The role of humic acids and biochar as specific sorbents of pesticides in soil

NASA Astrophysics Data System (ADS)

Ćwieląg-Piasecka, Irmina; Dębicka, Magdalena; Medyńska-Jureszek, Agnieszka; Weber, Jerzy; Jamroz, Elżbieta

2017-04-01

Pesticides are widely used in agriculture to prevent or control different pests and increase yield as well as products quality. Despite of the strict regulations concerning sustainable use of plant protection products, their residues are very often present in soil. Depending on their chemical and physical properties, they undergo various transformations in the soil. This results in their retention on different sorbents, degradation by microorganisms or leaching to the groundwater. Biochar is a carbon-rich byproduct of thermal biomass conversion, and due to its high sorption properties can be an efficient sorbent for pesticides in soil. The aim of the research was to compare the effect of two types of organic sorbents - humic acids (HA) and biochar (BC) - in sorption-desorption processes of different pesticides, which residues are commonly present in arable soils and thus are potentially harmful for the environment. The humic acids were extracted from topsoil horizon of arable cambisoil derived from loam (Lower Silesia, Poland) by Shnitzer's method, then purified using XAD resin and freeze-dried. Biochar was produced from wheat straw in gasification process at 550˚C, remaining 30 minutes in the reactor. Investigated pesticides belong to three different chemical classes: carbamates (carbaryl and carbofuran), phenoxyacetic acids (2,4-D and MCPA) and aniline derivatives (metolachlor), and are active substances of commonly used plant protection products in agriculture. To obtain the experimental goal the sorption experiment was conducted. To the investigated organic matter samples (HA or BC) aliquots of pesticides solutions in 10M CaCl2 were added and the mixtures were shaken for 24h. Afterwards the samples were centrifuged and supernatants analyzed by LC-MS/MS for the pesticides content. After that the same samples were refilled with CaCl2 and analyzed in the same way for desorption studies. Humic acids exhibited strong affinity for the ionic substances (2,4-D, MCPA), for which high percentage uptake was obtained (about 70% of the compound sorbed). Retention of carbamates on HA were much weaker, on contrary to their behavior towards BC - the uptake of carbamates on BC was nearly total (in the range from 90 to nearly 100%). Metolachlor was sorbed comparably strong both by HA and BC. Noticeable desorption occurred only in case of 2,4-D bound to HA, which might suggest the moderately strong bonding type. On the other hand, in case of BC desorption was completely inhibited due to stronger type of interaction with investigated substances. The obtained results indicate that the sorption behaviour of HA and BC is completely different, depending on the chemical structure both of the organic sorbents and pesticides used. Hydrophobic surface of adopted BC may preferentially attract pesticides of nonpolar and nonionic structural features. Soil humic acids, which are main sorbents of organic pollutants in soil, bind chemicals through the ionic, hydrogen and covalent bonding as well as hydrophobic bonding or van der Waals forces, which in some cases may result in a weaker pesticide retention.

DEGRADATION OF THE CHLORINATED PHENOXYACETATE HERBICIDES 2,4-DICHLOROPHENOXYACETIC ACID AND 2,4,5- TRICHLOROPHENOXYACETIC BY PURE AND MIXED BACTERIAL CULTURES

EPA Science Inventory

Combined cell suspensions of the 2,4,5-trichlorophenoxyacetic acid (2,4,5-T)-metabolizing organism Pseudomonas cepacia AC1100, and the 2,4-dichlorophenoxyacetic acid (2,4-D)-metabolizing organism Alcaligenes eutrophus JMP134 were shown to effectively degrade either of these compo...

Deaths from pesticide poisoning in England and Wales: 1945-1989.

PubMed

Casey, P; Vale, J A

1994-02-01

1. Data on deaths from pesticide poisoning occurring in England and Wales between 1945 and 1989 (no data are available for 1954) have been collated; pesticides were responsible for only 1012 (1.1%) of the 87,385 deaths from poisoning (excluding those due to carbon monoxide) occurring over this 44 year period. At least 73% of all pesticide fatalities were due to suicide and overall there was a predominance of males (male:female ratio 2.4:1). No deaths from pesticide poisoning in children under 10 years have been reported since 1974 although almost 50% of suspected pesticide poisoning incidents involve this age group. 2. Herbicides were responsible for 787 (78%) fatal poisonings, 110 (11%) were caused by insecticides, 69 (6.8%) by rodenticides, 30 (3.0%) by wood preservatives and 16 (1.6%) by other pesticides. 3. The herbicide, paraquat, was responsible for 570 of 1012 (56%) deaths and, although there has been a progressive decline in the annual number of deaths from paraquat poisoning since 1982, paraquat remains the most common cause of fatal pesticide poisoning in England and Wales. 4. Sodium chlorate caused 113 (11.2%) deaths, most of these fatalities occurring between 1965 and 1983; only one death has been recorded since 1984. The phenoxyacetate herbicides resulted in 50 deaths; 2,4-D was implicated most commonly. Sixty-eight deaths were due to organophosphorus insecticides; demeton-S-methyl, malathion and mevinphos were involved most frequently. Only eight deaths resulted from organochlorine insecticides and two of these also involved an organophosphorus insecticide.(ABSTRACT TRUNCATED AT 250 WORDS)

Colloidal Assemblies Effect on Chemical Reactions

DTIC Science & Technology

1988-12-01

phenoxyacetic acid (2,4,5-T) and 2,4,5-trichlorophenol on TiO led to complete mineralization into CO and HCl. In the degradatior of 2,4,5-T several...for the reasons already given. Of course this effect is much more evident in the acidic medium than in the alkaline me- dium where a very large amount...nearly similar times (see Fig.42). The results of Table 4 also indicate that a HC104 effect exists, and at higher concentrations of this acid the

Formation of 6-Aminopenicillanic Acid, Penicillins, and Penicillin Acylase by Various Fungi

PubMed Central

Cole, M.

1966-01-01

Several penicillin-producing fungi were examined for ability to produce 6-aminopenicillanic acid (6-APA) and penicillin acylase. 6-APA was found in corn steep liquor fermentations of Trichophyton mentagrophytes, Aspergillus ochraceous, and three strains of Penicillium sp. 6-APA was not detected in fermentations of Epidermophyton floccosum although penicillins were produced. 6-APA formed a large part of the total antibiotic production of T. mentagrophytes. The types of penicillins produced by various fungi were identified by paper chromatography, and it was found that all cultures produced benzylpenicillin. T. mentagrophytes and A. ochraceous showed increased yields of benzylpenicillin and the formation of phenoxymethylpenicillin in response to the addition to the fermentation medium of phenylacetic acid and phenoxyacetic acid, respectively. Washed mycelia of the three Penicillium spp. and two high penicillin-yielding strains of P. chrysogenum possessed penicillin acylase activity against phenoxymethylpenicillin. A. ochraceous, T. mentagrophytes, E. floccosum, and Cephalosporium sp. also had penicillin acylase activity against phenoxymethylpenicillin. Only two of the above fungi, T. mentagrophytes and E. floccosum, showed significant penicillin acylase activity against benzylpenicillin; in both cases it was very low. The acylase activity of A. ochraceous was considerably increased by culturing in the presence of phenoxyacetic acid. It is concluded that 6-APA frequently but not invariably accompanies the formation of penicillin, and that penicillin acylase activity against phenoxymethylpenicillin is present in all penicillin-producing fungi. PMID:5950252

Pd-loaded carbon felt as the cathode for selective dechlorination of 2,4-dichlorophenoxyacetic acid in aqueous solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsyganok, A.I.; Yamanaka, Ichiro; Otsuka, Kiyoshi

1998-11-01

Electrocatalytic reductive dehalogenation of 2,4-dichlorophenoxyacetic acid (2,4-D) to phenoxyacetic acid in aqueous solution containing MeOH, trifluoroacetic acid, and tetraalkylammonium salt was studied. A Teflon-made two-compartment flow-through cell with a permeable carbon felt cathode and a platinum foil anode was employed. Several noble metals were tested as electrocatalysts. Palladium-loaded carbon felt was found to be the most suitable significantly enhanced its electrocatalytic activity toward 2,4-D dechlorination. The reaction was hypothesized to proceed at carbon-palladium interface areas through 4-chlorine cleavage to form 2-chlorophenoxyacetic acid as the main reaction intermediate.

Fatal overdose of 2,4-dichlorophenoxyacetic acid (2,4-D).

PubMed

Keller, T; Skopp, G; Wu, M; Aderjan, R

1994-03-01

An ingestion of an unknown quantity of U 46 D-Fluid (500 g dichlorophenoxyacetic acid/l) in a suicide is described. Although 2,4-dichlorophenoxyacetic acid (2,4 D) is widely used as a herbicide, intoxications are relatively rare. Quantitation of 2,4-D was performed by diethyl ether extraction from acidified samples (viscera) or by deproteinization (blood, plasma) with methanol before HPLC analysis. Postmortem concentrations of 2,4-D in body fluids and tissues are given. The proposed method resulted in a rapid procedure most useful in cases of deliberate poisoning with phenoxyacetic herbicides.

Direct access to highly crystalline mesoporous nano TiO2 using sterically bulky organic acid templates

NASA Astrophysics Data System (ADS)

Bakre, Pratibha V.; Tilve, S. G.

2018-05-01

Sterically bulky monocarboxylic acid templates pivalic acid and phenoxyacetic acid are reported for the first time as organic templates in the sol-gel synthesis of TiO2. Mesoporous nanoparticulates of pure anatase phase and of well defined size were synthesized. The characterization of the materials prepared was done by various methods such as XRD, SEM, TEM, FTIR, UV-DRS, BET, etc. The prepared TiO2 samples were evaluated for the day light photodegradation of methylene blue by comparing with Degussa P25 and templates free synthesized TiO2 and were found to be more efficient.

[Evaluation of human health risk for a population from Cali, Colombia, by exposure to lead, cadmium, mercury, 2,4-dichloro-phenoxyacetic acid and diuron associated with water and food consumption].

