortality of leopard frogs and an indirect effect induced by diazinon that caused 24% mortality of leopard frogs. When pesticides were combined, the mix of herbicides had no negative effects on the survival and metamorphosis of amphibians, but the mix of insecticides and the mix of all ten pesticides eliminated 99% of leopard frogs. Interestingly, these mixtures did not cause mortality in the gray tree frogs and, as a result, the gray tree frogs grew nearly twice as large due to reduced competition with leopard frogs. In short, wetland communities can be dramatically impacted by low concentrations of pesticides (both separate and combined) and these results offer important insights for the

  5. Pesticides in surface water of the Mid-Atlantic region

    USGS Publications Warehouse

    Ferrari, Matthew J.; Ator, Scott W.; Blomquist, Joel D.; Dysart, Joel E.

    1997-01-01

    Water-quality data from 463 surface-water sites were compiled and analyzed to document the occurrence and distribution of pesticides in surface water of the Mid-Atlantic region as part of the Mid-Atlantic Integrated Assessment program of the U.S. Environmental Protection Agency. Those data collected by the U.S. Geological Survey from October 1973 through March 1997 were used in the analyses. Data are available for a large part of the Mid-Atlantic region, but large spatial gaps in the data do exist. USGS data bases contained analyses of surface-water samples for 127 pesticide compounds, including 12 degradates, but only 16 of the compounds were commonly detected. Atrazine, metolachlor, simazine, prometon, alachlor, tebuthiuron, cyanazine, diazinon, carbaryl, chlorpyrifos, pendimethalin, 2,4-D, dieldrin, DCPA, metribuzin, and desethylatrazine (an atrazine degradate) were detected in more than 100 of the samples analyzed. At least one pesticide was detected in about 75 percent of the samples collected and at more than 90 percent of the sites sampled. Concentrations greater than the Federal Maximum Contaminant Level (MCL) for drinking water of 3 micrograms per liter (ug/L) for atrazine were found in 67 of 2,076 samples analyzed; concentrations greater than the MCL of 2ug/L for alachlor were found in 13 of 1,693 samples analyzed, and concentrations greater than the MCL of 4 ug/L for simazine were found in 17 of 1,995 samples analyzed. Concentrations of four pesticides were greater than Federal Health Advisory levels for drinking water, and concentrations of nine pesticides were greater than Federal Ambient Water-Quality Criteria for the Protection of Aquatic Organisms. Streams draining basins with different land uses tend to have different pesticide detection frequencies and median concentrations. Median concentrations of herbicides tend to be highest in streams draining basins in which the major land use is agriculture, whereas median concentrations of insecticides

  6. Quality-assurance design applied to an assessment of agricultural pesticides in ground water from carbonate bedrock aquifers in the Great Valley of eastern Pennsylvania

    USGS Publications Warehouse

    Breen, Kevin J.

    2000-01-01

    Assessments to determine whether agricultural pesticides are present in ground water are performed by the Commonwealth of Pennsylvania under the aquifer monitoring provisions of the State Pesticides and Ground Water Strategy. Pennsylvania?s Department of Agriculture conducts the monitoring and collects samples; the Department of Environmental Protection (PaDEP) Laboratory analyzes the samples to measure pesticide concentration. To evaluate the quality of the measurements of pesticide concentration for a groundwater assessment, a quality-assurance design was developed and applied to a selected assessment area in Pennsylvania. This report describes the quality-assurance design, describes how and where the design was applied, describes procedures used to collect and analyze samples and to evaluate the results, and summarizes the quality assurance results along with the assessment results. The design was applied in an agricultural area of the Delaware River Basin in Berks, Lebanon, Lehigh, and Northampton Counties to evaluate the bias and variability in laboratory results for pesticides. The design?with random spatial and temporal components?included four data-quality objectives for bias and variability. The spatial design was primary and represented an area comprising 30 sampling cells. A quality-assurance sampling frequency of 20 percent of cells was selected to ensure a sample number of five or more for analysis. Quality-control samples included blanks, spikes, and replicates of laboratory water and spikes, replicates, and 2-lab splits of groundwater. Two analytical laboratories, the PaDEP Laboratory and a U.S. Geological Survey Laboratory, were part of the design. Bias and variability were evaluated by use of data collected from October 1997 through January 1998 for alachlor, atrazine, cyanazine, metolachlor, simazine, pendimethalin, metribuzin, and chlorpyrifos. Results of analyses of field blanks indicate that collection, processing, transport, and laboratory

  7. Contributing recharge areas, groundwater travel time, and groundwater water quality of the Missouri River alluvial aquifer near the City of Independence, Missouri, well field, 1997-2008

    USGS Publications Warehouse

    Kelly, Brian P.

    2011-01-01

    recharge area (CRA) of the Independence well field. Statistical summaries and the spatial and temporal variability of water quality in the Missouri River alluvial aquifer near the Independence well field were characterized from analyses of 598 water samples. Water-quality constituent groups include dissolved oxygen and physical properties, nutrients, major ions and trace elements, wastewater indicator compounds, fuel compounds, and total benzene, toluene, ethylbenzene, and xylene (BTEX), alachlor, and atrazine. The Missouri Secondary Maximum Contaminant Level (SMCL) for iron was exceeded in almost all monitoring wells. The Missouri Maximum Contaminant Level (MCL) for arsenic was exceeded 32 times in samples from monitoring wells. The MCL for barium was exceeded five times in samples from one monitoring well. The SMCL for manganese was exceeded 160 times in samples from all monitoring wells and the combined well-field sample. The most frequently detected wastewater indicator compounds were N,N-diethyl-meta-toluamide (DEET), phenol, caffeine, and metolachlor. The most frequently detected fuel compounds were toluene and benzene. Alachlor was detected in 22 samples and atrazine was detected in 37 samples and the combined well-field sample. The MCL for atrazine was exceeded in one sample from one monitoring well. Samples from monitoring wells with median concentrations of total inorganic nitrogen larger than 1 milligram per liter (mg/L) are located near agricultural land and may indicate that agricultural land practices are the source of nitrogen to groundwater. Largest median values of specific conductance; total inorganic nitrogen; dissolved calcium, magnesium, sodium, iron, arsenic, manganese, bicarbonate, and sulfate and detections of wastewater indicator compounds generally were in water samples from monitoring wells with CRAs that intersect the south bank of the Missouri River. Zones of higher specific conductance were located just upstream from the Independen

  8. Ground-water monitoring plan, water quality, and variability of agricultural chemicals in the Missouri River alluvial aquifer near the City of Independence, Missouri, well field, 1998-2000

    USGS Publications Warehouse

    Kelly, Brian P.

    2002-01-01

    wells. The highest total BTEX concentration was less than the MCL of toluene, ethyl benzene, or xylene but greater than the MCL for benzene. Total BTEX was not detected in samples from any well more than once. Atrazine was detected in samples from nine wells, and exceeded the MCL once in a sample from one well. Alachlor was detected in samples from 22 wells but the MCL was never exceeded in any sample. Samples from five wells analyzed for a large number of organic compounds indicate concentrations of volatile organic compounds did not exceed the MCL for drinking water. No semi-volatile organic compounds were detected; dieldrin was detected in one well sample, and no other pesticides, herbicides, polychlorinated biphenyls, or polychlorinated napthalenes were detected. Dissolved ammonia, dissolved nitrite plus nitrate, dissolved orthophosphorus, alachlor, and atrazine analyses were used to determine the spatial and temporal variability of agricultural chemicals in ground water. Detection frequencies for dissolved ammonia increased with well depth, decreased with depth for dissolved nitrite plus nitrate, and remained relatively constant with depth for dissolved orthophosphorus. Maximum concentrations of dissolved ammonia, dissolved nitrite plus nitrate, and dissolved orthophosphorus were largest in the shallowest wells and decreased with depth, which may indicate the land surface as the source. However, median concentrations increased with depth for dissolved ammonia, were less than the detection limit for dissolved nitrite plus nitrate, and decreased with depth for dissolved orthophosphorus. This pattern does not indicate a well-defined single source for these constituents. Dissolved orthophosphorus median concentrations were similar, but decreased slightly with depth, and may indicate the land surface as the source. Seasonal variability of dissolved ammonia, dissolved nitrite plus nitrate, a

  9. Vertical gradients in water chemistry in the central High Plains aquifer, southwestern Kansas and Oklahoma panhandle, 1999

    USGS Publications Warehouse

    McMahon, Peter B.

    2001-01-01

    in sediments of Permian age by ground water was the likely source of calcium, sulfate, sodium, and chloride in those waters. Calcium-sodium-sulfate waters dominated, and concentrations of dissolved solids were as large as 4,916 mg/L near the water table in the area of downward leakage. Dissolution of minerals in sedimentary deposits of marine origin in upstream areas of the Arkansas River drainage were the likely sources of calcium, sodium, and sulfate in those waters. Nitrate was detected throughout the aquifer and the background concentration was estimated to be 2.45 mg/L as N. The largest nitrate concentrations (8.28, 22, and 54.4 mg/L as N) occurred in recently recharged water collected adjacent to irrigated fields. Three pesticides (atrazine, metolachlor, simazine) and five pesticide degradation products (alachlor ethanesulfonic acid, alachlor oxanilic acid, deethylatrazine, metolachlor ethanesulfonic acid, metolachlor oxanilic acid) were detected in recently recharged water from six water-table wells. Five of the six wells were adjacent to irrigated fields. These data indicate that concentrations of nitrate and pesticides increased over time in some areas of the aquifer as a result of agricultural activities. Results from this study indicate that vertical gradients in water chemistry existed in the central High Plains aquifer. The chemical gradients resulted from chemical inputs to the aquifer from underlying sediments of Permian age, from the Arkansas River, and from agricultural activities. In areas where those chemical inputs occurred, water quality in the aquifer was impaired and may not have been suitable for some intended uses.

  10. Modelling pesticide volatilization after soil application using the mechanistic model Volt'Air

    NASA Astrophysics Data System (ADS)

    Bedos, Carole; Génermont, Sophie; Le Cadre, Edith; Garcia, Lucas; Barriuso, Enrique; Cellier, Pierre

    Volatilization of pesticides participates in atmospheric contamination and affects environmental ecosystems including human welfare. Modelling at relevant time and spatial scales is needed to better understand the complex processes involved in pesticide volatilization. Volt'Air-Pesticides has been developed following a two-step procedure to study pesticide volatilization at the field scale and at a quarter time step. Firstly, Volt'Air-NH 3 was adapted by extending the initial transfer of solutes to pesticides and by adding specific calculations for physico-chemical equilibriums as well as for the degradation of pesticides in soil. Secondly, the model was evaluated in terms of 3 pesticides applied on bare soil (atrazine, alachlor, and trifluralin) which display a wide range of volatilization rates. A sensitivity analysis confirmed the relevance of tuning to K h. Then, using Volt'Air-Pesticides, environmental conditions and emission fluxes of the pesticides were compared to fluxes measured under 2 environmental conditions. The model fairly well described water temporal dynamics, soil surface temperature, and energy budget. Overall, Volt'Air-Pesticides estimates of the order of magnitude of the volatilization flux of all three compounds were in good agreement with the field measurements. The model also satisfactorily simulated the decrease in the volatilization rate of the three pesticides during night-time as well as the decrease in the soil surface residue of trifluralin before and after incorporation. However, the timing of the maximum flux rate during the day was not correctly described, thought to be linked to an increased adsorption under dry soil conditions. Thanks to Volt'Air's capacity to deal with pedo-climatic conditions, several existing parameterizations describing adsorption as a function of soil water content could be tested. However, this point requires further investigation. Practically speaking, Volt'Air-Pesticides can be a useful tool to make

  11. Herbicide and nitrate distribution in central Iowa rainfall

    SciTech Connect

    Hatfield, J.L.; Prueger, J.H.; Pfeiffer, R.L.; Wesley, C.K.

    1996-03-01

    Herbicides are detected in rainfall; however, these are a small fraction of the total applied. This study was designed to evaluate monthly and annual variation in atrazine (6-chloro-N-ethyl-N{prime}-(1-methylethyl)-1,3,5-triazine-2,4-diamine), alachlor (2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)acetamide), metolachlor (2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide), and NO{sub 3}-N concentrations in rainfall over Walnut Creek watershed south of Ames, IA. The study began in 1991 and continued through 1994. Within the watershed, two wet/dry precipitation samplers were positioned 4 km apart. Detections varied during the year with >90% of the herbicide detections occurring in April through early July. Concentrations varied among events from nondetectable amounts to concentrations of 154 {mu}g L{sup {minus}1}, which occurred when atrazine was applied during an extremely humid day immediately followed by rainfall of <10 mm that washed spray drift from the atmosphere. This was a local scale phenomenon, because the other collector had a more typical concentration of 1.7 {mu}g L{sup {minus}1} with an 8-mm rainfall. VAriation between the two collectors suggests that local scale meteorological processes affect herbicide movement. Yearly atrazine deposition totals were >100 {mu}g m{sup {minus}2} representing <0.1% of the amount applied. Nitrate-N concentrations in precipitation were uniformly distributed throughout the year and without annual variation in the concentrations. Deposition rates of NO{sub 3}-N were about 1.2 g m{sup {minus}2}. Annual loading onto the watershed was about 25% of the amount applied from all forms of N fertilizers. Movement and rates of deposition provide an understanding of the processes and magnitude of the impact of agriculture on the environment. 7 refs., 5 figs., 3 tabs.

  12. Effects of low-dose exposure to pesticide mixture on physiological responses of the Pacific oyster, Crassostrea gigas.

    PubMed

    Geret, F; Burgeot, T; Haure, J; Gagnaire, B; Renault, T; Communal, P Y; Samain, J F

    2013-12-01

    This study investigated the effects on the physiology of Pacific oyster, Crassostrea gigas, of a mixture of pesticides containing 0.8 μg L(-1) alachlor, 0.6 μg L(-1) metolachlor, 0.7 μg L(-1) atrazine, 0.6 μg L(-1) terbuthylazine, 0.5 μg L(-1) diuron, 0.6 μg L(-1) fosetyl aluminum, 0.05 μg L(-1) carbaryl, and 0.7 μg L(-1) glyphosate for a total concentration of 4.55 μg L(-1) . The total nominal concentration of pesticides mixture corresponds to the pesticide concentrations in the shellfish culture area of the Marennes-Oleron basin. Two varieties of C. gigas were selected on the foreshore, based on their characteristics in terms of resistance to summer mortality, to assess the effects of the pesticide mixture after 7 days of exposure under controlled conditions. The early effects of the mixture were assessed using enzyme biomarkers of nitrogen metabolism (GS, glutamine synthetase), detoxification metabolism (GST, glutathione S-transferase), and oxidative stress (CAT, catalase). Sublethal effects on hemocyte parameters (phagocytosis and esterase activity) and DNA damages (DNA adducts) were also measured. Changes in metabolic activities were characterized by increases in GS, GST, and CAT levels on the first day of exposure for the "resistant" oysters and after 3-7 days of exposure for the "susceptible" oysters. The formation of DNA adducts was detected after 7 days of exposure. The percentage of hemocyte esterase-positive cells was reduced in the resistant oysters, as was the hemocyte phagocytic capacity in both oyster varieties after 7 days of exposure to the pesticide mixture. This study highlights the need to consider the low doses and the mixture of pesticides to evaluate the effects of these molecules on organisms. PMID:22012874

  13. Determination of enzyme kinetics and glutathione conjugates of chlortetracycline and chloroacetanilides using liquid chromatography-mass spectrometry.

    PubMed

    Farkas, Michael; Berry, James O; Aga, Diana S

    2007-07-01

    Glutathione S-transferases (GSTs) isolated from chlortetracycline (CTC)-treated maize catalyzed the conjugation of glutathione (GSH) with CTC, producing stable conjugates that were structurally characterized using liquid chromatography-ion-trap mass spectrometry (LC-IT-MS). Enzyme-mediated dechlorination of CTC resulted during GSH conjugation as revealed by the mass spectra of the CTC-GSH conjugate, which was characterized by the loss of the chlorine isotopic signature, and shorter chromatographic retention time relative to the chlorinated parent compound. Several fragmentation patterns in the mass spectrum of the CTC-GSH conjugate can be used to verify the identity of the enzyme reaction products. The expected molecular ion [M + H](+) of the CTC-GSH conjugate (m/z 751) with chlorine removal was not observed in the positive electrospray ionization. Instead, a base peak of m/z 677, corresponding to the loss of glycine (MW = 75 Da), was observed. When m/z 677 was subjected to further fragmentation, characteristic peaks corresponding to the loss of glutamic acid (m/z = 129) and water (m/z 18) were observed in the MS/MS spectrum. The catalytic activity of the CTC-induced GST towards dechlorination of chloroacetanilide herbicides (alachlor, metolachlor and propachlor), which are known to be detoxified in plants via the glutathione pathway, was also evaluated in vitro. Glutathione conjugates of chloroacetanilides also showed the losses of m/z 129 and m/z 18 that are characteristic of GSH conjugates when characterized by LC-IT-MS. Interestingly, the sensitivity of LC-IT-MS made it possible, for the first time, to detect chloroacetanilides that are conjugated with two GSH molecules, in addition to the known single GSH conjugates. This research demonstrates a more sensitive and specific method of measuring enzyme reaction products using LC-IT-MS. PMID:17592585

  14. Agricultural pesticides in six drainage basins used for public water supply in New Jersey, 1990

    USGS Publications Warehouse

    Ivahnenko, Tamara; Buxton, D.E.

    1994-01-01

    A reconnaissance study of six drainage basins in New Jersey was conducted to evaluate the presence of pesticides from agricultural runoff in surface water. In the first phase of the study, surface-water public-supply drainage basins throughout New Jersey that could be affected by pesticide applications were identified by use of a Geographic Information System. Six basins--Lower Mine Hill Reservoir, South Branch of the Raritan River, Main Branch of the Raritan River, Millstone River, Manasquan River, and Matchaponix Brook--were selected as those most likely to be affected by pesticides on the basis of calculated pesticide-application rates and percentage of agricultural land. The second phase of the project was a short-term water-quality reconnaissance of the six drainage basins to determine whether pesticides were present in the surface waters. Twenty-eight surface-water samples (22 water-quality samples, 3 sequentially collected samples, and 3 trip blanks), and 6 samples from water-treatment facilities were collected. Excluding trip blanks, samples from water-treatment facilities, and sequentially collected samples, the pesticides detected in the samples and the percentage of samples in which they were detected, were as follows: atrazine and metolachlor, 86 percent; alachlor, 55 percent; simazine, 45 percent; diazinon, 27 percent; cyanazine and carbaryl, 23 percent; linuron and isophenfos, 9 percent; and chlorpyrifos, 5 percent.Diazinon, detected in one stormflow sample collected from Matchaponix Brook on August 6, 1990, was the only compound to exceed the U.S. Environmental Protection Agency's recommended Lifetime Health Advisory Limit. Correlation between ranked metolachlor concentrations and ranked flow rates was high, and 25 percent of the variance in metolachlor concentrations can be attributed to variations in flow rate. Pesticide residues were detected in samples of pretreated and treated water from water-treatment facilities. Concentrations of all

  15. Determination of pesticides by solid phase extraction followed by gas chromatography with nitrogen-phosphorous detection in natural water and comparison with solvent drop microextraction.

    PubMed

    López-Blanco, C; Gómez-Alvarez, S; Rey-Garrote, M; Cancho-Grande, B; Simal-Gándara, J

    2006-02-01

    The European Union specifies that drinking water can contain pesticide residues at concentrations of up to 0.1 microg/L each and 0.5 microg/L in total, and that 1-3 microg/L of pesticides can be present in surface water, but the general idea is to keep discharges, emissions and losses of priority hazardous substances close to zero for synthetic substances. Therefore, in order to monitor pesticide levels in water, analytical methods with low quantification limits are required. The method proposed here is based on solid phase extraction (SPE) followed by gas chromatography with a nitrogen-phosphorous detector (GC-NPD). During method development, six organophosphate pesticides (azinphos-ethyl, chlorfenvinphos, chlorpyriphos, ethoprophos, fenamiphos and malathion) and two organonitrogen pesticides (alachlor and deltamethrin) were considered as target analytes. Elution conditions that could influence the efficiency of the SPE were studied. The optimized methodology exhibited good linearity, with determination coefficients of better than 0.996. The analytical recovery for the target analytes ranged from 70 to 100%, while the within-day precision was 4.0-11.5%. The data also showed that the nature of the aqueous matrice (ultrapure, surface or drinking water) had no significant effect on the recovery. The quantification limits for the analytes were found to be 0.01-0.13 microg/L (except for deltamethrin, which was 1.0 microg/L). The present methodology is easy, rapid and gives better sensitivity than solvent drop microextraction for the determination of organonitrogen and organophosphate pesticides in drinking water at levels associated with the legislation. PMID:16402179

  16. Ground-water quality in the Lake Champlain basin, New York, 2004

    USGS Publications Warehouse

    Nystrom, Elizabeth A.

    2006-01-01

    Water samples were collected from 11 public-supply wells and 11 private domestic wells in the Lake Champlain basin in New York during the fall of 2004 to characterize the chemical quality of ground water. Wells were selected for sampling based on location and focused on areas of greatest ground-water use. Samples were analyzed for 219 physical properties and constituents, including inorganic compounds, nutrients, metals, radionuclides, pesticides and pesticide degradates, volatile organic compounds, and bacteria. Sixty-eight constituents were detected at concentrations above laboratory reporting levels. The cation and anion with the highest median concentration were calcium (34.8 mg/L) bicarbonate (134 mg/L), respectively. The predominant nutrient was nitrate, which was detected in 14 (64 percent) of the 22 samples. The two metals with the highest median concentrations were iron (175 ?g/L) and strontium (124 ?g/L); concentrations of iron, manganese, aluminum, and zinc exceeded U.S. Environmental Protection Agency secondary drinking-water standards in one or more samples. Radon concentrations were less than 1,000 picocuries per liter (pCi/L) in most samples, but concentrations as high as 6,900 pCi/L were detected and, in eight samples, exceeded the U.S. Environmental Protection Agency proposed maximum contaminant level (300 pCi/L) for radon. The most frequently detected pesticides were degradates of the broadleaf herbicides metolachlor, alachlor, and atrazine. Volatile organic compounds were detected in only three samples; those that were detected typically were fuel oxygenates, such as methyl tert-butyl ether. Coliform bacteria were detected in four samples, two of which also tested positive for E. coli.

  17. Effects of trace elements and pesticides on dephosphorylation of RNA and DNA added to soils

    SciTech Connect

    Frankenberger, W.T. Jr.; Johanson, J.B.; Lund L.J.

    1986-01-01

    This study was carried out to assess the effects of 14 trace elements, 12 herbicides, and two fungicides on dephosphorylation of yeast ribonucleic acid (RNA) and deoxyribonucleic acid (DNA) added to soils (Xerollic Calciorthids and Typic Haploxeralfs). The cumulative amount of ortho phosphate (Pi) released from nucleic acids increased linearly with time of incubation (up to 72 h), decreased with profile depth, and was highly influenced by soil pH. When trace elements were applied and compared by using 2.5 mmol kg/sup -1/ of soil, the average inhibition in dephosphorylation of RNA and DNA in two soils ranged from 17% with Co(II) to 52% with Cu(II). The most effective inhibitors of nucleic acid dephosphorylation were Ag(I), Cu(I), Cd(II), Cu(II), Mn(II), Ni(II), and Pb(II) (avg inhibition greater than or equal to 35%). Other elements that inhibited dephosphorylation of RNA and DNA added to soils included Ba(II), Co(II), Hg(II), Zn(II), Ti(IV), V(IV), and W(VI). When the pesticides were compared by using 5 mg of active ingredient kg/sup -1/ of soil, the average inhibition in nucleic acid dephosphorylation ranged from 14% with butylate to 39% with chloramben. The most effective inhibitors (> 25%) were atrazine, naptalam, chloramben, dicamba, trifluralin, and maneb. Other pesticides that inhibited RNA and DNA dephosphorylation in soils included cyanazine, 2,4-D, dinitroamine, EPTC plus R-25788, alachlor, paraquat, butylate, and captan.

  18. Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory; determination of pesticides in water by C-18 solid-phase extraction and capillary-column gas chromatography/mass spectrometry with selected-ion monitoring

    USGS Publications Warehouse

    Zaugg, Steven D.; Sandstrom, Mark W.; Smith, Steven G.; Fehlberg, Kevin M.

    1995-01-01

    A method for the isolation of 41 pesticides and pesticide metabolites in natural-water samples using C-18 solid-phase extraction and determination by capillary-column gas chromatography/mass spectrometry with selected-ion monitoring is described. Water samples are filtered to remove suspended particulate matter and then are pumped through disposable solid-phase extraction columns containing octadecyl-bonded porous silica to extract the pesticides. The columns are dried using carbon dioxide or nitrogen gas, and adsorbed pesticides are removed from the columns by elution with 3.0 milliliters of hexane-isopropanol (3:1). Extracted pesticides are determined by capillary- column gas chromatography/mass spectrometry with selected-ion monitoring of three characteristic ions. The upper concentration limit is 4 micrograms per liter (g/L) for most pesticides, with the exception of widely used corn herbicides--atrazine, alachlor, cyanazine, and metolachlor--which have upper concentration limits of 20 g/L. Single- operator method detection limits in reagent-water samples range from 0.001 to 0.018 g/L. Average short-term single-operator precision in reagent- water samples is 7 percent at the 0.1- and 1.0-g/L levels and 8 percent at the 0.01-g/L level. Mean recoveries in reagent-water samples are 73 percent at the 0.1- and 1.0-g/L levels and 83 percent at the 0.01-g/L level. The estimated holding time for pesticides after extraction on the solid-phase extraction columns was 7 days. An optional on-site extraction procedure allows for samples to be collected and processed at remote sites where it is difficult to ship samples to the laboratory within the recommended pre-extraction holding time.