PubMed

Echeverry, Ghisliane; Zapata, Andrés Mauricio; Páez, Martha Isabel; Méndez, Fabián; Peña, Miguel

2015-08-01

Exposure to pollutants such as pesticides and heavy metals has been linked to health problems. Several studies have revealed the presence of these contaminants in Cali; however, there is no information available about the main routes of exposure and risk of these contaminants. To estimate the risk associated with the intake of cadmium, lead and mercury, and pesticides 2,4-D and diuron through the consumption of water and food in a population in Cali. Population and environmental data were obtained, and a risk assessment was performed using United States Environmental Protection Agency guidelines. The concentrations of the evaluated pollutants were below permissible levels as established by the Colombian Ministerio de Ambiente, Vivienda y Desarrollo Territorial (3 µg/L -1 of cadmium; 10 µg/L -1 of lead; 1 µg/L -1 of mercury; 1 µg/L -1 of 2,4 D; 1 µg/L -1 of diuron). Salema butterfish ( Peprilus snyderi ) samples contained levels of cadmium between 20 and 80 µg/kg -1 , which are below the permissible limit set by the World Health Organization (100 µg/kg -1 ). The results of the risk assessment indicated that the carcinogenic and non-carcinogenic attributable risk to population health from the intake of food contaminants was below the maximum level permitted by the United States Environmental Protection Agency. It is believed that the findings in previous studies on pollutants may have been due to specific contamination events; therefore, monitoring and early warning about water intake is recommended. Furthermore, the report of cadmium being found in fish consumed as food suggests the need for quality control by regulators.

Exploring the functional diversity of the supraglacial environment: Microbial degradation of the pesticide 2,4-D on the Greenland Ice Sheet

NASA Astrophysics Data System (ADS)

Stibal, M.; Bælum, J.; Holben, W. E.; Jacobsen, C. S.

2012-12-01

The surface of the Greenland ice sheet (GrIS) harbours a diverse community of heterotrophic microorganisms. Organic compounds of anthropogenic origin, including pesticides, are deposited on the GrIS; however, the fate of these compounds in the ice is currently unknown. In this study we determine the potential of the microbial community from the surface of the GrIS to mineralise the pesticide 2,4-dichlorophenoxyacetic acid (2,4-D). It is one of the most easily degraded compounds among the phenoxyacetic acid pesticides, and the ability to mineralise 2,4-D has been found to be widespread in microbial communities around the globe. Functional genes involved in the degradation pathway have also been characterised. Thus, 2,4-D represents a very suitable model compound to use in order to gain an insight into pollutant degradation dynamics in the rapidly changing Arctic region. We collected surface ice cores on the GrIS and incubated them for up to 529 days in microcosms simulating in situ conditions. We measured mineralisation of side-chain- and ring-labelled 14C-2,4-D in the samples and performed quantitative PCR targeting the tfdA gene, encoding an enzyme catalysing the first step in the degradation pathway of 2,4-D, in the DNA extracted from the ice after the experiments. We show that the microbial community on the surface of the GrIS is of low diversity, but contains microbes capable of degrading 2,4-D. The low diversity of the community and the similarity of the detected clones to those from other icy environment clones suggest that the bacterial community on the GrIS is selected from a pool of propagules deposited on the surface of the ice sheet, based on the level of adaptation to the conditions in the surface ice. The 2,4-D degraders are likely present in very low numbers, and they can mineralise 2,4-D at a rate of up to 1 nmol per m2 per day, equivalent to ~26 ng C m-2 d-1. We contend that the surface of the GrIS should not be considered to be a mere reservoir of all atmospheric contaminants, as it is likely that some deposited compounds will be removed from the system via biodegradation processes before their potential release due to the accelerated melting of the ice sheet.

Anaerobic degradation of veratrylglycerol-beta-guaiacyl ether and guaiacoxyacetic acid by mixed rumen bacteria.

PubMed Central

Chen, W; Supanwong, K; Ohmiya, K; Shimizu, S; Kawakami, H

1985-01-01

Veratrylglycerol-beta-guaiacyl ether (0.2 g/liter), a lignin model compound, was found to be degraded by mixed rumen bacteria in a yeast extract medium under strictly anaerobic conditions to the extent of 19% within 24 h. Guaiacoxyacetic acid, 2-(o-methoxyphenoxy)ethanol, vanillic acid, and vanillin were detected as degradation products of veratrylglycerol-beta-guaiacyl ether by thin-layer chromatography, gas chromatography, and gas chromatography-mass spectrometry. Guaiacoxyacetic acid (0.25 g/liter), when added into the medium as a substrate, was entirely degraded within 36 h, resulting in the formation of phenoxyacetic acid, guaiacol, and phenol. These results suggest that the beta-arylether bond, an important intermonomer linkage in lignin, can be cleaved completely by these rumen anaerobes. PMID:3841472

Phenoxyacetic acid degradation by the 2,4-dichlorophenoxyacetic acid (TFD) pathway of plasmid pJP4: mapping and characterization of the TFD regulatory gene, tfdR.

PubMed Central

Harker, A R; Olsen, R H; Seidler, R J

1989-01-01

Plasmid pJP4 enables Alcaligenes eutrophus JMP134 to degrade 3-chlorobenzoate and 2,4-dichlorophenoxyacetic acid (TFD). Plasmid pRO101 is a derivative of pJP4 obtained by insertion of Tn1721 into a nonessential region of pJP4. Plasmid pRO101 was transferred by conjugation to several Pseudomonas strains and to A. eutrophus AEO106, a cured isolate of JMP134. AEO106(pRO101) and some Pseudomonas transconjugants grew on TFD. Transconjugants with a chromosomally encoded phenol hydroxylase also degraded phenoxyacetic acid (PAA) in the presence of an inducer of the TFD pathway, namely, TFD or 3-chlorobenzoate. A mutant of one such phenol-degrading strain, Pseudomonas putida PPO300(pRO101), grew on PAA as the sole carbon source in the absence of inducer. This isolate carried a mutant plasmid, designated pRO103, derived from pRO101 through the deletion of a 3.9-kilobase DNA fragment. Plasmid pRO103 constitutively expressed the TFD pathway, and this allowed the metabolism of PAA in the absence of the inducer, TFD. Complementation of pRO103 in trans by a DNA fragment corresponding to the fragment deleted in pRO101 indicates that a negative control-regulatory gene (tfdR) is located on the BamHI E fragment of pRO101. Other subcloning experiments resulted in the cloning of the tfdA monooxygenase gene on a 3.5-kilobase fragment derived from pRO101. This subclone, in the absence of other pRO101 DNA, constitutively expressed the tfdA gene and allowed PPO300 to grow on PAA. Preliminary evidence suggests that the monooxygenase activity encoded by this DNA fragment is feedback-inhibited by phenols. Images PMID:2914848

Some aspects of the etiology of non-Hodgkin's lymphoma.

PubMed Central

Hardell, L; Lindström, G; van Bavel, B; Fredrikson, M; Liljegren, G

1998-01-01

In epidemiologic studies, non-Hodgkin's lymphoma (NHL) has been associated with exposure to chemicals such as phenoxyacetic acids; chlorophenols; dioxins; organic solvents including benzene, polychlorinated biphenyls, chlordanes; and immunosuppressive drugs. Experimental evidence and clinical observations indicate that these chemicals may impair the immune system. The risk is increased for NHL in persons with acquired and congenital immune deficiency as well as autoimmune disorders. Also, certain viruses have been suggested to be of etiologic significance for NHL. In some cases of NHL the common mechanism for all these agents and conditions may be immunosuppression, possibly in combination with viruses. PMID:9599716

Comparison of the solid-phase fragment condensation and phase-change approaches in the synthesis of salmon I calcitonin.

PubMed

Gatos, D; Tzavara, C

2001-02-01

Salmon I calcitonin was synthesized using both phase-change and conventional solid-phase fragment condensation (SPFC) approaches, utilizing the Rink amide linker (Fmoc-amido-2,4-dimethoxybenzyl-4-phenoxyacetic acid) combined with 2-chlorotrityl resin and the Fmoc/tBu(Trt)-based protection scheme. Phase-change synthesis, performed by the selective detachment of the fully protected C-terminal 22-mer peptide-linker from the resin and subsequent condensation in solution with the N-terminal 1-10 fragment, gave a product of slightly less purity (85 vs. 92%) than the corresponding synthesis on the solid-phase. In both cases salmon I calcitonin was easily obtained in high purity.

Metabolism of 4-Chloro-2-Methylphenoxyacetic Acid by Soil Bacteria

PubMed Central

Bollag, J.-M.; Helling, C. S.; Alexander, M.

1967-01-01

A microorganism capable of degrading 4-chloro-2-methylphenoxyacetic acid (MCPA) was isolated from soil and identified as Flavobacterium peregrinum. All of the chlorine of MCPA was released as chloride, and the carboxyl-carbon was converted to volatile products by growing cultures of the bacterium, but a phenol accumulated in the medium. The phenol was identified as 4-chloro-2-methylphenol on the basis of its gas chromatographic and infrared characteristics. Extracts of cells of F. peregrinum and of a phenoxyacetate-metabolizing Arthrobacter sp. dehalogenated MCPA and several catechols but not 4-chloro-2-methylanisole. The Arthrobacter sp. cell extract was fractionated, and an enzyme preparation was obtained which catalyzed the conversion of MCPA to 4-chloro-2-methylphenol. The latter compound was not metabolized unless reduced nicotinamide adenine dinucleotide phosphate was added to the fractionated extract. The phenol in turn was apparently oxidized to a catechol by components of the enzyme preparation. PMID:16349751

Characterization of 2,4-dichlorophenoxyacetic acid and 2,4,5-trichlorophenoxyacetic acid-degrading fungi in Vietnamese soils.

PubMed

Itoh, Kazuhito; Kinoshita, Masahiro; Morishita, Shigeyuki; Chida, Masateru; Suyama, Kousuke

2013-04-01

Sixty-nine fungal strains were isolated countrywide from 10 Vietnamese soils, in areas both with and without a history of exposure to Agent Orange, and their degrading activities on the phenoxy acid herbicides 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), as well as related compounds, were examined. Among taxonomically various fungi, 45, 12 and 4% of the isolates degraded phenoxyacetic acid (PA), 2,4-D and 2,4,5-T, respectively. While the PA-degrading fungi were distributed to all sites and among many genera, the 2,4-D-degraders were found only in order Eurotiales in class Eurotiomycetes. All of the 2,4,5-T-degrading fungal strains were phylogenetically close to Eupenicillium spp. and were isolated from southern Vietnam. As a degradation intermediate, the corresponding phenol compounds were detected in some strains. The degradation substrate spectrum for 26 compounds of Eupenicillium spp. strains including 2,4,5-T-degraders and -non-degraders seemed to be related to phylogenetic similarity and soil sampling location of the isolates. These results suggest that the heavily contaminated environments enhanced the adaptation of the phylogenetic group of Eupenicillium spp. toward to obtain the ability to degrade 2,4,5-T. © 2012 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

Pesticide tolerant and phosphorus solubilizing Pseudomonas sp. strain SGRAJ09 isolated from pesticides treated Achillea clavennae rhizosphere soil.

PubMed

Rajasankar, R; Manju Gayathry, G; Sathiavelu, A; Ramalingam, C; Saravanan, V S

2013-05-01

In this study, an attempt was made to identify an effective phosphate solubilizing bacteria from pesticide polluted field soil. Based on the formation of solubilization halo on Pikovskaya's agar, six isolates were selected and screened for pesticide tolerance and phosphate (P) solubilization ability through liquid assay. The results showed that only one strain (SGRAJ09) obtained from Achillea clavennae was found to tolerate maximum level of the pesticides tested and it was phylogenetically identified as Pseudomonas sp. It possessed a wide range of pesticide tolerance, ranging from 117 μg mL(-1) for alphamethrin to 2,600 μg mL(-1) for endosulfan. The available P concentrations increased with the maximum and double the maximum dose of monocrotophos and imidacloprid, respectively. On subjected to FT-IR and HPLC analysis, the presence of organic acids functional group in the culture broth and the production of gluconic acid as dominant acid aiding the P solubilization were identified. On comparison with control broth, monocrotophos and imidacloprid added culture broth showed quantitatively high organic acids production. In addition to gluconic acid production, citric and acetic acids were also observed in the pesticide amended broth. Furthermore, the Pseudomonas sp. strain SGRAJ09 possessed all the plant growth promoting traits tested. In presence of monocrotophos and imidacloprid, its plant growth promoting activities were lower than that of the pesticides unamended treatment.

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; Boehlke, Adam R.; Fishman, Neil S.; Battaglin, William A.; Kuivila, Kathryn

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.

Effects of Post-Pyrolysis Air Oxidation of Biomass Chars on Adsorption of Neutral and Ionizable Compounds.

PubMed

Xiao, Feng; Pignatello, Joseph J

2016-06-21

This study was conducted to understand the effects of thermal air oxidation of biomass chars experienced during formation or production on their adsorptive properties toward various compounds, including five neutral nonpolar and polar compounds and seven weak acids and bases (pKa = 3-5.2) selected from among industrial chemicals and the triazine and phenoxyacetic acid herbicide classes. Post-pyrolysis air oxidation (PPAO) at 400 °C of anoxically prepared wood and pecan shell chars for up to 40 min enhanced the mass-normalized adsorption at pH ∼ 7.4 of all test compounds, especially the weak acids and bases, by up to 100-fold. Both general and specific effects were identified. The general effect results from "reaming" of pores by the oxidative removal of pore wall matter and/or tarry deposits generated during the pyrolysis step. Reaming creates new surface area and enlarges nanopores, which helps relieve steric hindrance to adsorption. The specific effect results from creation of new acidic functionality that provides sites for the formation of very strong, charge-assisted hydrogen bonds (CAHB) with solutes having comparable pKa. The CAHB hypothesis was supported by competition experiments and the finding that weak acid anion adsorption increased with surface carboxyl content, despite electrostatic repulsion from the growing negative charge. The results provide insight into the effects of air oxidation on pollutant retention.

Small (13)C/(12)C fractionation contrasts with large enantiomer fractionation in aerobic biodegradation of phenoxy acids.

PubMed

Qiu, Shiran; Gözdereliler, Erkin; Weyrauch, Philip; Lopez, Eva C Magana; Kohler, Hans-Peter E; Sørensen, Sebastian R; Meckenstock, Rainer U; Elsner, Martin

2014-05-20

Phenoxy acid herbicides are important groundwater contaminants. Stable isotope analysis and enantiomer analysis are well-recognized approaches for assessing in situ biodegradation in the field. In an aerobic degradation survey with six phenoxyacetic acid and three phenoxypropionic acid-degrading bacteria we measured (a) enantiomer-specific carbon isotope fractionation of MCPP ((R,S)-2-(4-chloro-2-methylphenoxy)-propionic acid), DCPP ((R,S)-2-(2,4-dichlorophenoxy)-propionic acid), and 4-CPP ((R,S)-2-(4-chlorophenoxy)-propionic acid); (b) compound-specific isotope fractionation of MCPA (4-chloro-2-methylphenoxyacetic acid) and 2,4-D (2,4-dichlorophenoxyacetic acid); and (c) enantiomer fractionation of MCPP, DCPP, and 4-CPP. Insignificant or very slight (ε = -1.3‰ to -2.0‰) carbon isotope fractionation was observed. Equally small values in an RdpA enzyme assay (εea = -1.0 ± 0.1‰) and even smaller fractionation in whole cell experiments of the host organism Sphingobium herbicidovorans MH (εwc = -0.3 ± 0.1‰) suggest that (i) enzyme-associated isotope effects were already small, yet (ii) further masked by active transport through the cell membrane. In contrast, enantiomer fractionation in MCPP, DCPP, and 4-CPP was pronounced, with enantioselectivities (ES) of -0.65 to -0.98 with Sphingomonas sp. PM2, -0.63 to -0.89 with Sphingobium herbicidovorans MH, and 0.74 to 0.97 with Delftia acidovorans MC1. To detect aerobic biodegradation of phenoxypropionic acids in the field, enantiomer fractionation seems, therefore, a stronger indicator than carbon isotope fractionation.

Effect of long-term exposure to pesticides on plasma esterases from plastic greenhouse workers.

PubMed

Hernández, Antonio; Gómez, M Amparo; Pena, Gloria; Gil, Fernando; Rodrigo, Lourdes; Villanueva, Enrique; Pla, Antonio

2004-07-23

Previous reports in animals considered beta-glucuronidase activity as a novel biomarker of anticholinesterase (organophosphates and carbamates) pesticides exposure. Acid phosphatase activity was also shown to increase after organophosphates exposure. In addition, there is evidence that the paraoxonase status influences sensitivity to specific pesticides. In this study, activities of beta-glucuronidase, acid phosphatase, cholinesterase, and paraoxonase were measured in plasma from plastic greenhouse workers exposed over the long term to different pesticides, including organophosphates and carbamates, in order to evaluate the potential chronic toxicity of pesticides at occupational level. Our results show that activities of paraoxonase and cholinesterase were decreased in applicators of pesticides compared to non-applicators. Likewise, it was found that activities of beta-glucuronidase and acid phosphatase were associated with pesticide exposure in humans, and that both biochemical parameters were related to each other. Interestingly, the paraoxonase B allele (phenotyped in plasma) was associated with a higher risk of inhibition of cholinesterase activity above a 25% level, which supports the hypothesis that paraoxonase phenotypes are associated with susceptibility of humans to anticholinesterase pesticides toxicity. Copyright Taylor and Francis Inc.

40 CFR 180.1019 - Sulfuric acid; exemption from the requirement of a tolerance.

Code of Federal Regulations, 2011 CFR

2011-07-01

... AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD... good agricultural practice when used as a herbicide in the production of garlic and onions, and as a... from the use of sulfuric acid as an inert ingredient in a pesticide product used in irrigation...

75 FR 46924 - Notice of Receipt of Several Pesticide Petitions Filed for Residues of Pesticide Chemicals in or...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-04

... high and adverse human health impacts or environmental effects from exposure to the pesticides... regulator, trinexapac-ethyl: 4-(cyclopropyl-[alpha]-hydroxy-methylene)- 3,5-dioxo-cyclohexanecarboxylic acid...,5-dioxo-cyclohexanecarboxylic acid, in or on grass, forage, grown for seed at 1.60 ppm; grass, hay...

Evaluation of ozonation technique for pesticide residue removal and its effect on ascorbic acid, cyanidin-3-glucoside, and polyphenols in apple (Malus domesticus) fruits.

PubMed

Swami, Saurabh; Muzammil, Raunaq; Saha, Supradip; Shabeer, Ahammed; Oulkar, Dasharath; Banerjee, Kaushik; Singh, Shashi Bala

2016-05-01

Ozonated water dip technique was evaluated for the detoxification of six pesticides, i.e., chlorpyrifos, cypermethrin, azoxystrobin, hexaconazole, methyl parathion, and chlorothalonil from apple fruits. Results revealed that ozonation was better than washing alone. Ozonation for 15 min decreased residues of the test pesticides in the range of from 26.91 to 73.58%, while ozonation for 30 min could remove the pesticide residues by 39.39-95.14 % compared to 19.05-72.80 % by washing. Cypermethrin was the least removed pesticide by washing as well as by ozonation. Chlorothalonil, chlorpyrifos, and azoxystrobin were removed up to 71.45-95.14 % in a 30-min ozonation period. In case of methyl parathion removal, no extra advantage could be obtained by ozonation. The HPLC analysis indicated that ozonation also affected adversely the ascorbic acid and cyanidin-3-glucoside content of apples. However, 11 polyphenols studied showed a mixed trend. Gallic acid, 3,4-dihydroxybenzoic acid, catechin, epicatechin, p-coumaric acid, quercetin-3-O-glucoside, quercetin, and kaempferol were found to decrease while syringic acid, rutin, and resveratrol were found to increase in 30-min ozonation.

MULTIRESIDUE DETERMINATION OF ACIDIC PESTICIDES IN WATER BY HPLC/DAD WITH CONFIRMATION BY GC/MS USING CONVERSION TO THE METHYL ESTER WITH TRIMETHYLSILYDIAZOMETHANE

EPA Science Inventory

A multiresidue pesticide methodology has been studied and results for acidics are reported here with base/neutral to follow. This work studies a literature procedure as a possible general approach to many pesticides and potentially other analytes that are considered to be liquid...

75 FR 70254 - Typographical Error in Summary Notice of Filing in Docket for Polymerized Fatty Acid Esters With...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-11-17

... Notice of Filing in Docket for Polymerized Fatty Acid Esters With Aminoalcohol Alkoxylates; Correction... (NOF) for Pesticide Petition (PP) 0E7699 for polymerized fatty acid esters with aminoalcohol... Pesticide Petition (PP) 0E7699 for polymerized fatty acid esters with aminoalcohol alkoxylates submitted by...