  19. Can we predict community-wide effects of herbicides from toxicity tests on macrophyte species?

    PubMed

    Coutris, Claire; Merlina, Georges; Silvestre, Jérôme; Pinelli, Eric; Elger, Arnaud

    2011-01-17

    Macrophyte communities play an essential role in the way freshwater ecosystems function. It is thus of great concern to understand how environmental factors, especially anthropogenic ones, influence their composition and diversity. The aim of this study was to examine whether the effects of a herbicide mixture (50% atrazine, 35% isoproturon, 15% alachlor) on single macrophyte species can be used to predict its impact at a community level. In a first experiment we tested the sensitivity of six species (Azolla filiculoides, Ceratophyllum demersum, Elodea canadensis, Lemna minor, Myriophyllum spicatum and Vallisneria spiralis) grown separately and exposed to 0.6-600 μg L(-1) of the herbicide mixture. In a second experiment, conducted in microcosms, we tested the effects of herbicides on macrophyte assemblages composed of the same six species exposed to 0, 6 or 60 μg L(-1) of the herbicide mixture. Species grown separately exhibited growth inhibition at 60 and 600 μg L(-1). At 600 μg L(-1) the sensitivity differed significantly between species. V. spiralis was the most resistant species, C. demersum, M. spicatum and E. canadensis exhibited intermediate sensitivities, and A. filiculoides and L. minor were the most sensitive species. In microcosms, community biomass and Shannon evenness index were reduced after 8 weeks at 60 μg L(-1). Communities also exhibited changes in their composition: the relative and absolute abundance of C. demersum increased at 6 μg L(-1), while the relative abundance of V. spiralis increased at 60 μg L(-1). These results are in agreement with the individual responses of these species to the herbicides. It is therefore concluded that short-term effects of herbicides on simple macrophyte communities can be predicted from the sensitivity of individual species. However, further investigations are required to examine whether longer term effects can be predicted as well, especially in more complex communities. PMID:20926143

  20. Characterization of environmental chemicals with potential for DNA damage using isogenic DNA repair-deficient chicken DT40 cell lines

    PubMed Central

    Yamamoto, Kimiyo N.; Hirota, Kouji; Kono, Koichi; Takeda, Shunichi; Sakamuru, Srilatha; Xia, Menghang; Huang, Ruili; Austin, Christopher P.; Witt, Kristine L.; Tice, Raymond R.

    2012-01-01

    Included among the quantitative high throughput screens (qHTS) conducted in support of the U.S. Tox21 program are those being evaluated for the detection of genotoxic compounds. One such screen is based on the induction of increased cytotoxicity in 7 isogenic chicken DT40 cell lines deficient in DNA repair pathways compared to the parental DNA repair-proficient cell line. To characterize the utility of this approach for detecting genotoxic compounds and identifying the type(s) of DNA damage induced, we evaluated nine of 42 compounds identified as positive for differential cytotoxicity in qHTS (actinomycin D, adriamycin, alachlor, benzotrichloride, diglycidyl resorcinol ether, lovastatin, melphalan, trans-1,4-dichloro-2-butene, tris(2,3-epoxypropyl)isocyanurate) and one non-cytotoxic genotoxic compound (2-aminothiamine) for (1) clastogenicity in mutant and wild-type cells; (2) the comparative induction of γH2AX positive foci by melphalan; (3) the extent to which a 72-hr exposure duration increased assay sensitivity or specificity; (4) the use of 10 additional DT40 DNA repair-deficient cell lines to better analyze the type(s) of DNA damage induced; and (5) the involvement of reactive oxygen species in the induction of DNA damage. All compounds but lovastatin and 2-aminothiamine were more clastogenic in at least one DNA repair-deficient cell line than the wild-type cells. The differential responses across the various DNA repair-deficient cell lines provided information on the type(s) of DNA damage induced. The results demonstrate the utility of this DT40 screen for detecting genotoxic compounds, for characterizing the nature of the DNA damage, and potentially for analyzing mechanisms of mutagenesis. PMID:21538559

  1. Agricultural chemicals in near-surface aquifers in the mid-continental United States, 1991

    SciTech Connect

    Kolpin, D.W. ); Burkart, M.R. )

    1993-03-01

    The occurrence and distribution of selected herbicides, atrazine metabolites, and nitrate were determined for unconsolidated and bedrock aquifers within 50 feet of land surface (near-surface) in the corn and soybean producing region of the mid-continental US. At least one herbicide or atrazine metabolite was detected (reporting limit, 0.05 micrograms per liter) in 24 percent of 579 water samples collected during the spring and summer of 1991. No herbicide exceeded maximum contaminant levels or health advisories. Most frequently detected was desethylatrazine (18.1 percent) followed by atrazine (17.4 percent), deisopropylatrazine (5.7 percent) and prometon (5.0 percent). Metolachlor, alachlor, metribuzin, simazine, and cyanazine were found in fewer than 3 percent of the samples. Excess nitrate (more than 3.0 mg/L) was found in 29 percent of the samples; 6 percent exceeded 10 mg/L. Few herbicide detections or excess nitrate concentrations occurred in the eastern part of the study region even though this area had an intense use of herbicides and nitrogen-fertilizer. The source of prometon, the second most frequently detected herbicide, may be associated with nonagricultural land use such as golf courses and residential areas. Significant seasonal differences between the spring and summer sampling periods were found in herbicide detections, but not in excess nitrate. The frequency of herbicide detections and excess nitrate were greater in near-surface unconsolidated aquifers than found in near-surface bedrock aquifers. Depth to the top of the aquifer was inversely related to the frequency of both herbicide detection and excess nitrate. The proximity of sampling sites to streams affected the frequency of herbicide detection.

  2. New insight into pesticide partition coefficient Kd for modelling pesticide fluvial transport: application to an agricultural catchment in south-western France.

    PubMed

    Boithias, Laurie; Sauvage, Sabine; Merlina, Georges; Jean, Séverine; Probst, Jean-Luc; Sánchez Pérez, José Miguel

    2014-03-01

    Pesticides applied on crops are leached with rainfall to groundwater and surface water. They threat the aquatic environment and may render water unfit for human consumption. Pesticide partitioning is one of the pesticide fate processes in the environment that should be properly formalised in pesticide fate models. Based on the analysis of 7 pesticide molecules (alachlor, atrazine, atrazine's transformation product deethylatrazine or DEA, isoproturon, tebuconazole and trifluralin) sampled from July 2009 to October 2010 at the outlet of the river Save (south-western France), the objectives of this study were (1) to check which of the environmental factors (discharge, pH, concentrations of total suspended matter (TSM), dissolved organic carbon (DOC) and particulate organic carbon (POC) could control the pesticide sorption dynamic, and (2) to establish a relationship between environmental factors, the partition coefficient Kd and the octanol/water distribution coefficient Kow. The comparison of physico-chemical parameters values during low flow and high flow shows that discharge, TSM and POC are the factors most likely controlling the pesticide sorption processes in the Save river network, especially for lower values of TSM (below 13mgL(-1)). We therefore express Kd depending on the widely literature-related variable Kow and on the commonly simulated variable TSM concentration. The equation can be implemented in any model describing the fluvial transport and fate of pesticides in both dissolved and sorbed phases, thus, Kd becomes a variable in time and space. The Kd calculation method can be applied to a wide range of catchments and organic contaminants. PMID:24275149

  3. Atmospheric pressure glow discharge desorption mass spectrometry for rapid screening of pesticides in food.

    PubMed

    Jecklin, Matthias Conradin; Gamez, Gerardo; Touboul, David; Zenobi, Renato

    2008-09-01

    Flowing afterglow atmospheric pressure glow discharge tandem mass spectrometry (APGD-MS/MS) is used for the analysis of trace amounts of pesticides in fruit juices and on fruit peel. The APGD source was rebuilt after Andrade et al. (Andrade et al., Anal. Chem. 2008; 80: 2646-2653; 2654-2663) and mounted onto a hybrid quadrupole time-of-flight mass spectrometer. Apple, cranberry, grape and orange juices as well as fruit peel and salad leaves were spiked with aqueous solutions containing trace amounts of the pesticides alachlor, atrazine, carbendazim, carbofuran, dinoseb, isoproturon, metolachlor, metolcarb, propoxur and simazine. Best limits of determination (LODs) of pesticides in the fruit juices were achieved for metolcarb (1 microg/L in apple juice), carbofuran and dinoseb (2 microg/L in apple juice); for the analysis of apple skin best LODs were 10 pg/cm(2) of atrazine, metolcarb and propoxur which corresponds to an estimated concentration of 0.01 microg/kg apple, taking into account the surface area and the weight of the apple. The measured LODs were within or below the allowed maximum residue levels (MRLs) decreed by the European Union (1-500 microg/kg for pesticides in fruit juice and 0.01-5 microg/kg for apple skin). No sample pretreatment (extraction, pre-concentration, chromatographic separation) was necessary to analyze these pesticides by direct desorption/ionization using APGD-MS and to identify them using MS/MS. This makes APGD-MS a powerful high-throughput tool for the investigation of very low amounts of pesticides in fruit juices and on fruit peel/vegetable skin. PMID:18697232

  4. Data on selected herbicides and two triazine metabolites in precipitation of the Midwestern and Northeastern United States, 1990-91

    USGS Publications Warehouse

    Goolsby, D.A.; Scribner, E.A.; Thurman, E.M.; Pomes, M.L.; Meyer, M.T.

    1995-01-01

    Weekly precipitation (rain and snow) samples were collected from 81 National Atmospheric Deposition Program/National Trends Network sites in the Midwestern and Northeastern United States for the analysis of herbicides. In addition, five high- elevation background sites along the Rocky Mountains and in Alaska were sampled to provide data on herbicides in precipitation at sites far from the study area. The study began in March 1990 and continued through September 1991. The precipitation samples were shipped to the Central Analytical Laboratory operated by the Illinois State Water Survey for analyses of inorganic compounds. Subsamples of the precipitation were shipped to the U.S. Geological Survey laboratory in Lawrence, Kansas, for the analysis of 11 herbicides and 2 triazines metabolites. This report provides descriptions of the study area, sample-collection methods, laboratory methods, and quality assurance. The report also includes a compilation of herbicide concentration data from both enzyme-linked immunosorbent assay and gas chromatography/mass spectrometry methods. Laboratory analyses consisted of 6,230 samples that were analyzed by enzyme-linked immunosorbent assay using alachlor and atrazine microtiter plates and 2,341 samples that were confirmed by gas chromatography/mass spectrometry analysis. Graphical and statistical comparisons of the two analytical methods are given in this report. Data from this study have been useful in determining the spatial and temporal distribution of herbicide concentrations and deposition in precipitation of over a 26-State area of the Midwestern and Northeastern United States. The data also provide evidence of long-range atmospheric transport of herbicides and triazine metabolites.

  5. The w/w+ SMART is a useful tool for the evaluation of pesticides.

    PubMed

    Aguirrezabalaga, I; Santamaría, I; Comendador, M A

    1994-07-01

    Genotype-dependent variability in the response of several Drosophila strains to hexamethylphosphoramide (HMPA) has been studied using the white/white+ (w/w+) somatic mutation and recombination test (SMART). Among the tester strains, there were three wild-type laboratory strains (Leiden-S, Oregon-K and 91-C) and three insecticide-resistant strains (Haag-79, Hikone-R and 91-R). The response to HMPA of larvae from a cross between two wild-type strains (Leiden-S and Berlin-K) was also measured. The strains have been evaluated in terms of spontaneous frequencies of mosaic eyes, lowest effective dose and dose-response relationship. Strong variability was found among the strains, the best performance to HMPA being obtained with the strain Oregon-K. In addition, a series of pesticides structurally related to HMPA, such as dimefox, hexamethylmelamine, hexazinone, alachlor, CAM, pirimicarb, dimetilan, thiram and methabenzthiazuron have been tested with the Oregon-K strain. Some of these pesticides had already been shown to be genotoxic in other systems, whereas others have either not been tested or gave negative results in in vitro systems. Although genotoxicity was expressed only within a narrow dose range, all pesticides were genotoxic in the w/w+ system with the Oregon-K strain. Thus, these compounds may be a genotoxic hazard to man. These results suggest the suitability of the strain Oregon-K for genotoxicity testing with the w/w+ eye mosaic system, although more information about the performance of this strain with other compounds must be obtained.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:7968576

  6. Occurrence of pesticides in groundwater and sediments and mineralogy of sediments and grain coatings underlying the Rutgers Agricultural Research and Extension Center, Upper Deerfield, New Jersey, 2007

    USGS Publications Warehouse

    Reilly, Timothy J.; Smalling, Kelly L.; Meyer, Michael T.; Sandstrom, Mark W.; Hladik, Michelle L.; Boehlke, Adam R.; Fishman, Neil S.; Battaglin, William A.; Kuivila, Kathryn M.