Effects of chlorpyrifos and chlorantraniliprole on fermentation quality of alfalfa (Medicago sativa L.) silage inoculated with or without Lactobacillus plantarum LP.

PubMed

Zhang, Qing; Yu, Zhu; Wang, Xianguo; Na, Risu

2017-03-01

The effects of pesticides and Lactobacillus plantarum (LP) on fermentation quality of alfalfa (Medicago sativa L.) silage were investigated. Chlorpyrifos and chlorantraniliprole were sprayed on the surface of alfalfa plants at 658.6 and 45.0 g active ingredient/ha, respectively. Alfalfa plants were harvested on day 5 post-application and ensiled with or without LP. Chlorpyrifos and chlorantraniliprole decreased the yeast count of alfalfa material (P < 0.05). Both pesticides increased the butyric acid content of alfalfa silage (P < 0.001). Chlorpyrifos increased pH and decreased lactic acid, acetic acid and short-chain fatty acid contents (P < 0.05). LP decreased pH and butyric acid content, and increased lactic acid and short-chain fatty acid contents of alfalfa silage treated with pesticides (P < 0.05). LP increased the concentration of chlorpyrifos residue in alfalfa silage (P < 0.05). Chlorpyrifos and chlorantraniliprole affected the microbial communities of the material before ensiling, especially coliform bacteria and yeast; the two pesticide residues were reduced after the fermentation of alfalfa silage and affected the fermentation process, whereas LP improved the fermentation quality of pesticides-contaminated alfalfa silage and slowed down the dissipation of chlorpyrifos. © 2016 Japanese Society of Animal Science.

40 CFR 180.155 - 1-Naphthaleneacetic acid; tolerances for residues.

Code of Federal Regulations, 2011 CFR

2011-07-01

... (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD Specific... established for the combined residues of the plant growth regulator 1-naphthaleneacetic acid and its...

40 CFR 180.155 - 1-Naphthaleneacetic acid; tolerances for residues.

Code of Federal Regulations, 2010 CFR

2010-07-01

... (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD Specific... established for the combined residues of the plant growth regulator 1-naphthaleneacetic acid and its...

Lead isotopic compositions of common arsenical pesticides used in New England

USGS Publications Warehouse

Ayuso, Robert; Foley, Nora; Robinson, Gilpin; Wandless, Gregory; Dillingham, Jeremy

2004-01-01

The three most important arsenical pesticides and herbicides that were extensively used on apple, blueberry, and potato crops in New England from mid-1800s to recent times are lead arsenate, calcium arsenate, and sodium arsenate. Lead arsenate was probably the most heavily used of the arsenical pesticides until it was banned in 1988. Other metal-arsenic pesticides were also used but in lesser amounts. A recent report identified areas in New England where arsenical pesticides were used extensively (Robinson and Ayuso, 2004). On the basis of factor analysis of metal concentrations in stream sediment samples, a positive correlation with pesticide use was shown in regions having stream sediment sample populations that contained concentrations of high arsenic and lead. Lead isotope compositions of stream sediments from areas with heavy use of the pesticides could not be entirely explained by lead originating from rock sulfides and their weathering products. An industrial lead contribution (mostly from atmospheric deposition of lead) was suggested in general to explain the lead isotopic distributions of the stream sediments that could not be accounted for by the natural lead in the environment. We concluded that when agricultural land previously contaminated with arsenical pesticides is urbanized, pesticide residues in the soils and stream sediments could be released into the groundwater. No lead isotopic data characterizing the compositions of pesticides were available for comparison. We have determined the lead isotopic compositions of commonly used pesticides in New England, such as lead arsenate, sodium metaarsenite, and calcium arsenate, in order to assist in future isotopic comparisons and to better establish anthropogenic sources of Pb and As. New data are also presented for copper acetoarsenite (or Paris green), methyl arsonic acid and methane arsonic acid, as well as for arsanilic acid, all of which are used as feed additives to promote swine and poultry growth. The new data characterize these anthropogenic sources. The data show that the arsenical pesticides have similar compositions: 208Pb/207Pb = 2.3839-2.4721, 206Pb/207Pb = 1.1035-1.2010, and 206Pb/204Pb = 17.070-18.759 and, more importantly, that the pesticides overlap the composition of the stream sediments that represent the areas with the most extensive agricultural use. Copper acetoarsenite (Paris green), arsenic oxide, methyl arsonic acid, methane arsonic acid, and arsanilic acid were also analyzed and have lead isotope compositions that range widely. An important source of arsenic and metals to most of the stream sediment samples in New England appears to be weathering products from rocks and industrial lead, but the extensive use of arsenical pesticides and herbicides up to about the 1960s can also be a significant anthropogenic source in agricultural regions.

40 CFR 180.202 - p-Chlorophenoxyacetic acid; tolerances for residues.

Code of Federal Regulations, 2010 CFR

2010-07-01

... (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD Specific... established for the combined residues of the plant regulator p-chlorophenoxyacetic acid and its metabolite p...

40 CFR 180.202 - p-Chlorophenoxyacetic acid; tolerances for residues.

Code of Federal Regulations, 2011 CFR

2011-07-01

... (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD Specific... established for the combined residues of the plant regulator p-chlorophenoxyacetic acid and its metabolite p...

Alterations in the fatty acid profile, antioxidant enzymes and protein pattern of Biomphalaria alexandrina snails exposed to the pesticides diazinon and profenfos.

PubMed

Bakry, Fayez A; El-Hommossany, Karem; Abd El-Atti, Mahmoud; Ismail, Somaya M

2016-04-01

The use of pesticides is widespread in agricultural activities. These pesticides may contaminate the irrigation and drainage systems during agriculture activities and pests' control and then negatively affect the biotic and a biotic component of the polluted water courses. The present study aimed to evaluate the effect of the pesticides diazinon and profenfos on some biological activities of Biomphalaria alexandrina snails such as fatty acid profile, some antioxidant enzymes (thioredoxin reductase (TrxR), sorbitol dehydrogenase (SDH), superoxide dismutase (SOD), catalase (CAT) as well as glutathione reductase (GR) and lipid peroxidation (LP)) and protein patterns in snails' tissues exposed for 4 weeks to LC10 of diazinon and profenfos. The results showed that the two pesticides caused considerable reduction in survival rates and egg production of treated snails. Identification of fatty acid composition in snail tissues treated with diazinon and profenfos pesticides was carried out using gas-liquid chromatography (GLC). The results declared alteration in fatty acid profile, fluctuation in percentage of long chain and short chain fatty acid contributions either saturated or unsaturated ones, and a decrease in total lipid content in tissues of snails treated with these pesticides. The data demonstrate that there was a significant inhibition in the activities of tissues SOD, CAT, glutathione reductase (GR), TrxR, and SDH in tissues of treated snails, while a significant elevation was detected in LP as compared to the normal control. On the other hand, the electrophoretic pattern of total protein showed differences in number and molecular weights of protein bands due to the treatment of snails. It was concluded that the residues of diazinon and profenfos pesticides in aquatic environments have toxic effects onB. alexandrina snails. © The Author(s) 2013.

The use of gamma radiation for removal of pesticides from waste water

NASA Astrophysics Data System (ADS)

Dessouki, A. M.; Aly, H. F.; Sokker, H. H.

1999-01-01

In the present study, a try was made to explain the degradation kinetics due to irradiation of aqueous solutions of some active ingredient pesticides. These pesticides are as follows: one type of triazine herbicide Ametryn and one type of carbamate insecticide (Applaud) and two types of chlorinated organic pesticides, Aldrin and Chlorothalonil. Factors affecting the radiolysis of these pesticides such as the pesticide concentration, irradiation dose, dose rate and pH of the solutions were studied. Ametryn, Applaud, Chlorothalonil and Aldrin insecticides were degraded by γ-radiation and in the case of the chlorinated pesticides hydrochloric acid was detected. The pH effect has proved to vary according to the type of the pesticide and little degradation was observed in allkaline medium, while more degradation of the pesticides in the neutral medium was observed depending on the type of pesticide and on its chemical structure. However, the degradation in the acid medium was even higher. A drop in pH was observed and may be attributed to the degradation of the pesticide molecules to lower molecular weight compounds, such as organic acids. A combined treatment of gamma irradiation and conventional methods was applied and the effect of different additives such as nitrogen and oxygen showed that nitrogen did not enhance the degradation, while an enhancement in the degradation process was observed when oxygen was added. Experiments on the adsorption of these pesticides on certain polymeric materials and on Granular Activated Carbon (GAC), showed that GAC has the highest adsorption capacity. It may be concluded that the radiation degradation followed by adsorption of the toxic pesticide pollutants and their removal from wastewater down to concentrations not exceeding the maximum permissible concentration (MPC), according to international standards, proved to be better than the conventional methods of purification.

Adsorption of MCPA on goethite and humic acid-coated goethite.

PubMed

Iglesias, A; López, R; Gondar, D; Antelo, J; Fiol, S; Arce, F

2010-03-01

Anionic pesticides are adsorbed on the mineral oxide fraction of the soil surface but considerably less on the organic fraction, so that the presence of organic matter causes a decrease in the amount of pesticide adsorbed, and may affect the mechanism of adsorption. In the present study we investigated the adsorption of the weak acid pesticide MCPA on the surface of goethite and of humic acid-coated goethite, selected as models of the mineral oxide fraction and organic components present in soil systems. Adsorption of the anionic form of the pesticide on goethite fitted an S-type isotherm and the amount adsorbed increased as the ionic strength decreased and the pH of the medium decreased. Application of the charge distribution multi site complexation model (CD-MUSIC model) enabled interpretation of the results, which suggested the formation of inner and outer sphere complexes between the pesticide and the singly-coordinated surface sites of goethite. Less pesticide was adsorbed on the humic acid-coated goethite than on the bare goethite and the pattern fitted an L-type isotherm, which indicates a change in the mechanism of adsorption. Simplified calculations with the CD-MUSIC model enabled interpretation of the results, which suggested that the pesticide molecules form the same type of surface complexes as in the previous case. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

40 CFR 180.180 - Orthoarsenic acid; tolerance for residues.

Code of Federal Regulations, 2010 CFR

2010-07-01

...) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD Specific Tolerances..., 1995, for combined As 2O 3 is established for residues of the defoliant orthoarsenic acid in or on the...