    2014-01-01

    Water and sediment samples were collected from June through October 2007 from seven plots at the Rutgers Agricultural Research and Extension Center in Upper Deerfield, New Jersey, and analyzed for a suite of pesticides (including fungicides) and other physical and chemical parameters (including sediment mineralogy) by the U.S. Geological Survey. Plots were selected for inclusion in this study on the basis of the crops grown and the pesticides used. Forty-one pesticides were detected in 14 water samples; these include 5 fungicides, 13 herbicides, 1 insecticide, and 22 pesticide degradates. The following pesticides and pesticide degradates were detected in 50 percent or more of the groundwater samples: 1-amide-4-hydroxy-chorothalonil, alachlor sulfonic acid, metolachlor oxanilic acid, metolachlor sulfonic acid, metalaxyl, and simazine. Dissolved-pesticide concentrations ranged from below their instrumental limit of detection to 36 micrograms per liter (for metolachlor sulfonic acid, a degradate of the herbicide metolachlor). The total number of pesticides found in groundwater samples ranged from 0 to 29. Fourteen pesticides were detected in sediment samples from continuous cores collected within each of the seven sampled plots; these include 4 fungicides, 2 herbicides, and 7 pesticide degradates. Pesticide concentrations in sediment samples ranged from below their instrumental limit of detection to 34.2 nanograms per gram (for azoxystrobin). The total number of pesticides found in sediment samples ranged from 0 to 8. Quantitative whole-rock and grain-coating mineralogy of sediment samples were determined by x-ray diffraction. Whole-rock analysis indicated that sediments were predominantly composed of quartz. The materials coating the quartz grains were removed to allow quantification of the trace mineral phases present.

  7. Water-quality assessment of the Ozark Plateaus study unit, Arkansas, Kansas, Missouri, and Oklahoma- summary of information on pesticides, 1970-90

    USGS Publications Warehouse

    Bell, Richard W.; Joseph, Robert L.; Freiwald, David A.

    1996-01-01

    Historical pesticide data from 1970-90 were compiled for 140 surface-water, 92 ground-water, 55 streambed-sediment, and 120 biological-tissue sampling sites within the Ozark Plateaus National Water-Quality Assessment Program study unit. Surface-water, bed-sediment, and biological-tissue sites have drainage basins predominantly in the Springfield and Salem Plateaus; ground-water sites are predominantly located in the Osage Plains and Mississippi Alluvial Plain. Many sites were sampled only once or twice during this period. A large percentage of the samples were collected in the mid-1970's and early 1980's for surface water, 1990 for ground water, the late 1980's for surface water, 1990 for ground water, the late 1980's for bed sediment, and the early 1980's for biological tissue. Pesticide use was approximately 4.2 million pounds per year of active ingredients from 1982-85 in the study unit and was generally greatest in the Springfield and Salem Plateaus pasturelands and in the Osage Plains and Mississippi Alluvial Plain cropland areas. The most frequently applied pesticide in the study unit was 2,4-D. Alachlor was the second most applied pesticide. Corn, pasture, rice, sorghum, and soybeans received approximately 90 percent of the pesticides applied within the study unit. The highest pesticide application rate per acre occurred on these crops in the Osage Plains and Mississippi Alluvial Plain. Pastureland was the predominant crop type in 50 of the 94 counties in the study unit. Toxaphene, the pesticide having the most number of detections in surface water, was found in 17 of 866 samples from 5 of 112 sites. Concentrations ranged from 0.1 to 6.0 micrograms per liter. Six other pesticides or pesticide metabolites were detected in 12 or more surface-water samples: DDE, dieldrin, DDT, aldrin, 2,4-D, and lindane. The maximum concentration for these pesticides was less than 1.0 micrograms per liter. Atrazine, the pesticide having the most number of detections in ground

  8. Altitude, age, and quality of groundwater, Papio-Missouri River Natural Resources District, eastern Nebraska, 1992 to 2009

    USGS Publications Warehouse

    McGuire, Virginia L.; Ryter, Derek W.; Flynn, Amanda S.

    2012-01-01

    the 21 pesticides detected (alachlor, atrazine, and metolachlor) have established health-based criteria; all detections of these compounds were at concentrations less than their USEPA standards. From 2007 to 2009, 1 or more pesticide compounds were detected in 16 of the 82 network wells and in 18 of the 26 wells in well nests. From 2007 to 2009, the individual pesticide compounds that were detected most frequently were alachlor ethane sulfonic acid, a degradate of alachlor; deethylcyanazine acid, a degradate of cyanazine; and atrazine. Analytes with concentrations that exceeded 30 percent of the applicable Nebraska Title-118 standard were identified so that the PMRNRD can plan to monitor groundwater in the area and consider possible actions should the analyte concentrations continue to rise. The analytical results from the most recent samples collected in the network wells and all the wells in well nests from 1992 to 2009 indicate that, in at least 1 sample, there was a concentration that exceeded 30 percent of the Nebraska Title-118 standard for at least 1 of 3 major ions (chloride, fluoride, and sulfate), 1 nutrient (nitrate-N), 1 pesticide (atrazine), or 3 trace elements (arsenic, iron, and manganese). In addition, 30 percent of the USEPA MCL or Nebraska Title-118 standard for gross alpha activity likely was exceeded in samples from three wells screened in the Dakota aquifer. Study findings indicate that some alternatives to the current PMRNRD groundwater-sampling approach that could be considered are to collect fewer samples for nutrient analysis and to collect samples periodically for determining concentrations of additional analytes, particularly the analytes with concentrations that were at least 30 percent or more than the Nebraska Title-118 standard.

  9. Compound specific isotope analysis to investigate pesticide degradation in lysimeter experiments at field conditions

    NASA Astrophysics Data System (ADS)

    Ryabenko, Evgenia; Elsner, Martin; Bakkour, Rani; Hofstetter, Thomas; Torrento, Clara; Hunkeler, Daniel

    2015-04-01

    The frequent detection of organic micropollutants such as pesticides, consumer care products or pharmaceuticals in water is an increasing concern for human and ecosystem health. Degradation analysis of these compounds can be challenging in complex systems due to the fact that metabolites are not always found and mass balances frequently cannot be closed. Many abiotic and biotic degradation pathways cause, however, distinct isotope fractionation, where light isotopes are transferred preferentially from the reactant to the product pool (normal isotope fractionation). Compound-specific isotope analysis (CSIA) of multiple elements is a particularly powerful method to evaluate organic micropollutant transformation, because it can even give pathway-specific isotope fractionation (1,2). Available CSIA field studies, however, have focused almost exclusively on volatile petroleum and chlorinated hydrocarbons, which are present in high concentrations in the environment and can be extracted easily from water for GC-IRMS analysis. In the case of micropollutants, such as pesticides, CSIA in more challenging since it needs to be conducted at lower concentrations and requires pre-concentration, purification and high chromatographic performance (3). In this study we used lysimeters experiments to analyze transformation of atrazine, acetochlor, metolachlor and chloridazone by studying associated isotope fractionation. The project combines a) analytical method development for CSIA, b) identification of pathways of micropollutant degradation and c) quantification of transformation processes under field condition. The pesticides were applied both, at the soil surface and below the top soil under field-relevant concentrations in May 2014. After typical irrigation of the lysimeters, seepage water was collected in 50L bottles and stored for further SPE and CSIA. Here we present the very first result of a) analytical method development, b) improvement of SPE methods for complex pesticide

  10. Seasonal exposures to triazine and other pesticides in surface waters in the western Highveld corn-production region in South Africa

    USGS Publications Warehouse

    Du Preez, L.H.; Jansen Van Rensburg, P.J.; Jooste, A.M.; Carr, J.A.; Giesy, J.P.; Gross, T.S.; Kendall, R.J.; Smith, E.E.; Van Der Kraak, G.; Solomon, K.R.

    2005-01-01

    The objective of this study was to characterize concentrations of atrazine, terbuthylazine, and other pesticides in amphibian habitats in surface waters of a corn-production area of the western Highveld region (North-West Province) of South Africa. The study was conducted from November 2001 to June 2002, coinciding with the corn-production season. Pesticide residues were measured at regular intervals in surface water from eight ponds, three in a non-corn-growing area (NCGA) and five within the corn-growing area (CGA). Measured atrazine concentrations differed significantly among sites and between samples. In the five CGA sites, the maximum atrazine concentrations measured during the study ranged from 1.2 to 9.3 ??g/L. Although no atrazine was recorded as being applied in the catchment of the three NCGA sites, maximum concentrations from 0.39 to 0.84 ??g/L were measured during the study, possibly as a result of atmospheric transport. Maximum measured concentrations of terbuthylazine ranged from 1.22 to 2.1 ??g/L in the NCGA sites and from 1.04 to 4.1 ??g/L in the CGA sites. The source of terbuthylazine in the NCGA sites may have been in use other than in corn. The triazine degradation products, deisopropylatrazine (DIA) and deethylatrazine (DEA) and diaminochlorotriazine (DACT) were also found in water from both the CGA and NCGA sites. Concentrations of DIA were ??? 1 ??g/L throughout the season, while DEA concentrations were mostly 2 ??g/L in some locations. Concentrations of DACT were highly variable (LOD to 8 ??g/L) both before and after planting and application, suggesting that they resulted from historical use of triazines in the area. Other herbicides such as simazine and acetochlor were only detected infrequently and pesticides such as S-metolachlor, cypermethrin, monocrotophos, and terbuphos, known to be used in the CGA, were not detected in any of the samples. Because of dilution by higher than normal rainfall in the study period, these concentrations may

  11. Compound-specific stable isotope analysis of herbicides in stream water: a combined monitoring and modeling approach to assess pollutant degradation at catchment scale

    NASA Astrophysics Data System (ADS)

    Lutz, Stefanie; Van der Velde, Ype; Elsayed, Omniea; Imfeld, Gwenael; Lefrancq, Marie; Payraudeau, Sylvain; Van Breukelen, Boris

    2014-05-01

    Compound-specific stable isotope analysis (CSIA) measures the isotopic composition of a compound, i.e. the relative abundance of light and heavy stable isotopes of an element contained in the compound (e.g. 12C and 13C). As degradation processes may induce a change in isotopic composition (i.e. isotope fractionation), CSIA allows distinguishing degradation from non-destructive processes such as dilution or sorption. CSIA can be combined with model-assisted interpretation to evaluate degradation of contaminants in the environment. Although CSIA methods have also been developed for diffuse pollutants such as pesticides and nitrate, they have not yet been continuously applied in monitoring of diffuse pollution in surface water. Results of a virtual experiment of isotope fractionation at hillslope scale have suggested that CSIA qualifies as a feasible and useful complement to concentration measurements of diffuse pollutants (Lutz et al., 2013). We now present the first continuously measured concentration and carbon CSIA data of herbicides from a 49-ha agricultural catchment (Alsace, France). Stream concentrations of two chloroacetanilide herbicides, i.e. S-metolachlor and acetochlor, were highest (65 μg/L) following an extreme rainfall event in the first month after herbicide application, and subsequently decreased to background concentration level (0.1 μg/L). This decrease was accompanied by an increase of more than 2 ‰ in carbon isotope ratios, which was also observed in surface runoff samples from a plot experiment in the study catchment. The increase of carbon isotope ratios over time indicates the occurrence of herbicide degradation during transport to the stream, and thus demonstrates the advantage of CSIA over pesticide concentration measurements only. Despite providing evidence of herbicide degradation, the field CSIA data do not allow for a comprehensive characterization of herbicide sources, fate and transport in the study catchment. Therefore, we

  12. Compound-specific stable isotope analysis of pesticides: a combined monitoring and modeling approach to assess pesticide fate and degradation at catchment scale

    NASA Astrophysics Data System (ADS)

    van Breukelen, B. M.; Lutz, S.; Van der Velde, Y.; Elsayed, O. F.; LeFrancq, M.; Payraudeau, S.; Imfeld, G.

    2014-12-01

    Compound-specific stable isotope analysis (CSIA) has proven useful in asessing the fate of groundwater contamination. However, although evidence of diffuse pesticide degradation is crucial, and CSIA methods have been developed for several pesticides, there is a clear lack of field CSIA data of pesticides. This study now presents the first analysis of field CSIA data from a 47-ha agricultural headwater catchment (Alteckendorf, Alsace, France) in the period March to August 2012. Measured stream concentrations of the two investigated chloroacetanilide herbicides (S-metolachlor and acetochlor) were highest (65 μg/L) following an intense rainfall event in the first month after herbicide application. Carbon isotope ratios increased with more than 2 ‰ in 3 months, which indicates the occurrence of herbicide degradation during transport to the stream. Previously, field CSIA data have also been simulated with reactive transport models to evaluate degradation of groundwater contaminants. This study now presents such a model-assisted interpretation of CSIA data for the first time at catchment scale, which aims at exploring the added value of CSIA in monitoring and modelling of pesticide pollution. The conceptual mathematical model succeeded in reproducing the general trend in concentrations and carbon isotope ratios of metolachlor. It also allowed for the quantification of metolachlor degradation (above 70 % during the study period), and yielded a mass export of 1.8 % of the applied pesticide, which is in agreement with the measured pesticide export. The field concentration and CSIA data informed the model building by indicating the importance of overland flow, and slow pesticide degradation in groundwater compared to the upper soil zone. Moreover, incorporation of the field CSIA data into model calibration slightly reduced model uncertainty in the quantification of pesticide degradation. We suggest that a finer temporal CSIA resolution than possible in this study

  13. Glyphosate, other herbicides, and transformation products in Midwestern streams, 2002

    USGS Publications Warehouse

    Battaglin, W.A.; Kolpin, D.W.; Scribner, E.A.; Kuivila, K.M.; Sandstrom, M.W.