40 CFR 180.180 - Orthoarsenic acid; tolerance for residues.

Code of Federal Regulations, 2011 CFR

2011-07-01

...) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD Specific Tolerances..., 1995, for combined As 2O 3 is established for residues of the defoliant orthoarsenic acid in or on the...

40 CFR 180.1210 - Phosphorous acid; exemption from the requirement of a tolerance.

Code of Federal Regulations, 2011 CFR

2011-07-01

... AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD... exemption from the requirement of a tolerance is established for residues of phosphorous acid and its... and in or on potatoes when applied as a post-harvest treatment at 35,600 ppm or less phosphorous acid...

40 CFR 180.1210 - Phosphorous acid; exemption from the requirement of a tolerance.

Code of Federal Regulations, 2010 CFR

2010-07-01

... AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD... exemption from the requirement of a tolerance is established for residues of phosphorous acid and its... and in or on potatoes when applied as a post-harvest treatment at 35,600 ppm or less phosphorous acid...

40 CFR 180.1225 - Decanoic acid; exemption from the requirement of a tolerance.

Code of Federal Regulations, 2011 CFR

2011-07-01

... AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD... exemption from the requirement of a tolerance is established for residues of decanoic acid in or on all raw... acid (up to 170 ppm per application) on food contact surfaces such as equipment, pipelines, tanks, vats...

Design of a New Glutamine-Fipronil Conjugate with α-Amino Acid Function and its Uptake by A. thaliana Lysine Histidine Transporter 1 ( AtLHT1).

PubMed

Jiang, Xunyuan; Xie, Yun; Ren, Zhanfu; Ganeteg, Ulrika; Lin, Fei; Zhao, Chen; Xu, Hanhong

2018-06-26

Creating novel pesticides with phloem-mobility is essential for controlling insects in vascular tissue and root, and conjugating existing pesticides with amino acid is an effective approach. In order to obtain highly phloem-mobile candidate for efficient pesticide, an electro-neutral L-glutamine-fipronil conjugate (L-GlnF) retaining α-amino acid function was designed and synthesized to fit the substrate specificity of amino acid transporter. Cotyledon uptake and phloem loading tests with Ricinus communis have verified that L-GlnF was phloem mobile, and its phloem mobility was higher than its enantiomer D-GlnF and other previously reported amino acid-fipronil conjugates. Inhibition experiments then suggested that the uptake of L-GlnF was, at least partially, mediated by active transport mechanism. This inference was further strengthened by assimilation experiments with Xenopus oocytes and genetically modified Arabidopsis thaliana, which showed direct correlation between the uptake of L-GlnF and expression of amino acid transporter AtLHT1. Thus, conjugation with L-Gln appears to be a potential strategy to ensure the uptake of pesticides via endogenous amino acid transport system.

CHIRAL PESTICIDES: OCCURRENCE AND SIGNIFICANCE

EPA Science Inventory

Like amino acids, certain pesticides exist in "left-handed" and "right-handed" (chiral) forms. Commercially available chiral pesticides are produced as racemic mixtures in which the ratio of the two forms (or enantiomers) is 1:1. Enantiomers have the same ...

Containing arsenic-enriched groundwater tracing lead isotopic compositions of common arsenical pesticides in a coastal Maine watershed

USGS Publications Warehouse

Ayuso, Robert A.; Foley, Nora K.; Robinson, Glipin R.; Colvin, A.S.; Lipfert, G.; Reeve, A.S.

2006-01-01

Arsenical pesticides and herbicides were extensively used on apple, blueberry, and potato crops in New England during the first half of the twentieth century. Lead arsenate was the most heavily used arsenical pesticide until it was officially banned. Lead arsenate, calcium arsenate, and sodium arsenate have similar Pb isotope compositions: 208Pb207Pb = 2.3839-2.4722, and 206Pb207Pb = 1.1035-1.2010. Other arsenical pesticides such as copper acetoarsenite (Paris green), methyl arsonic acid and methane arsonic acid, as well as arsanilic acid are widely variable in isotope composition. Although a complete understanding of the effects of historical use of arsenical pesticides is not available, initial studies indicate that arsenic and lead concentrations in stream sediments in New England are higher in agricultural areas that intensely used arsenical pesticides than in other areas. The Pb isotope compositions of pesticides partially overlap values of stream sediments from areas with the most extensive agricultural use. The lingering effects of arsenical pesticide use were tested in a detailed geochemical and isotopic study of soil profiles from a watershed containing arsenic-enriched ground water in coastal Maine. Acid-leach compositions of the soils represent lead adsorbed to mineral surfaces or held in soluble minerals (Fe- and Mn-hydroxides, carbonate, and some micaceous minerals), whereas residue compositions likely reflect bedrock compositions. The soil profiles contain labile Pb (acid-leach) showing a moderate range in 206Pb 207Pb (1.1870-1.2069), and 208Pb207Pb (2.4519-2.4876). Isotope values vary as a function of depth: the lowest Pb isotope ratios (e.g.,208Pb206Pb) representing labile lead are in the uppermost soil horizons. Lead contents decrease with depth in the soil profiles. Arsenic contents show no clear trend with depth. A multi-component mixing scheme that included lead from the local parent rock (Penobscot Formation), lead derived from combustion of fossil fuels, and possibly lead from other anthropogenic sources (e.g., pesticides), could account for Pb isotope variations in the soil profiles. In agricultural regions, our preliminary data show that the extensive use of arsenical pesticides and herbicides can be a significant anthropogenic source of arsenic and lead to stream sediments and soils.

Urinary pesticide metabolites in school students from northern Thailand.

PubMed

Panuwet, Parinya; Prapamontol, Tippawan; Chantara, Somporn; Barr, Dana B

2009-05-01

We evaluated exposure to pesticides among secondary school students aged 12-13 years old in Chiang Mai Province, Thailand. Pesticide-specific urinary metabolites were used as biomarkers of exposure for a variety of pesticides, including organophosphorus insecticides, synthetic pyrethroid insecticides and selected herbicides. We employed a simple solid-phase extraction with analysis using isotope dilution high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS). A total of 207 urine samples from Thai students were analyzed for 18 specific pesticide metabolites. We found 14 metabolites in the urine samples tested; seven of them were detected with a frequency > or=17%. The most frequently detected metabolites were 2-[(dimethoxyphosphorothioyl) sulfanyl] succinic acid (malathion dicarboxylic acid), para-nitrophenol (PNP), 3,5,6-trichloro-2-pyridinol (TPCY; metabolite of chlorpyrifos), 2,4-dichlorophenoxyacetic acid (2,4-D), cis- and trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylic acids (c-DCCA and t-DCCA; metabolite of permethrin) and 3-phenoxybenzoic acid (3-PBA; metabolite of pyrethroids). The students were classified into 4 groups according to their parental occupations: farmers (N=60), merchants and traders (N=39), government and company employees (N=52), and laborers (N=56). Children of farmers had significantly higher urinary concentrations of pyrethroid insecticide metabolites than did other children (p<0.05). Similarly, children of agricultural families had significantly higher pyrethroid metabolite concentrations. Males had significantly higher values of PNP (Mann-Whitney test, p=0.009); however, no other sex-related differences were observed. Because parental occupation and agricultural activities seemed to have little influence on pesticide levels, dietary sources were the likely contributors to the metabolite levels observed.

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.

Uptake of 4-chloro-2-methylphenoxyacetic acid (MCPA) from the apical membrane of Caco-2 cells by the monocarboxylic acid transporter

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kimura, Osamu; Tsukagoshi, Kensuke; Endo, Tetsuya

2008-03-15

The cellular uptake mechanism of 4-chloro-2-methylphenoxyacetic acid (MCPA), a phenoxyacetic acid derivative, was investigated using Caco-2 epithelial cells. The cells were incubated with 50 {mu}M MCPA at pH 6.0 and 37 deg. C, and the uptake of MCPA from the apical membranes was measured. The uptake of MCPA was significantly decreased by incubation at low temperature (4 {sup o}C) and markedly increased by lowering the extracellular pH. Pretreatment with a protonophore, carbonylcyanide-p-(trifluoromethoxy)phenylhydrazone (25 {mu}M), or metabolic inhibitors, 2,4-dinitrophenol (1 mM) and sodium azide (10 mM), significantly decreased the uptake of MCPA by 53%, 45% and 48%, respectively. Coincubation of MCPAmore » with 10 mM L-lactic acid or {alpha}-cyano-4-hydroxycinnamate, which is a substrate or an inhibitor of the monocarboxylic acid transporters (MCTs), significantly decreased the uptake of MCPA by 31% and 20%, respectively, and coincubation with benzoic acid profoundly decreased the uptake by 68%. In contrast, coincubation with succinic acid (a dicarboxylic acid) did not affect the uptake. Kinetic analysis of initial MCPA uptake suggested that MCPA is taken up via a carrier-mediated process [K{sub m} = 1.37 {+-} 0.15 mM, V{sub max} = 115 {+-} 6 nmol (mg protein){sup -1} (3 min){sup -1}]. Lineweaver-Burk plots show that benzoic acid competitively inhibits the uptake of MCPA with a K{sub i} value of 4.68 {+-} 1.76 mM. A trans-stimulation effect on MCPA uptake was found in cells preloaded with benzoic acid. These results suggest that the uptake of MCPA from the apical membrane of Caco-2 cells is mainly mediated by common MCTs along with benzoic acid but also in part by L-lactic acid.« less

40 CFR 455.21 - Specialized definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... AND STANDARDS PESTICIDE CHEMICALS Organic Pesticide Chemicals Manufacturing Subcategory § 455.21... to this subpart. (c) Organic pesticide chemicals means the sum of all organic active ingredients... used as reaction medium, spent acids, spent bases, contact cooling water, water of reaction, air...

40 CFR 180.1196 - Peroxyacetic acid; exemption from the requirement of a tolerance.

Code of Federal Regulations, 2011 CFR

2011-07-01

... AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD... antimicrobial treatment in solutions containing a diluted end use concentration of peroxyacetic acid up to 100... food commodities when used in sanitizing solutions containing a diluted end-use concentration of...

STORAGE STABILITY OF PESTICIDES IN EXTRACT SOLVENTS AND SAMPLING MEDIA

EPA Science Inventory

Demonstrating that pesticides are stable in field media and their extracts over extended storage periods allows operational flexibility and cost efficiency. Stability of the 31 neutral pesticides and 2 acid herbicides of the Agricultural Health Study exposure pilot was evaluate...