    2005-01-01

    The use of glyphosate has increased rapidly, and there is limited understanding of its environmental fate. The objective of this study was to document the occurrence of glyphosate and the transformation product aminomethylphosphonic acid (AMPA) in Midwestern streams and to compare their occurrence with that of more commonly measured herbicides such as acetochlor, atrazine, and metolachlor. Water samples were collected at sites on 51 streams in nine Midwestern states in 2002 during three runoff events: after the application of pre-emergence herbicides, after the application of post-emergence herbicides, and during harvest season. All samples were analyzed for glyphosate and 20 other herbicides using gas chromatography/mass spectrometry or high performance liquid chromatography/mass spectrometry. The frequency of glyphosate and AMPA detection, range of concentrations in runoff samples, and ratios of AMPA to glyphosate concentrations did not vary throughout the growing season as substantially as for other herbicides like atrazine, probably because of different seasonal use patterns. Glyphosate was detected at or above 0.1 μg/1 in 35 percent of pre-emergence, 40 percent of post-emergence, and 31 percent of harvest season samples, with a maximum concentration of 8.7 μg/1. AMPA was detected at or above 0.1 μg/1 in 53 percent of pre-emergence, 83 percent of post-emergence, and 73 percent of harvest season samples, with a maximum concentration of 3.6 μg/1. Glyphosate was not detected at a concentration at or above the U.S. Environmental Protection Agency's maximum contamination level (MCL) of 700 μg/1 in any sample. Atrazine was detected at or above 0.1 μg/1 in 94 percent of pre-emergence, 96 percent of post-emergence, and 57 percent of harvest season samples, with a maximum concentration of 55 μg/1. Atrazine was detected at or above its MCL (3 μg/1) in 57 percent of pre-emergence and 33 percent of post-emergence samples

  14. Compilation of Data to Support Development of a Pesticide Management Plan by the Yankton Sioux Tribe, Charles Mix County, South Dakota

    USGS Publications Warehouse

    Schaap, Bryan D.

    2004-01-01

    The U.S. Environmental Protection Agency is working with the Yankton Sioux Tribe to develop a pesticide management plan to reduce potential for contamination of ground water that may result from the use of registered pesticides. The purpose of this study was to compile technical information to support development of a pesticide management plan by the Yankton Sioux Tribe for the area within the Yankton Sioux Reservation, Charles Mix County, South Dakota. Five pesticides (alachlor, atrazine, cyanazine, metolachlor, and simazine) were selected by the U.S. Environmental Protection Agency for the management plan approach because they had been identified as probable or possible human carcinogens and they often had been associated with ground-water contamination in many areas and at high concentrations. This report provides a compilation of data to support development of a pesticide management plan. Available data sets are summarized in the text of this report, and actual data sets are provided in one Compact Disk?Read-Only Memory that is included with the report. The compact disk contains data sets pertinent to the development of a pesticide management plan. Pesticide use for the study area is described using information from state and national databases. Within South Dakota, pesticides commonly are applied to corn and soybean crops, which are the primary row crops grown in the study area. Water-quality analyses for pesticides are summarized for several surface-water sites. Pesticide concentrations in most samples were found to be below minimum reporting levels. Topographic data are presented in the form of 30-meter digital elevation model grids and delineation of drainage basins. Geohydrologic data are provided for the surficial deposits and the bedrock units. A high-resolution (30-by-30 meters) land-cover and land-use database is provided and summarized in a tabular format. More than 91 percent of the study area is used for row crops, pasture, or hay, and almost 6

  15. Water-Quality Assessment of the Trinity River Basin, Texas - Pesticides in Streams Draining an Urban and an Agricultural Area, 1993-95

    USGS Publications Warehouse

    Land, Larry F.; Brown, Mariann F.

    1996-01-01

    Water and bed-sediment samples from streams draining an urban and an agricultural area in the Trinity River Basin, Texas, were analyzed. The samples were collected during March 1993?September 1995 by the Trinity River Basin study-unit team of the National Water-Quality Assessment Program. A comparison of pesticide data for water samples from seven streams in the Dallas-Fort Worth urban area with five streams in an agricultural area in the west-central part of the Trinity River Basin showed detections of 24 herbicides in urban-area streams and 19 herbicides in agricultural-area streams and 10 insecticides in each area. Atrazine, a herbicide, was detected in all samples from both areas. Diazinon, an insecticide, was detected in all samples collected in urban-area streams and in about 60 percent of the samples collected in agricultural-area streams. Concentrations of alachlor, atrazine, fluometuron, metolachlor, and pendimethalin (herbicides) were always greater in agricultural-area streams, and prometon and simazine concentrations were always greater in urban-area streams. Atrazine was the only herbicide with concentrations greater than a health advisory limit of 3 micrograms per liter. Concentrations were greater in about 20 percent of the samples; all were in the agricultural area and occurred during spring and during higher streamflow. Diazinon was the only insecticide with concentrations greater than the health advisory of 0.6 microgram per liter. Concentrations were greater in about 15 percent of the samples from the urban area. All exceedances were during spring through early fall and during all ranges of streamflow. In the agricultural area, atrazine and metolachlor concentrations peaked during spring and early summer and increased with increasing streamflow; in the urban area, carbaryl, chlorpyrifos, and diazinon peaked in April and remained relatively high during the summer and increased with increasing streamflow. A comparison of pesticide data for

  16. An overview on the advanced oxidation processes applied for the treatment of water pollutants defined in the recently launched Directive 2013/39/EU.

    PubMed

    Ribeiro, Ana R; Nunes, Olga C; Pereira, Manuel F R; Silva, Adrián M T

    2015-02-01

    Environmental pollution is a recognized issue of major concern since a wide range of contaminants has been found in aquatic environment at ngL(-1) to μgL(-1) levels. In the year 2000, a strategy was defined to identify the priority substances concerning aquatic ecosystems, followed by the definition of environmental quality standards (EQS) in 2008. Recently it was launched the Directive 2013/39/EU that updates the water framework policy highlighting the need to develop new water treatment technologies to deal with such problem. This review summarizes the data published in the last decade regarding the application of advanced oxidation processes (AOPs) to treat priority compounds and certain other pollutants defined in this Directive, excluding the inorganic species (cadmium, lead, mercury, nickel and their derivatives). The Directive 2013/39/EU includes several pesticides (aldrin, dichlorodiphenyltrichloroethane, dicofol, dieldrin, endrin, endosulfan, isodrin, heptachlor, lindane, pentachlorophenol, chlorpyrifos, chlorfenvinphos, dichlorvos, atrazine, simazine, terbutryn, diuron, isoproturon, trifluralin, cypermethrin, alachlor), solvents (dichloromethane, dichloroethane, trichloromethane and carbon tetrachloride), perfluorooctane sulfonic acid and its derivatives (PFOS), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), nonylphenol and octylphenol, as well as the three compounds included in the recommendation for the first watch list of substances (diclofenac, 17-alpha-ethinylestradiol (EE2) and 17-beta-estradiol (E2)). Some particular pesticides (aclonifen, bifenox, cybutryne, quinoxyfen), organotin compounds (tributyltin), dioxins and dioxin-like compounds, brominated diphenylethers, hexabromocyclododecanes and di(2-ethylhexyl)phthalate are also defined in this Directive, but studies dealing with AOPs are missing. AOPs are recognized tools to destroy recalcitrant compounds or, at least, to transform them into biodegradable species

  17. Probability of detecting atrazine/desethyl-atrazine and elevated concentrations of nitrate in ground water in Colorado

    USGS Publications Warehouse

    Rupert, Michael G.

    2003-01-01

    Draft Federal regulations may require that each State develop a State Pesticide Management Plan for the herbicides atrazine, alachlor, metolachlor, and simazine. Maps were developed that the State of Colorado could use to predict the probability of detecting atrazine and desethyl-atrazine (a breakdown product of atrazine) in ground water in Colorado. These maps can be incorporated into the State Pesticide Management Plan and can help provide a sound hydrogeologic basis for atrazine management in Colorado. Maps showing the probability of detecting elevated nitrite plus nitrate as nitrogen (nitrate) concentrations in ground water in Colorado also were developed because nitrate is a contaminant of concern in many areas of Colorado. Maps showing the probability of detecting atrazine and(or) desethyl-atrazine (atrazine/DEA) at or greater than concentrations of 0.1 microgram per liter and nitrate concentrations in ground water greater than 5 milligrams per liter were developed as follows: (1) Ground-water quality data were overlaid with anthropogenic and hydrogeologic data using a geographic information system to produce a data set in which each well had corresponding data on atrazine use, fertilizer use, geology, hydrogeomorphic regions, land cover, precipitation, soils, and well construction. These data then were downloaded to a statistical software package for analysis by logistic regression. (2) Relations were observed between ground-water quality and the percentage of land-cover categories within circular regions (buffers) around wells. Several buffer sizes were evaluated; the buffer size that provided the strongest relation was selected for use in the logistic regression models. (3) Relations between concentrations of atrazine/DEA and nitrate in ground water and atrazine use, fertilizer use, geology, hydrogeomorphic regions, land cover, precipitation, soils, and well-construction data were evaluated, and several preliminary multivariate models with various

  18. Methods of Analysis by the U.S. Geological Survey Organic Geochemistry Research Group-Determination of Dissolved Isoxaflutole and Its Sequential Degradation Products, Diketonitrile and Benzoic Acid, in Water Using Solid-Phase Extraction and Liquid Chromatography/Tandem Mass Spectrometry

    USGS Publications Warehouse

    Meyer, Michael T.; Lee, Edward A.; Scribner, Elisabeth A.

    2007-01-01

    An analytical method for the determination of isoxaflutole and its sequential degradation products, diketonitrile and a benzoic acid analogue, in filtered water with varying matrices was developed by the U.S. Geological Survey Organic Geochemistry Research Group in Lawrence, Kansas. Four different water-sample matrices fortified at 0.02 and 0.10 ug/L (micrograms per liter) are extracted by vacuum manifold solid-phase extraction and analyzed by liquid chromatography/tandem mass spectrometry using electrospray ionization in negative-ion mode with multiple-reaction monitoring (MRM). Analytical conditions for mass spectrometry detection are optimized, and quantitation is carried out using the following MRM molecular-hydrogen (precursor) ion and product (p) ion transition pairs: 357.9 (precursor), 78.9 (p), and 277.6 (p) for isoxaflutole and diketonitrile, and 267.0 (precursor), 159.0 (p), and 223.1 (p) for benzoic acid. 2,4-dichlorophenoxyacetic acid-d3 is used as the internal standard, and alachlor ethanesulfonic acid-d5 is used as the surrogate standard. Compound detection limits and reporting levels are calculated using U.S. Environmental Protection Agency procedures. The mean solid-phase extraction recovery values ranged from 104 to 108 percent with relative standard deviation percentages ranging from 4.0 to 10.6 percent. The combined mean percentage concentration normalized to the theoretical spiked concentration of four water matrices analyzed eight times at 0.02 and 0.10 ug/L (seven times for the reagent-water matrix at 0.02 ug/L) ranged from approximately 75 to 101 percent with relative standard deviation percentages ranging from approximately 3 to 26 percent for isoxaflutole, diketonitrile, and benzoic acid. The method detection limit (MDL) for isoxaflutole and diketonitrile is 0.003 ug/L and 0.004 ug/L for benzoic acid. Method reporting levels (MRLs) are 0.011, 0.010, and 0.012 ug/L for isoxaflutole, diketonitrile, and benzoic acid, respectively. On the basis

  19. Concentrations and transport of suspended sediment, nutrients, and pesticides in the lower Mississippi-Atchafalaya River subbasin during the 2011 Mississippi River flood, April through July

    USGS Publications Warehouse

    Welch, Heather L.; Coupe, Richard H.; Aulenbach, Brent T.