Choosing between atmospheric pressure chemical ionization and electrospray ionization interfaces for the HPLC/MS analysis of pesticides

USGS Publications Warehouse

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

2001-01-01

An evaluation of over 75 pesticides by high-performance liquid chromatography/mass spectrometry (HPLC/MS) clearly shows that different classes of pesticides are more sensitive using either atmospheric pressure chemical ionization (APCI) or electrospray ionization (ESI). For example, neutral and basic pesticides (phenylureas, triazines) are more sensitive using APCI (especially positive ion). While cationic and anionic herbicides (bipyridylium ions, sulfonic acids) are more sensitive using ESI (especially negative ion). These data are expressed graphically in a figure called an ionization-continuum diagram, which shows that protonation in the gas phase (proton affinity) and polarity in solution, expressed as proton addition or subtraction (pKa), is useful in selecting APCI or ESI. Furthermore, sodium adduct formation commonly occurs using positive ion ESI but not using positive ion APCI, which reflects the different mechanisms of ionization and strengthens the usefulness of the ionization-continuum diagram. The data also show that the concept of "wrong-way around" ESI (the sensitivity of acidic pesticides in an acidic mobile phase) is a useful modification of simple pKa theory for mobile-phase selection. Finally, this finding is used to enhance the chromatographic separation of oxanilic and sulfonic acid herbicides while maintaining good sensitivity in LC/MS using ESI negative.

Determination of pesticide epitopic density in protein immunoconjugates by electrospray mass spectrometry

NASA Astrophysics Data System (ADS)

Canosa, D.; Daniel, R.; Barceló, D.; Gelpí, E.; Le Goffic, F.; Abián, J.

1997-01-01

Several immunoconjugates of [beta]-lactoglobulin with different covalently bound pesticides (phenuron, chlortoluron, isoproturon, simazine, desethylatrazine, 2,4-dichlorophenoxyacetic acid) have been characterized by electrospray mass spectrometry (ESI-MS). The protein has 15 theoretical binding sites and the average number of pesticide molecules bound per protein ranged from two (phenuron) to 13 (2,4-dichlorophenoxyacetic acid). These results were compared with those obtained by a spectrophotometric method and by matrix-assisted laser desorption ionization (MALDI) mass spectrometry. The pesticide density in the immunoconjugate is very dependent on the pesticide structure, indicating that steric hindrance could be one of the limiting factors of the coupling procedure. The favored binding positions have been determined in the case of chlortoluron and isoproturon by ESI-MS analysis of the peptides obtained after enzymatic digestion of the protein with trypsin.

Characterization of pesticide exposure in a sample of pregnant women in Ecuador

PubMed Central

Handal, Alexis J.; Hund, Lauren; Páez, Maritza; Bear, Samantha; Greenberg, Carolyn; Fenske, Richard A.; Barr, Dana Boyd

2015-01-01

Background Few studies have detailed the prenatal pesticide exposure levels of women employed in or residing near large-scale agricultural industries. This study reports pesticide metabolite levels during and shortly after pregnancy in a pilot study of workers in Ecuador. Methods Urine samples were collected for 16 rose workers and 10 non-agricultural workers enrolled into the study in early pregnancy. We measured six nonspecific organophosphate dialkylphosphate (DAP) pesticide metabolites, two alkylenebis-dithiocarbamate pesticide metabolites (ethylene thiourea [ETU] and propylene thiourea [PTU]), 3,5,6-trichloro-2-pyridinol [TCPy], malathion dicarboxylic acid, and two pyrethroid metabolites (2,2-dimethylcyclopropanecarboxylic acid and 3-phenooxybenzoic acid). Results We collected 141 urine samples (mean: 5.4 per woman). We observed high detection frequencies for five DAP metabolites and ETU, PTU, and TCPy. We report elevated levels of ETU in the entire sample (median 4.24 ng/mL, IQR 2.23, 7.18), suggesting other possible non-occupational pathways of exposure. We found no statistical differences in pesticide levels by current employment status, though the highest pesticide levels were among rose workers. We observed within-woman correlation in TCPy and PTU levels, but not in ETU or DAP levels. Conclusions The present study is the first to characterize prenatal pesticide exposure levels among working women in Ecuador. Limitations include a small sample size and use of a convenience sample. Strengths include a longitudinal design and multiple urine samples per woman. Results provide an initial characterization of prenatal pesticide exposure levels and how these levels vary over pregnancy in a community impacted by agricultural industry and will inform further studies in the region. PMID:26311023

Acid Rain Contribution from Pesticide Distribution to Rice Farmers in Pati Regency

NASA Astrophysics Data System (ADS)

Qosim, Ahmad; Anies; Sunoko, Henna Rya

2018-02-01

Productivity rate of rice fields in Regency has been in a surplus condition annually. The fields have produced 7 to 8 tons per hectare, making the total annual rate of 600 tons. The regency, therefore, is considered to be capable of fulfilling its own need for rice and to contribute significantly to the rice needs in Central Java Province. Agriculture coexists with the presence of pesticides. While helping the farmers to combat the plant diseases, pesticides have still been greatly necessary by the local farmers. Distribution by means of transportation devices plays an important role for the dissemination of the pesticides from the producers to their end users. Problem arises due to emission produced during the transportation activities. Transportation emits SO2 as the major contributor to acid rain. To make worse, application in practice by the farmers also emit the similar substance. Annual use of pesticides in Pati Regency has reached 605 tons with SO2 emission of 13,697 kg. It is recommended that distribution management and selection of pesticides are performed by applying an integrated pest control in order to reduce the pesticide emission.

2,4-Dichlorophenoxyacetic acid (2,4-D)- and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T)-degrading gene cluster in the soybean root-nodulating bacterium Bradyrhizobium elkanii USDA94.

PubMed

Hayashi, Shohei; Sano, Tomoki; Suyama, Kousuke; Itoh, Kazuhito

2016-01-01

Herbicides 2,4-dichlorophenoxyacetic acid (2,4-D)- and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T)-degrading Bradyrhizobium strains possess tfdAα and/or cadABC as degrading genes. It has been reported that root-nodulating bacteria belonging to Bradyrhizobium elkanii also have tfdAα and cadA like genes but lack the ability to degrade these herbicides and that the cadA genes in 2,4-D-degrading and non-degrading Bradyrhizobium are phylogenetically different. In this study, we identified cadRABCK in the genome of a type strain of soybean root-nodulating B. elkanii USDA94 and demonstrated that the strain could degrade the herbicides when cadABCK was forcibly expressed. cadABCK-cloned Escherichia coli also showed the degrading ability. Because co-spiked phenoxyacetic acid (PAA) could induce the degradation of 2,4-D in B. elkanii USDA94, the lack of degrading ability in this strain was supposed to be due to the low inducing potential of the herbicides for the degrading gene cluster. On the other hand, tfdAα from B. elkanii USDA94 showed little potential to degrade the herbicides, but it did for 4-chlorophenoxyacetic acid and PAA. The 2,4-D-degrading ability of the cad cluster and the inducing ability of PAA were confirmed by preparing cadA deletion mutant. This is the first study to demonstrate that the cad cluster in the typical root-nodulating bacterium indeed have the potential to degrade the herbicides, suggesting that degrading genes for anthropogenic compounds could be found in ordinary non-degrading bacteria. Copyright © 2016 Elsevier GmbH. All rights reserved.

40 CFR 180.1225 - Decanoic acid; exemption from the requirement of a tolerance.

Code of Federal Regulations, 2010 CFR

2010-07-01

..., breweries, wineries, beverage and food processing plants. [68 FR 7939, Feb. 19, 2003; 68 FR 17308, Apr. 9... AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD... acid (up to 170 ppm per application) on food contact surfaces such as equipment, pipelines, tanks, vats...

Effect of 2,4-Dichlorophenoxyacetic Acid (2,4-D) on PCDD/F Emissions from Open Burning of Biomass

EPA Science Inventory

Use of pesticides prior to agricultural burning and overspray onto forests and grasslands prior to fires has been cited as a cause of halogenated organic compound emissions from biomass combustion. Some pesticides such as 2,4-dichlorophenoxyacetic acid (2,4-D) are used in conside...

A test house study of pesticides and pesticide degradation products following an indoor application.

PubMed

Starr, J M; Gemma, A A; Graham, S E; Stout, D M

2014-08-01

Preexisting pesticide degradates are a concern for pesticide biomonitoring studies as exposure to them may result in overestimation of pesticide exposure. The purpose of this research was to determine whether there was significant formation and movement, of pesticide degradates over a 5-week period in a controlled indoor setting after insecticide application. Movement of the pesticides during the study was also evaluated. In a simulated crack and crevice application, commercially available formulations of fipronil, propoxur, cis/trans-permethrin, and cypermethrin were applied to a series of wooden slats affixed to the wall in one room of an unoccupied test house. Floor surface samples were collected through 35 days post-application. Concentrations of the pesticides and the following degradates were determined: 2-iso-propoxyphenol, cis/trans 3-(2,2-dichlorovinyl)-3-3-dimethyl-(1-cyclopropane) carboxylic acid, 3-phenoxybenzoic acid, fipronil sulfone, fipronil sulfide, and fipronil desulfinyl. Deltamethrin, which had never been applied, and chlorpyrifos, which had been applied several years earlier, and their degradation products, cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid, and, 3,5,6-trichloro-2-pyridinol, respectively, were also measured. Propoxur was the only insecticide with mass movement away from the application site. There was no measurable formation or movement of the degradates. However, all degradates were present at low levels in the formulated product. These results indicate longitudinal repetitive sampling of indoor degradate levels during short-term studies, is unnecessary. Exposure to preexisting pesticide degradates may inflate estimates of exposure in biomonitoring studies where these compounds are used as biomarkers. To date, there is no published information on formation of pesticide degradates following an indoor application. We found that the study pesticides have low rates of degradation and are unlikely to be a significant factor affecting results of short-term (weeks) biomonitoring studies. Therefore, relatively few indoor samples are needed to estimate background levels of degradation products resulting from a recent pesticide application. Published 2014. This article is a U.S. Government work and is in the public domain in the USA.

Effect of handling and processing on pesticide residues in food- a review.