    2014-01-01

    High streamflow associated with the April–July 2011 Mississippi River flood forced the simultaneous opening of the three major flood-control structures in the lower Mississippi-Atchafalaya River subbasin for the first time in history in order to manage the amount of water moving through the system. The U.S. Geological Survey (USGS) collected samples for analysis of field properties, suspended-sediment concentration, particle-size, total nitrogen, nitrate plus nitrite, total phosphorus, orthophosphate, and up to 136 pesticides at 11 water-quality stations and 2 flood-control structures in the lower Mississippi-Atchafalaya River subbasin from just above the confluence of the upper Mississippi and Ohio Rivers downstream from April through July 2011. Monthly fluxes of suspended sediment, suspended sand, total nitrogen, nitrate plus nitrite, total phosphorus, orthophosphate, atrazine, simazine, metolachlor, and acetochlor were estimated at 9 stations and 2 flood-control structures during the flood period. Although concentrations during the 2011 flood were within the range of what has been observed historically, concentrations decreased during peak streamflow on the lower Mississippi River. Prior to the 2011 flood, high concentrations of suspended sediment and nitrate were observed in March 2011 at stations downstream of the confluence of the upper Mississippi and Ohio Rivers, which probably resulted in a loss of available material for movement during the flood. In addition, the major contributor of streamflow to the lower Mississippi-Atchafalaya River subbasin during April and May was the Ohio River, whose water contained lower concentrations of suspended sediment, pesticides, and nutrients than water from the upper Mississippi River. Estimated fluxes for the 4-month flood period were still quite high and contributed approximately 50 percent of the estimated annual suspended sediment, nitrate, and total phosphorus fluxes in 2011; the largest fluxes were estimated at

  20. Status of riverine soils of a Mediterranean river catchment (the Turia river, Spain) regarding potential contamination of heavy metals and pesticides

    NASA Astrophysics Data System (ADS)

    Andreu, Vicente; Gimeno-García, Eugenia; Pascual, Juan Antonio; Picó, Yolanda

    2016-04-01

    Rivers are sink structures receiving diffuse contamination mainly from agricultural practices. Hydrological dynamics of these watercourses favour, by one hand, the transport of contaminants (dissolved, complexed or adsorbed to suspended particles) and, by the other, their accumulation in sediments. These circumstances affect at different scales the quality of soils, waters, and the entire riverine ecosystems. In this work, 7 heavy metals and 50 pesticides were monitored in riverine soils of the Turia River catchment. From the source to the mounth, along the entiere river, 22 sampling points were selected for sampling according different lithologies, land uses, population size and the proximity to waste waters treatment plants (WWTPs). Cd, Co, Cr, Cu, Pb, Ni and Zn were analysed to determine its total and extractable contents in soils. Total content of metals was established by microwave acid digestion and the extractable fraction in soils and sediments by treatment with EDTA. Atomic Absorption Spectrometry, using graphite furnace when necessary, was used for the determination of the selected metals. Pesticide residues were extracted from the soil samples using the QuEchERS method and determined by Liquid Chromatograph-tandem Mass Spectrometry (LC-MS/MS). Recoveries ranged from 40 to 105 %. The limits of quantification ranged from 0.1 to 5.0 ng g-1. The higest levels of total and extractable Cd, Co, Cr and Ni were determined near the Benageber reservoir, located in the middle course of the river, where an important forest fires occurred a year ago. High levels of metals, mainly Cr and Zn, appeared headwaters in the Alfambra tributary. This deserves special mention because it was selected as a little impacted area that could serve as non-contaminated reference for the river. From the 50 pesticides condsidered, 26 were detected, with the highest levels for acetochlor (290.00 ng g-1) and a degradation product of terbutyazine - terbuthylazine deethyl - (234.75 ng g-1

  1. Assessmet of temporal distribution of pesticide residues in vineyard soils of La Rioja (Spain)

    NASA Astrophysics Data System (ADS)

    Pose Juan, Eva; Herrero Hernandez, Eliseo; Soledad Andrades, Maria; Rodriguez Cruz, Maria Sonia; Sanchez Martin, Maria Jesus

    2013-04-01

    The use and application of pesticides in vineyard is a common practice, which is important to prevent pest and diseases and improve the crop health and production, but on the other hand it could involve a potential risk for humans and the environment. For this reason, it is important to develop and validate a simple and fast multiresidue method to determine the presence of these compounds in soils. La Rioja region (Spain) is one of the most important wine-growing regions in Spain, which also entails that could be an important area of pesticide pollution. The objective of this work is to assess the temporal distribution of the possible pesticide pollution in soils from different areas of La Rioja (Spain). The pesticides selected in this study included fungicides (metalaxyl, and its metabolite CGA62826, pyrimethanil, tebuconazole, myclobutanil, kresoxim-methyl, triadimenol and flutriafol); herbicides (fluometuron, terbuthylazine and its metabolites desethylterbuthylazine and hydroxyterbuthylazine, lenacil, ethofumesate and acetochlor) and insecticides (methoxyfenozide and pirimicarb). The pesticide residues were evaluated by two analytical techniques, gas chromatography and liquid chromatography (GC-MS and LC-MS). The extraction procedure of pesticides from soils was optimized using two soil samples (blank soils) with different texture and characteristics collected from areas without pesticide application. Recoveries were studied in soil samples fortified with all pesticides at two levels of concentrations (the agronomic dose, 0.1 mg kg-1, and ten times this dose, 1 mg kg-1). Different extraction solvents were tested. The best results were obtained with methanol:acetone (50:50) mixture or methanol:CaCl2 0.01 M (50:50) mixture for hydroxyterbuthylazine and CGA62826. The accuracy (average recovery) and precision (reproducibility and repeatability) of the method were assessed using six replicates and the limits of detection (LODs) and quantification (LOQs) were

  2. Monitoring and modeling the fate of commonly used pesticides in surface water of the Lower Mekong Delta

    NASA Astrophysics Data System (ADS)

    van Toan, Pham; Sebesvari, Zita; Loan, Vo Phuong Hong; Renaud, Fabrice

    2010-05-01

    Introduction: The Lower Mekong Delta, one of the largest agricultural areas in Southeast Asia, has been reported to be increasingly polluted by agrochemicals since the beginning of the transformation processes in Vietnamese economy and specifically in the agricultural sector in 1986 (MRCS, 2007; Dasgupta et al., 2005; Dung, 2003; Phuong, 2003). Although pesticides have contributed significantly to enhancing agricultural productivity, these agrochemicals also have created risks to human health and environment (Margni, 2001; Phuong, 2003; Dasgupta et al., 2005) and lead to value loss of water resources (Phuong, 2003). While prohibited persistent organic pollutants such as HCHs and DDTs, were monitored and still detected in the Lower Mekong Delta in recent studies (Minh et al., 2007, Carvalho et al., 2008) little data exist on water pollution by recently used pesticides in the Delta. Aiming to fill this information gap, a study comprising three components was set up at two study sites of the Delta. Pesticide use and management was investigated through surveys and participatory rural appraisals with farmers; pesticide residue concentrations were determined in field outflows, connected irrigation canals and in drinking water and finally pesticide fate was predicted by using a coupled MIKE 11/ MIKE SHE model. This abstract focuses on the work done in the field of pesticide monitoring. The western study site (An Long Commune, Dong Thap province) represented an agricultural pattern with two intensive paddy rice crops per year and was heavily affected by flood in the rainy season. The second site located in the central part of the Delta (Ba Lang ward, Can Tho City) was characterized by a mix of paddy rice, vegetables and fruit trees. Fifteen pesticide compounds (buprofezin, butachlor, cypermethrin, difenozonazol, α-endosulfan, β-endosulfan, endosulfan-sulfate, fenobucarb, fipronil, hexaconazol, isoprothiolane, pretilachlor, profenofos, propanil, and propiconazol) were

  3. Monitoring and modeling the fate of commonly used pesticides in surface water of the Lower Mekong Delta

    NASA Astrophysics Data System (ADS)

    van Toan, Pham; Sebesvari, Zita; Loan, Vo Phuong Hong; Renaud, Fabrice

    2010-05-01

    Introduction: The Lower Mekong Delta, one of the largest agricultural areas in Southeast Asia, has been reported to be increasingly polluted by agrochemicals since the beginning of the transformation processes in Vietnamese economy and specifically in the agricultural sector in 1986 (MRCS, 2007; Dasgupta et al., 2005; Dung, 2003; Phuong, 2003). Although pesticides have contributed significantly to enhancing agricultural productivity, these agrochemicals also have created risks to human health and environment (Margni, 2001; Phuong, 2003; Dasgupta et al., 2005) and lead to value loss of water resources (Phuong, 2003). While prohibited persistent organic pollutants such as HCHs and DDTs, were monitored and still detected in the Lower Mekong Delta in recent studies (Minh et al., 2007, Carvalho et al., 2008) little data exist on water pollution by recently used pesticides in the Delta. Aiming to fill this information gap, a study comprising three components was set up at two study sites of the Delta. Pesticide use and management was investigated through surveys and participatory rural appraisals with farmers; pesticide residue concentrations were determined in field outflows, connected irrigation canals and in drinking water and finally pesticide fate was predicted by using a coupled MIKE 11/ MIKE SHE model. This abstract focuses on the work done in the field of pesticide monitoring. The western study site (An Long Commune, Dong Thap province) represented an agricultural pattern with two intensive paddy rice crops per year and was heavily affected by flood in the rainy season. The second site located in the central part of the Delta (Ba Lang ward, Can Tho City) was characterized by a mix of paddy rice, vegetables and fruit trees. Fifteen pesticide compounds (buprofezin, butachlor, cypermethrin, difenozonazol, α-endosulfan, β-endosulfan, endosulfan-sulfate, fenobucarb, fipronil, hexaconazol, isoprothiolane, pretilachlor, profenofos, propanil, and propiconazol) were

  4. Atmospheric transport, deposition, and fate of triazine herbicides and their metabolites in pristine areas at Isle Royale National Park

    USGS Publications Warehouse

    Thurman, E.M.; Cromwell, A.E.

    2000-01-01

    layer of the lakes increased during deposition periods and decreased later in the year. The fate of triazines in shallow lakes suggests faster degradation and shorter half-lives, while deeper lakes have residence times for atrazine that may exceed 10 years.Rainfall samples were collected at Isle Royale National Park, located in Lake Superior, and triazine herbicides were identified and quantified. Water samples were also collected from pristine lakes and analyzed for the presence of herbicides, and long-range atmospheric transport was determined using air-parcel, back-trajectory analysis. Results indicated that deposition was seasonal, with maximum concentrations occurring during the first week of June. Atrazine had the largest mass deposited on Isle Royal. Atrazine and deethylatrazine were the only herbicides detected in the surface-water samples. The annual mass of herbicides deposited by rainfall was calculated at 13.4, 3.7, and 54.0 ??g/m2, for 1992, 1993, and 1994, respectively. The source of the herbicides was attributed to Wisconsin, Minnesota, and Iowa, which are high-use areas for herbicides such as alachlor, atrazine, cyanazine, and metolachlor.

  5. Occurrence of selected pharmaceutical and non-pharmaceutical compounds, and stable hydrogen and oxygen isotope ratios, in a riverbank filtration study, Platte River, Nebraska, 2001 to 2003, Volume 1

    USGS Publications Warehouse

    Vogel, J.R.; Verstraeten, Ingrid M.; Coplen, T.B.; Furlong, E.T.; Meyer, M.T.; Barber, L.B.

    2005-01-01

    caffeine. Antibiotics were found in some of the wastewater samples and twice in Salt Creek. Antibiotics were not detected in any samples from the Platte River or the well field. Surface-water samples were analyzed for total organic carbon and ground-water samples were analyzed for dissolved organic carbon. Samples from all sites were analyzed for major ions. Herbicides commonly detected in surface, ground, and drinking water included acetachlor, alachlor, atrazine, and metolachlor as well as degradates of these compounds. Most of the samples from wastewater sites were found to contain predominantly acetamide degradates. High concentrations of several organic wastewater indicator compounds were detected at the wastewater sites and in Salt Creek. Several organic wastewater indicator compounds were detected multiple times in samples from the Platte River. Bromoform, a by-product of disinfection in the treatment plant, was found in samples from the finished drinking water. Stable hydrogen isotope ratios show a range in seasonal variation of -73.6 per mill to -38.1 per mill relative to Vienna Standard Mean Ocean Water (VSMOW) reference water and -69.2 per mill to -46.5 per mill for surface water and ground water, respectively. Oxygen isotope ratios for surface-water samples varied between -9.86 per mill and -5.05 per mill. Stable oxygen isotope ratios of ground waters varied between -9.62 per mill and -5.81 per mill.

  6. Ground-Water Quality in the Mohawk River Basin, New York, 2006

    USGS Publications Warehouse

    Nystrom, Elizabeth A.

    2008-01-01

    exceeded established State or Federal drinking-water standards of 10 mg/L as N for nitrate and 1 mg/L as N for nitrite. Ammonia concentrations were higher in samples from bedrock wells (median 0.349 mg/L as N) than in those from samples from sand and gravel wells (median 0.006 mg/L as N). The trace elements with the highest concentrations were strontium (median 549 micrograms per liter [?g/L]), iron (median 143 ?g/L), boron (median 35 ?g/L), and manganese (median 31.1 ?g/L). Concentrations of several trace elements, including boron, copper, iron, manganese, and strontium, were higher in samples from bedrock wells than those from sand and gravel wells. The highest radon-222 activities were in samples from bedrock wells (maximum 1,360 pCi/L); 44 percent of all samples exceeded a proposed U.S. Environmental Protection Agency drinking water standard of 300 pCi/L. Nine pesticides and pesticide degradates were detected in six samples at concentrations of 0.42 ?g/L or less; all were herbicides or their degradates, and most were degradates of alachlor, atrazine, and metolachlor. Six volatile organic compounds were detected in four samples at concentrations of 0.8 ?g/L or less, including four trihalomethanes, tetrachloroethene, and toluene; most detections were in sand and gravel wells and none of the concentrations exceeded drinking water standards. Coliform bacteria were detected in six samples but fecal coliform bacteria, including Escherichia coli, were not detected in any sample.

  7. Factors Affecting Spatial and Temporal Variability in Nutrient and Pesticide Concentrations in the Surficial Aquifer on the Delmarva Peninsula

    USGS Publications Warehouse

    Debrewer, Linda M.; Ator, Scott W.; Denver, Judith M.

    2007-01-01

    milligrams per liter (as nitrogen). In addition to land use in the aquifer recharge area, concentrations of nitrate in ground water are related to regional patterns in soil drainage that affect underlying aquifer redox conditions. Over the peninsula, nitrate concentrations are not related to recharge date of the water, but are positively correlated with depth in shallow wells screened beneath agricultural areas. Nitrate concentrations increased in oxic areas (dissolved oxygen greater than 1 milligram per liter) of the deeper part of the surficial aquifer used for domestic supply by an average of about 2 milligrams per liter between 1988 and 2001, although no changes were apparent in shallower parts of the aquifer over that same period. Water in the surficial aquifer generally flows from land-surface recharge to surface-water discharge areas in less than 30 years. As a result, the entire flow system in the surficial aquifer has likely been affected by human activities on and near the land surface over the past several decades. Pesticide compounds occurred widely at low levels throughout the surficial aquifer. The most commonly used herbicides (metolachlor, alachlor, and atrazine) were the most commonly detected. These pesticides primarily occurred in ground water in the form of degradation products. The widespread occurrence of these and other pesticide compounds reflects their abundant use as well as chemical properties and aquifer characteristics that allow their movement into ground water. Mixtures of pesticides are common. Most samples contained at least 3 different compounds; several samples contained as many as 11. Pesticide concentrations in the surficial aquifer are relatively high beneath recharge areas with well-drained soils in the shallow part of the aquifer and in oxic environments throughout the surficial aquifer. Concentrations are generally below existing drinking-water standards, although standards are not available for all of the pesticide compound

  8. Assessment of nutrients, suspended sediment, and pesticides in surface water of the upper Snake River basin, Idaho and western Wyoming, water years 1991-95

    USGS Publications Warehouse

    Clark, Gregory M.

    1997-01-01

    proportion to its discharge (less than 1 percent), the Twin Falls sewage-treatment plant was a major source of total phosphorus (13 percent). A comparison of discharge and loading in water year 1995 with estimates of instream transport showed a good correlation (relative difference of less than 15 percent) for discharge, total organic nitrogen, dissolved nitrite plus nitrate, total nitrogen, and total phosphorus. Estimates of dissolved ammonia and suspended sediment loads correlated poorly with instream transport; relative differences were about 79 and 61 percent, respectively. The pesticides EPTC, atrazine, desethylatrazine, metolachlor, and alachlor were the most commonly detected in the upper Snake River Basin and accounted for about 75 percent of all pesticide detections. All pesticides detected were at concentrations less than 1 microgram per liter and below water-quality criteria established by the U.S. Environmental Protection Agency. In samples collected from two small agriculturally dominated tributary basins, the largest number and concentrations of pesticides were detected in May and June following early growing season applications. At one of the sites, the pesticide atrazine and its metabolite desethylatrazine were detected throughout the year. On the basis of 37 samples collected basinwide in May and June 1994, total annual subbasin applications and instantaneous instream fluxes of EPTC and atrazine showed logarithmic relations with coefficients of determination (R2 values) of 0.55 and 0.62, respectively. At the time of sampling, the median daily flux of EPTC was about 0.0001 percent of the annual quantity applied, whereas the median daily flux of atrazine was between 0.001 and 0.01 percent.

  9. An overview comparing results from two decades of monitoring for pesticides in the Nation’s streams and rivers, 1992-2001 and 2002-2011

    USGS Publications Warehouse

    Stone, Wesley W.; Gilliom, Robert J.; Martin, Jeffrey D.

    2014-01-01

    This report provides an overview of the U.S. Geological Survey National Water-Quality Assessment program and National Stream Quality Accounting Network findings for pesticide occurrence in U.S. streams and rivers during 2002–11 and compares them to findings for the previous decade (1992–2001). In addition, pesticide stream concentrations were compared to Human Health Benchmarks (HHBs) and chronic Aquatic Life Benchmarks (ALBs). The comparisons between the decades were intended to be simple and descriptive. Trends over time are being evaluated separately in a series of studies involving rigorous trend analysis. During both decades, one or more pesticides or pesticide degradates were detected more than 90 percent of the time in streams across all types of land uses. For individual pesticides during 2002–11, atrazine (and degradate, deethylatrazine), carbaryl, fipronil (and degradates), metolachlor, prometon, and simazine were detected in streams more than 50 percent of the time. In contrast, alachlor, chlorpyrifos, cyanazine, diazinon, EPTC, Dacthal, and tebuthiuron were detected less frequently in streams during the second decade than during the first decade. During 2002–11, only one stream had an annual mean pesticide concentration that exceeded an HHB. In contrast, 17 percent of agriculture land-use streams and one mixed land-use stream had annual mean pesticide concentrations that exceeded HHBs during 1992–2001. The difference between the first and second decades in terms of percent of streams exceeding HHBs was attributed to regulatory changes. During 2002–11, nearly two-thirds of agriculture land-use streams and nearly one-half of mixed land-use streams exceeded chronic ALBs. For urban land use, 90 percent of the streams exceeded a chronic ALB. Fipronil, metolachlor, malathion, cis-permethrin, and dichlorvos exceeded chronic ALBs for more than 10 percent of the streams. For agriculture and mixed land-use streams, the overall percent of streams that

  10. Occurrence and distribution of selected contaminants in public drinking-water supplies in the surficial aquifer in Delaware

    USGS Publications Warehouse

    Ferrari, Matthew J.

    2001-01-01

    Water samples were collected from August through November 2000 from 30 randomly selected public drinking-water supply wells screened in the unconfined aquifer in Delaware, and analyzed to assess the occurrence and distribution of selected pesticide compounds, volatile organic compounds, major inorganic ions, and nutrients. Water from a subset of 10 wells was sampled and analyzed for radium and radon. The average age of ground water entering the well screens in all the wells was determined to be generally less than 20 years. Low concentrations of pesticide compounds and volatile organic compounds were detected throughout the State of Delaware, with several compounds often detected in each water sample. Pesticide and metabolite (pesticide degradation products) concentrations were generally less than 1 microgram per liter, and were detected in sam-ples from 27 of 30 wells. Of the 45 pesticides and 13 metabolites analyzed, 19 compounds (13 pesticides and 6 metabolites) were detected in at least 1 of the 30 samples. Desethylatrazine, alachlor ethane sulfonic acid, metolachlor ethane sulfonic acid, metolachlor, and atrazine were the most frequently detected pesticide compounds, and were present in at least half the samples. None of the pesticide detections was above the U.S. Environmental Protection Agency's Primary Maximum Contaminant Levels or Health Advisories. Volatile organic compounds also were present at low concentrations (generally less than 1 microgram per liter) in samples from all 30 wells. Of the 85 volatile organic com-pounds analyzed, 34 compounds were detected in at least 1 of the 30 samples. Chloroform, tetrachloroethene, and methyl tert-butyl ether were the most frequently detected volatile organic compounds, and were found in at least half the samples. None of the volatile organic compound detections was above U.S. Environmental Protection Agency's Primary Maximum Contaminant Levels or Health Advisories. A few samples contained compounds with

  11. Factors Affecting Occurrence and Distribution of Selected Contaminants in Ground Water From Selected Areas in the Piedmont Aquifer System, Eastern United States, 1993-2003

    USGS Publications Warehouse

    Lindsey, Bruce D.; Falls, William F.; Ferrari, Matthew J.; Zimmerman, Tammy M.; Harned, Douglas A.; Sadorf, Eric M.; Chapman, Melinda J.

    2006-01-01

    , dissolved oxygen concentration, lithology, depth to water, and soil-matrix characteristics. A linear regression model was used to determine that increases in the percentage of agricultural land use, the input of nitrogen from all sources, and dissolved oxygen were the most significant variables affecting increased concentration of nitrate. A logistic regression model was used to determine that those same factors were the most significant variables affecting whether or not the nitrate concentration would exceed 4 mg/L. Of the analysis of samples from 253 wells and 19 springs for 47 pesticides, no sample had a pesticide concentration that exceeded any USEPA MCL. The most frequently detected pesticide was desethyl atrazine, a degradation product of atrazine; the detection frequency was 47 percent. Other frequently detected pesticides included atrazine, metolachlor, simazine, alachlor, prometon, and dieldrin. Detection frequency was affected by the analytical reporting limits; the frequency of detection was somewhat lower when all pesticides were censored to the highest common detection limit. Source factors such as agricultural land use (for agricultural herbicides), urban land use (for insecticides), and the application rate were found to have positive statistical correlations with pesticide concentration. Transport factors such as depth to water and percentage of well-drained soils, sand, or silt typically were positively correlated with higher pesticide concentrations. Sampling for VOCs was conducted in 187 wells and 19 springs that were sampled for 59 VOCs. There were 137 detections of VOCs above the common censoring limit of 0.2 micrograms per liter. The most frequently detected VOCs were chloroform, a trihalomethane, and methyl-tert butyl ether (MTBE), a fuel oxygenate. Seventy-nine wells had at least one VOC detected. The detections were related to land use and well depth. Kendall's tau correlations indicated a significant positive correlation bet

  12. Occurrence, distribution, and transport of pesticides in agricultural irrigation-return flow from four drainage basins in the Columbia Basin Project, Washington, 2002-04, and comparison with historical data

    USGS Publications Warehouse

    Wagner, Richard J.; Frans, Lonna M.; Huffman, Raegan L.

    2006-01-01

    pendimethalin at Sand Hollow and statistically significant decreases were in concentrations of 2,6-diethylanaline, alachlor, atrazine, DCPA, and EPTC. A seasonal Kendall trend test on data from Lind Coulee indicated no statistically significant trends for any pesticide for 1994 through 2004. A comparison of pesticide concentrations detected in this study with those detected in previous U.S. Geological Survey National Water-Quality Assessment studies of the Central Columbia Plateau, Yakima River basin, and national agricultural studies indicated that concentrations in this study generally were in the middle to lower end of the concentration spectrum for the most frequently detected herbicides and insecticides, but that the overall rate of detection was near the high end. Thirty-one of the 42 herbicides, insecticides, and fungicides detected in surface-water samples were applied to the major agricultural crops in the drainage basins, and 11 of the detected pesticides are sold for residential application. Eight of the pesticides detected in surface-water samples were not reported as having any agricultural or residential use. The overall pattern of pesticide use depends on which crops are grown in each drainage basin. Drainage basins with predominantly more orchards have higher amounts of insecticides applied, whereas basins with larger percentages of field crops tend to have more herbicides applied. Pesticide usage was most similar in Crab Creek and Sand Hollow, where the largest total amounts applied were the insecticides azinphos-methyl, carbaryl, and chlorpyrifos and the herbicide EPTC. In Red Rock Coulee basin, DCPA was the most heavily applied herbicide, followed by the fungicide chlorothalonil, the herbicide EPTC, and the insecticides chlorpyrifos and azinphos-methyl. In Lind Coulee, which has a large percentage of dryland agricultural area, the herbicides 2,4-D and EPTC were applied in the largest amount, followed by the fungicide chlorothalonil. The

  13. Quality of Wisconsin stormwater, 1989-94

    USGS Publications Warehouse

    Bannerman, Roger T.; Legg, Andrew D.; Greb, Steven R.

    1996-01-01

    -sewer samples also exceeded Wisconsin's ground-water enforcement standards for pesticides, PCB's, phthalates, and chloride. Defined by criteria in this report, poten tial contaminants included five metals (lead, zinc, copper, silver, and cadmium), nine polycyclic aro matic hydrocarbons, Bis(2-ethylhexyl)phthalate, four pesticides (DDT, atrazine, alachlor, and 2,4 D), suspended solids, chlorides, total phosphorus, BOD 5-day, and bacteria. Wisconsin stormwater quality was similar to stormwater quality monitored in other states. Nearly one-half of median concentrations of con stituents in Wisconsin stormwater were within 30 percent of the medians from other states. The clos est agreement was seen for biochemical oxygen demand, total phosphorus, and total recoverable zinc. Similarities in stormwater quality for the storm sewer and urban streams indicated the storm sewers were a major source of water to the streams during storm events. Concentrations of potential contaminants in urban streams increased dramati cally during storm events as compared to baseflow concentrations.