PubMed

Bajwa, Usha; Sandhu, Kulwant Singh

2014-02-01

Pesticides are one of the major inputs used for increasing agricultural productivity of crops. The pesticide residues, left to variable extent in the food materials after harvesting, are beyond the control of consumer and have deleterious effect on human health. The presence of pesticide residues is a major bottleneck in the international trade of food commodities. The localization of pesticides in foods varies with the nature of pesticide molecule, type and portion of food material and environmental factors. The food crops treated with pesticides invariably contain unpredictable amount of these chemicals, therefore, it becomes imperative to find out some alternatives for decontamination of foods. The washing with water or soaking in solutions of salt and some chemicals e.g. chlorine, chlorine dioxide, hydrogen peroxide, ozone, acetic acid, hydroxy peracetic acid, iprodione and detergents are reported to be highly effective in reducing the level of pesticides. Preparatory steps like peeling, trimming etc. remove the residues from outer portions. Various thermal processing treatments like pasteurization, blanching, boiling, cooking, steaming, canning, scrambling etc. have been found valuable in degradation of various pesticides depending upon the type of pesticide and length of treatment. Preservation techniques like drying or dehydration and concentration increase the pesticide content many folds due to concentration effect. Many other techniques like refining, fermentation and curing have been reported to affect the pesticide level in foods to varied extent. Milling, baking, wine making, malting and brewing resulted in lowering of pesticide residue level in the end products. Post harvest treatments and cold storage have also been found effective. Many of the decontamination techniques bring down the concentration of pesticides below MRL. However, the diminution effect depends upon the initial concentration at the time of harvest, substrate/food and type of pesticide. There is diversified information available in literature on the effect of preparation, processing and subsequent handling and storage of foods on pesticide residues which has been compiled in this article.

Sub-lethal exposure of cockroaches to boric acid pesticide contributes to increased Bla g 2 excretion.

PubMed

Zhang, Y C; Perzanowski, M S; Chew, G L

2005-07-01

Several epidemiology studies have found an increase in the major cockroach allergen Bla g 2 with reported pesticide use. Our aim was to investigate the effect on the excretion of Bla g 1 and Bla g 2 allergens by cockroaches exposed to sub-lethal doses of the pesticides, boric acid and hydramethylnon gel. German cockroaches in separate colonies were fed either boric acid or hydramethylnon gel at concentrations of 0.2, 0.1 and 0.01% in their water supply over a 2 week period. Ten colonies were exposed to each treatment concentration. Bla g 1 and Bla g 2 in fecal pellets were measured by ELISA. Cockroaches exposed to boric acid excreted fecal pellets with significantly higher concentrations of Bla g 2 (35,400 U/g) than did controls (12,700 U/g) (P = 0.001). Bla g 1 concentrations were not significantly different. There was no difference in either Bla g 1 or Bla g 2 concentrations between cockroaches that ingested hydramethylnon gel and those in the controls colonies. The application of boric acid, a common pesticide, appears to paradoxically increase the production of Bla g 2, a major allergen, by the surviving cockroaches. This may have important implications in avoidance strategies.

Occurrence of pesticide non extractable residues in physical and chemical fractions from two natural soils.

NASA Astrophysics Data System (ADS)

Andreou, K.; Jones, K.; Semple, K.

2009-04-01

Distribution of pesticide non extractable residues resulted from the incubation of two natural soils with each of the isoproturon, diazinon and cypermethrin pesticide was assessed in this study. Pesticide non extractable residues distribution in soil physical and chemical fractions is known to ultimately affect their fate. This study aimed to address the fate and behaviour of the non extractable residues in the context of their association with soil physical and chemical fractions with varying properties and characteristics. Non extractable residues were formed from incubation of each pesticide in the two natural soils over a period of 24 months. Soils containing the non extractable residues were fractionated into three solid phase fractions using a physical fractionation procedure as follows: Sediment (SED, >20 μm), (II) Microaggregate (MA, 20-2 μm) and (III) Colloid phase (COL, 2-0.05 μm). Each soil fraction was then fractionated into organic carbon chemical fractionations as follows: Fulvic acid (FA), Humic acid (HA) and Humin (HM). Significant amount of the pesticides was lost during the incubation period. Enrichment factors for the organic carbon and the 14C-pesticide residues were higher in the MA and COL fraction rather than the SED fraction. Greater association and enrichment of the fulvic acid fraction of the organic carbon in the soil was observed. Non extractable residues at the FA fraction showed to diminish while in the HA fraction were increased with decreasing the fraction size. An appreciable amount of non extractable residues were located in the HM fraction but this was less than the amount recovered in the humic substances. Long term fate of pesticide non extractable residues in the soil structural components is important in order to assess any risk associated with them.

Effect of Exogenous Penicillin on Penicillin Biosynthesis

PubMed Central

Gordee, Elizabeth Z.; Day, L. E.

1972-01-01

The addition of phenoxymethylpenicillin (10 mg/ml) at any time during the penicillin fermentation inhibited further accumulation of the antibiotic in broth but had no effect on growth. Benzylpenicillin, 6-aminopenicillanic acid (6-APA), and some semisynthetic penicillins also showed this effect, but penicillin N, penicilloic acid, cephalosporin C, and 7-aminocephalosporanic acid did not limit penicillin accretion. Incorporation of radioactive precursors (cysteine, valine, and sodium phenoxyacetate) into penicillin in the presence of inhibitory concentrations of the antibiotic indicated that penicillin synthesis continued despite the lack of accretion of the antibiotic in broth. The rates of penicillin synthesis in a 48-hr and a 136-hr culture were compared by short-term exposure to Na235SO4, and no significant difference in the biosynthetic rate was observed. Exogenous penicillin in the range of 1 to 15 mg/ml of culture broth had no effect on utilization of acetate or glucose by Penicillium chrysogenum. The antibiotic-synthesizing capacity of the organism was not irreversibly inhibited by exogenous penicillin. The degradation of penicillin during the fermentation was also studied. Penicillin V was stable in broth filtrate. Catabolic enzymes such as penicillinase and penicillin-acylase were not demonstrated in whole broth, nor was the accumulation of 6-APA, penicilloic acid, or other degradation products detected. An examination of the intracellular penicillin concentration and the amount of penicillin associated with the mycelium revealed that cells contained significantly more penicillin late in the fermentation than earlier in the cycle. This cell-associated antibiotic may be a regulatory factor in further penicillin synthesis. PMID:4208897

The metabolism of the anti-inflammatory drug eterylate in rat, dog and man.

PubMed

Wood, S G; John, B A; Chasseaud, L F; Johnstone, I; Biggs, S R; Hawkins, D R; Priego, J G; Darragh, A; Lambe, R F

1983-12-01

Oral doses of 14C-eterylate were well absorbed by rat and man and excreted mainly in the urine (94% dose by rat in three days and 91% by man in five days). Oral doses to dogs were excreted in similar proportions in both the urine and faeces, although faecal 14C was probably derived in part, from biliary-excreted material. Peak plasma 14C and drug concn. were generally reached between one and three hours after oral doses. In humans, only two metabolites, salicylic acid and 4-acetamido-phenoxyacetic acid, were detected in plasma. The latter was cleared more rapidly than the former and hence plasma salicyclate concn. reached a peak (10.9 and 19.8 micrograms/ml in Subjects 1 and 2, respectively) and initially declined with a half-life of about two-three hours. Plasma 4-acetamidophenoxyacetic acid concn. reached a peak (4.3, 10.0 micrograms/ml, respectively) and declined with a half-life of about one hour. Tissue concn. of 14C were generally greater in dogs than in rats. Highest conc. occurred at three hours in dogs and at one hour in rats. Apart from those in the liver and kidneys, tissue concn. were lower than those in the corresponding plasma. Unchanged drug was not detected in urine or plasma of any species and was rapidly metabolized in human plasma. The major 14C components in human urine were identified as salicyluric acid and 4-acetamidophenoxyacetic acid; minor metabolites were salicylic acid, gentisic acid and paracetamol. These metabolites were also detected in rat urine albeit in different proportions to those in human urine. Dog urine contained less of these metabolites and a major proportion of the 14C was associated with relatively non-polar components. Although salicylic acid and 4-acetamidophenoxyacetic acid were the only major circulating metabolites in man and rat, dog plasma also contained the non-polar urine metabolites.

Exposure of German residents to ethylene and propylene glycol ethers in general and after cleaning scenarios.

PubMed

Fromme, H; Nitschke, L; Boehmer, S; Kiranoglu, M; Göen, T

2013-03-01

Glycol ethers are a class of semi-volatile substances used as solvents in a variety of consumer products like cleaning agents, paints, cosmetics as well as chemical intermediates. We determined 11 metabolites of ethylene and propylene glycol ethers in 44 urine samples of German residents (background level study) and in urine samples of individuals after exposure to glycol ethers during cleaning activities (exposure study). In the study on the background exposure, methoxyacetic acid and phenoxyacetic acid (PhAA) could be detected in each urine sample with median (95th percentile) values of 0.11 mgL(-1) (0.30 mgL(-1)) and 0.80 mgL(-1) (23.6 mgL(-1)), respectively. The other metabolites were found in a limited number of samples or in none. In the exposure study, 5-8 rooms were cleaned with a cleaner containing ethylene glycol monobutyl ether (EGBE), propylene glycol monobutyl ether (PGBE), or ethylene glycol monopropyl ether (EGPE). During cleaning the mean levels in the indoor air were 7.5 mgm(-3) (EGBE), 3.0 mgm(-3) (PGBE), and 3.3 mgm(-3) (EGPE), respectively. The related metabolite levels analysed in the urine of the residents of the rooms at the day of cleaning were 2.4 mgL(-1) for butoxyacetic acid, 0.06 mgL(-1) for 2-butoxypropionic acid, and 2.3 mgL(-1) for n-propoxyacetic acid. Overall, our study indicates that the exposure of the population to glycol ethers is generally low, with the exception of PhAA. Moreover, the results of the cleaning scenarios demonstrate that the use of indoor cleaning agents containing glycol ethers can lead to a detectable internal exposure of residents. Copyright © 2012 Elsevier Ltd. All rights reserved.

Interaction of pesticides with natural organic material

USGS Publications Warehouse

Wershaw, R. L.; Burcar, P.J.; Goldberg, M.C.