  14. Probability of detecting atrazine/desethyl-atrazine and elevated concentrations of nitrate (NO2+NO3-N) in ground water in the Idaho part of the upper Snake River basin

    USGS Publications Warehouse

    Rupert, Michael G.

    1998-01-01

    Draft Federal regulations may require that each State develop a State Pesticide Management Plan for the herbicides atrazine, alachlor, cyanazine, metolachlor, and simazine. This study developed maps that the Idaho State Department of Agriculture might use to predict the probability of detecting atrazine and desethyl-atrazine (a breakdown product of atrazine) in ground water in the Idaho part of the upper Snake River Basin. These maps can be incorporated in the State Pesticide Management Plan and help provide a sound hydrogeologic basis for atrazine management in the study area. Maps showing the probability of detecting atrazine/desethyl-atrazine in ground water were developed as follows: (1) Ground-water monitoring data were overlaid with hydrogeologic and anthropogenic data using a geographic information system to produce a data set in which each well had corresponding data on atrazine use, depth to ground water, geology, land use, precipitation, soils, and well depth. These data then were downloaded to a statistical software package for analysis by logistic regression. (2) Individual (univariate) relations between atrazine/desethyl-atrazine in ground water and atrazine use, depth to ground water, geology, land use, precipitation, soils, and well depth data were evaluated to identify those independent variables significantly related to atrazine/ desethyl-atrazine detections. (3) Several preliminary multivariate models with various combinations of independent variables were constructed. (4) The multivariate models which best predicted the presence of atrazine/desethyl-atrazine in ground water were selected. (5) The multivariate models were entered into the geographic information system and the probability maps were constructed. Two models which best predicted the presence of atrazine/desethyl-atrazine in ground water were selected; one with and one without atrazine use. Correlations of the predicted probabilities of atrazine/desethyl-atrazine in ground water with

  15. Historical water-quality data for the High Plains Regional Ground-Water Study Area in Colorado, Kansas, Nebraska, New Mexico, Oklahoma, South Dakota, Texas, and Wyoming, 1930-98

    USGS Publications Warehouse

    Litke, David W.

    2001-01-01

    The High Plains aquifer underlies 174,000 square miles in parts of eight States and includes eight primary hydrogeologic units, including the well-known Ogallala Formation. The High Plains aquifer is an important resource, providing water for 27 percent of the Nation?s irrigated agricultural lands in an otherwise dry landscape. Since the 1980?s there has been concern over the sustainability of the aquifer due to water-level declines caused by substantial pumping. Water quality of the aquifer is a more recent concern. As part of the U.S. Geological Survey?s National Water-Quality Assessment Program, historical water-quality data have been gathered for the High Plains Regional Ground-Water Study Area into a retrospective data base, which can be used to evaluate the occurrence and distribution of water-quality constituents of concern.Data from the retrospective data base verify that nitrate, pesticides, and dissolved solids (salinity) are important water-quality concerns in the High Plains study area. Sixteen percent of all measured nitrate concentrations were larger than the U.S. Environmental Protection Agency drinking-water standard of 10 milligrams per liter. In about 70 percent of the counties within the High Plains study area, nitrate concentrations for 1980-98 were significantly larger than for 1930-69. While nitrate concentrations are largest where depth to water is shallow, concentrations also have increased in the Ogallala Formation where depth to water is large. Pesticide data primarily are available only in the northern half of the study area. About 50 pesticides were detected in the High Plains study area, but only four pesticides (atrazine, alachlor, cyanazine, and simazine) had concentrations exceeding a drinking-water standard. The occasional detection of pesticides in deeper parts of the Ogallala Formation indicates that contamination pathways exist. Dissolved solids, which are a direct measure of salinity, had 29 percent of measured concentrations in

  16. Pesticides and their metabolites in three small public water-supply reservoir systems, western New York, 1998-99

    USGS Publications Warehouse

    Phillips, Patrick J.; Eckhardt, David A.; Rosenmann, Larry

    2000-01-01

    Twenty five pesticides or pesticide metabolites were detected in samples collected from May, 1998 through January, 1999 in three small public- supply reservoirs in western New York.Samples were collected at tributaries and reservoir outlets for comparison with samples from the water-supply intakes. No samples from public-water-supply intakes exceeded any Federal or State water-quality standards, although some samples from tributaries did exceed a few standards. The maximum concentrations of the most frequently detected pesticides in water-supply intake samples were between 10 and 50 percent of the lowest applicable water quality standard. Pesticides that exceeded water-quality standards at the tributary sites were the herbicides atrazine, alachlor, and cyanazine, and the insecticide p,p?-DDE. Land use in the watersheds that surround these reservoirs is largely agricultural; thus, the results do not necessarily represent conditions in other water-supply reservoirs in New York State. The most frequently detected pesticides or pesticide metabolites were the corn herbicides atrazine and metolachlor, and two metabolites of metolachlor -metolachlor ethanesulfonic acid (ESA)and metolachlor oxanilic acid (OA). More than half of the samples from the three water-supply intake sites contained at least one of these compounds at concentrations greater than 0.2 ?g/L (micrograms per liter); the concentrations ranged from 0.01 to nearly 10 ?g/L. Many samples contained metabolites of other commonly used herbicides at concentrations greater than those of their parent compounds. Only two insecticides or insecticide metabolites were detected (carbofuran and p,p?-DDE and concentrations of these compounds were less than 0.1 ?g/L. The total concentration of pesticides and metabolites at the three water-supply intake sites are correlated with land use. The highest concentrations were in the watershed with the greatest percentage of row-crop land use,and the lowest concentrations were in

  17. Anthropogenic Organic Compounds in Source and Finished Groundwater of Community Water Systems in the Piedmont Physiographic Province, Potomac River Basin, Maryland and Virginia, 2003-04

    USGS Publications Warehouse

    Banks, William S.L.; Reyes, Betzaida

    2009-01-01

    frequently during the first phase. A total of 48 different anthropogenic organic compounds were detected in samples collected from source and finished water. There were a similar number of compounds detected in finished water (41) and in source water (39). The most commonly detected group of anthropogenic organic compounds in finished water was trihalomethanes - compounds associated with the disinfection of drinking water. This group of compounds accounted for 30 percent of the detections in source water and 44 percent of the detections in finished water, and were generally found in higher concentrations in finished water. Excluding trihalomethanes, the number of total detections was about the same in source-water samples (33) as it was in finished-water samples (35). During both phases of the study, two measurements for human-health assessment were used. The first, the Maximum Contaminant Level for drinking water, is set by the U.S. Environmental Protection Agency and represents a legally enforceable maximum concentration of a contaminant permitted in drinking water. The second, the Health-Based Screening Level, was developed by the U.S. Geological Survey, is not legally enforceable, and represents a limit for more chronic exposures. Maximum concentrations for each detected compound were compared with either the Maximum Contaminant Level or the Health-Based Screening Level when available. More than half of the compounds detected had either a Maximum Contaminant Level or a Health-Based Screening Level. A benchmark quotient was set at 10 percent (greater than or equal to 0.1) of the ratio of the detected concentration of a particular compound to its Maximum Contaminant Level, or Health-Based Screening Level. This was considered a threshold for further monitoring. During phase one, when only source water was sampled, seven compounds (chloroform, benzene, acrylonitrile, methylene chloride, atrazine, alachlor, and dieldrin) met or exceeded a benchmark quotient. No de

  18. Occurrence and distribution of organic chemicals and nutrients and comparison of water-quality data from public drinking-water supplies in the Columbia aquifer in Delaware, 2000-08

    USGS Publications Warehouse

    Reyes, Betzaida

    2010-01-01

    The U.S. Geological Survey, in cooperation with the Delaware Department of Natural Resources and Environmental Control and the Delaware Geological Survey, conducted a groundwater-quality investigation to (a) describe the occurrence and distribution of selected contaminants, and (b) document any changes in groundwater quality in the Columbia aquifer public water-supply wells in the Coastal Plain in Delaware between 2000 and 2008. Thirty public water-supply wells located throughout the Columbia aquifer of the Delaware Coastal Plain were sampled from August through November of 2008. Twenty-two of the wells in the sampling network for this project were previously sampled in 2000. Eight new wells were selected to replace wells no longer in use. Groundwater collected from the wells was analyzed for the occurrence and distribution of selected pesticides, pesticide degradates, volatile organic compounds, nutrients, and major inorganic ions. Nine of the wells were analyzed for radioactive elements (radium-226, radium-228, and radon). Groundwater-quality data were compared for sites sampled in both 2000 and 2008 to document any changes in water quality. One or more pesticides were detected in samples from 29 of the 30 wells. There were no significant differences in pesticide and pesticide degradate concentrations and similar compounds were detected when comparing sampling results from 2000 and 2008. Pesticide and pesticide degradate concentrations were generally less than 1 microgram per liter. Twenty-four compounds, 14 pesticides, and 10 pesticide degradates were detected in at least one sample; the pesticide degradates, metolachlor ethanesulfonic acid, deethylatrazine, and alachlor ethanesulfonic acid were the most frequently detected compounds, each found in more than 50 percent of samples. Almost 80 percent of the detected pesticides were agricultural herbicides, which reflects the prevalence and wide distribution of agriculture in sampled areas, as well the dominance of

  19. Effect of urbanization on the water resources of eastern Chester County, Pennsylvania

    USGS Publications Warehouse

    Sloto, R.A.

    1987-01-01

    The effects of human activity on the water resources of a 207-square-mile area of eastern Chester County was evaluated. The most serious consequence of urbanization is the contamination of ground water by volatile organic compounds, which were detected in 39 percent of the 70 wells sampled. As many as nine compounds were found in one water sample, and the concentration of total volatile organic compounds was as high as 17,400 ug/L (micrograms per liter). In the Chester Valley, volatile organic compounds are moving down the hydraulic gradient caused by quarry dewatering. Movement through the quarries reduces concentrations of these compounds and removes most of them. Phenol was detected in 28 percent of 54 wells sampled, with concentrations up to 7 ug/L. Metals, except for iron and manganese, and other trace constituents generally are not a water-quality problem. However, ground water in an area in Chester Valley has been contaminated by concentrations of boron as high as 20,000 ug/L and lithium as high as 13,000 ug/L. The ground water discharges to Valley Creek, where concentrations of boron are as high as 130 ug/L and lithium as high as 800 ug/L. Concentrations of chloride as high as 2,100 mg/L (milligrams per liter) were found in a well at a former highway salt storage site. Wells completed in carbonate rock downgradient from the Pennsylvania Turnpike had chloride concentrations as high as 350 mg/L. The base-neutral organic compounds bis(2-ethylhexyl) phthalate, di-n-butyl phthalate, and 1,2-dichlorobenzene, and the pesticides alachlor, aldrian, diazanon, DDD, DDT, dieldrin, methyl parathion, picloram, and 2,4-D were detected in a few water samples in low concentrations, However, these organic compounds do not present a widespread water-quality problem. Neither acid organic compounds nor polychlorinated napthalenes (PCN) were detected in ground water. The growth of public water and sewer systems has resulted in a significant interbasin transfer of water

  20. Groundwater quality in the Columbia Plateau, Snake River Plain, and Oahu basaltic-rock and basin-fill aquifers in the Northwestern United States and Hawaii, 1992-2010

    USGS Publications Warehouse

    Frans, Lonna M.; Rupert, Michael G.; Hunt, Charles D., Jr.; Skinner, Kenneth D.

    2012-01-01

    decades in the oxygen-rich groundwater of the Columbia Plateau and the Snake River Plain, so prudent groundwater protection measures are critical to protect drinking water resources by reducing nitrate leaching from the land surface. Nitrate logistic regression models indicated that areas with a high percentage of land in crops (such as potatoes or sugarcane) and soils with low amounts of organic matter are most likely to have elevated nitrate concentrations in the groundwater. Areas where agricultural activities were absent had much lower probabilities of detecting elevated nitrate concentrations. The Columbia Plateau had a much higher probability of having elevated nitrate concentrations, with most of the land area having greater than a 50 percent probability of elevated nitrate concentrations. Oahu and the Snake River Plain had a much lower probability of having elevated nitrate concentrations because of their lower percentage of agricultural land. Pesticides were detected at many sites in groundwater of the Columbia Plateau, Snake River Plain, and Oahu but generally at low concentrations below human-health benchmarks. Atrazine and its degradate (a compound produced from the breakdown of a parent pesticide), deethylatrazine, were the most commonly detected pesticides in groundwater sampled in the Columbia Plateau and Snake River Plain. Bromacil was the most commonly detected pesticide on Oahu. The other pesticides most commonly detected in the study areas include simazine, hexazinone, metribuzin, diuron, prometon, metolachlor, p,p'-DDE, dieldrin, 2-4-D, and alachlor. DDE (a degradate of DDT) and dieldrin are still being detected in groundwater despite having been banned for more than 30 years. Codetection of multiple pesticides in water from a single well was common. The widespread occurrence of pesticides in groundwater in the study areas indicates that the groundwater is highly susceptible to pesticide contamination. Some pesticides were detected in groundwater