1969-01-01

Two examples of the interaction of pesticides with natural organic materials have been investigated. Sodium humate solubilizes DDT in water and humic acid strongly sorbs 2,4,5-T. These two types of interactions are indicative of the types that one would expect when any organic pesticide is applied to a natural soil-water system.

76 FR 6347 - (S,S)-Ethylenediamine Disuccinic Acid Trisodium Salt; Exemption From the Requirement of a Tolerance

Federal Register 2010, 2011, 2012, 2013, 2014

2011-02-04

... pesticide formulations applied to growing crops or to raw agricultural commodities after harvest under EPA... chelating agent in pesticide formulations applied to growing crops or to raw agricultural commodities after... pesticide formulations applied to growing crops or to raw agricultural commodities after harvest is safe...

75 FR 1773 - Notice of Receipt of a Pesticide Petition Filed for Residues of Polymeric Polyhydroxy Acid in or...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-01-13

... (NAICS code 111). Animal production (NAICS code 112). Food manufacturing (NAICS code 311). Pesticide manufacturing (NAICS code 32532). This listing is not intended to be exhaustive, but rather provides a guide for... Environmental protection, Agricultural commodities, Feed additives, Food additives, Pesticides and pests...

Demonstration of spread-on peel-off consumer products for sampling surfaces contaminated with pesticides and chemical warfare agent signatures.

PubMed

Behringer, Deborah L; Smith, Deborah L; Katona, Vanessa R; Lewis, Alan T; Hernon-Kenny, Laura A; Crenshaw, Michael D

2014-08-01

A terrorist attack using toxic chemicals is an international concern. The utility of rubber cement and latex body paint as spray-on/spread-on peel-off collection media for signatures attributable to pesticides and chemical warfare agents from interior building and public transportation surfaces two weeks post-deposition is demonstrated. The efficacy of these media to sample escalator handrail, stainless steel, vinyl upholstery fabric, and wood flooring is demonstrated for two pesticides and eight chemicals related to chemical warfare agents. The chemicals tested are nicotine, parathion, atropine, diisopropyl methylphosphonate, dimethyl methylphosphonate, dipinacolyl methylphosphonate, ethyl methylphosphonic acid, isopropyl methylphosphonic acid, methylphosphonic acid, and thiodiglycol. Amounts of each chemical found are generally greatest when latex body paint is used. Analytes with low volatility and containing an alkaline nitrogen or a sulfur atom (e.g., nicotine and parathion) usually are recovered to a greater extent than the neutral phosphonate diesters and acidic phosphonic acids (e.g., dimethyl methylphosphonate and ethyl methylphosphonic acid). Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

Residential agricultural pesticide exposures and risks of selected birth defects among offspring in the San Joaquin Valley of California.

PubMed

Carmichael, Suzan L; Yang, Wei; Roberts, Eric; Kegley, Susan E; Brown, Timothy J; English, Paul B; Lammer, Edward J; Shaw, Gary M

2016-01-01

We examined associations of birth defects with residential proximity to commercial agricultural pesticide applications in California. Subjects included 367 cases representing five types of birth defects and 785 nonmalformed controls born 1997 to 2006. Associations with any versus no exposure to physicochemical groups of pesticides and specific chemicals were assessed using logistic regression adjusted for covariates. Overall, 46% of cases and 38% of controls were classified as exposed to pesticides within a 500 m radius of mother's address during a 3-month periconceptional window. We estimated odds ratios (ORs) for 85 groups and 95 chemicals with five or more exposed cases and control mothers. Ninety-five percent confidence intervals (CI) excluded 1.0 for 11 ORs for groups and 22 ORs for chemicals, ranging from 1.9 to 3.1 for groups and 1.8 to 4.9 for chemicals except for two that were <1 (noted below). For groups, these ORs were for anotia/microtia (n = 95 cases) and dichlorophenoxy acids/esters and neonicotinoids; anorectal atresia/stenosis (n = 77) and alcohol/ethers and organophosphates (these ORs were < 1.0); transverse limb deficiencies (n = 59) and dichlorophenoxy acids/esters, petroleum derivatives, and triazines; and craniosynostosis (n = 79) and alcohol/ethers, avermectins, neonicotinoids, and organophosphates. For chemicals, ORs were: anotia/microtia and five pesticides from the groups dichlorophenoxy acids/esters, copper-containing compounds, neonicotinoids, organophosphates, and triazines; transverse limb deficiency and six pesticides - oxyfluorfen and pesticides from the groups copper-containing compounds, 2,6-dinitroanilines, neonicotinoids, petroleum derivatives and polyalkyloxy compounds; craniosynostosis and 10 pesticides - oxyfluorfen and pesticides from the groups alcohol/ethers, avermectins, n-methyl-carbamates, neonicotinoids, ogranophosphates (two chemicals), polyalkyloxy compounds (two chemicals), and pyrethroids; and congenital diaphragmatic hernia (n = 62) and a copper-containing compound. © 2015 Wiley Periodicals, Inc.

40 CFR 180.311 - Cacodylic acid; tolerances for residues.

Code of Federal Regulations, 2010 CFR

2010-07-01

...) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD Specific Tolerances... raw agricultural commodity as follows: Commodity Parts per million Cotton, undelinted seed 2.8 (b...

Influence of environmental factors on pesticide adsorption by black carbon: pH and model dissolved organic matter.

PubMed

Qiu, Yuping; Xiao, Xiaoyu; Cheng, Haiyan; Zhou, Zunlong; Sheng, G Daniel

2009-07-01

Loading two organic acids of known molecular structures onto a black carbon was conducted to study the influence of pH and dissolved organic matter on the adsorption of pesticides. Tannic acid at the loading rates of 100 and 300 micromol/g reduced the surface area of black carbon by 18 and 63%, respectively. This was due principally to the blockage of micropores, as verified by measured pore volumes and pore-size distributions. With a comparatively much smaller molecular structure, gallic acid did not apparently influence these properties. The intrinsic acidities of the two acids increased the surface acidity from 1.88 mmol/g of black carbon to 1.93-2.02 mmol/g after DOM loading, resulting in a reduction in isoelectric point pH from 1.93 to 1.66-1.82. The adsorption of propanil, 2,4-D and prometon by black carbon free and loaded of DOM was dependent on pH because major adsorptive forces were the interactions between neutral pesticide molecules and uncharged carbon surfaces. The adsorption was diminished considerably by the deprotonation of 2,4-D and protonation of prometon, as well as the surface charge change of black carbon. Tannic acid of 100 and 300 micromol/g on black carbon reduced the pesticide adsorption at the equilibrium concentration of 10 mg/L by an average of 46 and 81%, respectively, consistent with the reductions of 42 and 81% in micropore volume. At the equilibrium concentration of 30 mg/L, the mesopore surface became the additional adsorptive domain for propanil. Loading tannic acid made the mesopore surface less accessible, due presumably to the enhanced obstruction by tannic acid.

Relationship between Urinary Pesticide Residue Levels and Neurotoxic Symptoms among Women on Farms in the Western Cape, South Africa

PubMed Central

Motsoeneng, Portia M.; Dalvie, Mohamed A.

2015-01-01

Background: This cross-sectional study aimed to investigate the relationship between urinary pesticide residue levels and neurotoxic symptoms amongst women working on Western Cape farms in South Africa. Method: A total of 211 women were recruited from farms (n = 121) and neighbouring towns (n = 90). Participant assessment was via a Q16 questionnaire, reporting on pesticide exposures and measurement of urinary OP metabolite concentrations of dialkyl phosphates (DAP) and chlorpyriphos, 3,5,6-trichloropyridinol (TCPY) and of pyrethroid (PYR) metabolite concentrations (3- phenoxybenzoic acid (3PBA), 4-fluoro-3-phenoxybenzoic acid (4F3PBA), cis-2,2-dibromovinyl-2,2-dimethylcyclopropane-1-carboxylic acid (DBCA), and the cis- and trans isomers of 2,2-dichlorovinyl-2,2-dimethylcyclopropane-1-carboxylic acid. Results: Median urinary pesticide metabolites were slightly (6%–49%) elevated in the farm group compared to the town group, with 2 metabolites significantly higher and some lower in the farm group. The prevalence of all Q16 symptoms was higher amongst farm women compared to town women. Three Q16 symptoms (problems with buttoning, reading and notes) were significantly positively associated with three pyrethroid metabolites (cis- and trans-DCCA and DBCA), although associations may due to chance as multiple comparisons were made. The strongest association for a pyrethroid metabolite was between problems with buttoning and DBCA (odds ratio (OR) = 8.93, 95% confidence interval (CI):1.71–46.5. There was no association between Q16 symptoms and OP metabolites. Conclusions: Women farm residents and rural women from neighbouring towns in the Western Cape are exposed to OP and PYR pesticides. The study did not provide strong evidence that pesticides are associated with neurotoxic symptoms but associations found could be explored further. PMID:26042367

Examining impacts of current-use pesticides in Southern Ontario using in situ exposures of the amphipod Hyalella azteca.

PubMed

Bartlett, Adrienne J; Struger, John; Grapentine, Lee C; Palace, Vince P

2016-05-01

In situ exposures with Hyalella azteca were used to assess impacts of current-use pesticides in Southern Ontario, Canada. Exposures were conducted over 2 growing seasons within areas of high pesticide use: 1 site on Prudhomme Creek and 3 sites on Twenty Mile Creek. Three sites on Spencer Creek, an area of low pesticide use, were added in the second season. Surface water samples were collected every 2 wk to 3 wk and analyzed for a suite of pesticides. Hyalella were exposed in situ for 1 wk every 4 wk to 6 wk, and survival and acetylcholinesterase (AChE) activity were measured. Pesticides in surface waters reflected seasonal use patterns: lower concentrations in spring and fall and higher concentrations during summer months. Organophosphate insecticides (chlorpyrifos, azinphos methyl, diazinon) and acid herbicides (2,4-dichlorophenoxyacetic acid [2,4-D], mecoprop) were routinely detected in Prudhomme Creek, whereas neutral herbicides (atrazine, metolachlor) dominated the pesticide signature of Twenty Mile Creek. Spencer Creek contained fewer pesticides, which were measured at lower concentrations. In situ effects also followed seasonal patterns: higher survival and AChE activity in spring and fall, and lower survival and AChE activity during summer months. The highest toxicity was observed at Prudhomme Creek and was primarily associated with organophosphates. The present study demonstrated that current-use pesticides in Southern Ontario were linked to in situ effects and identified sites of concern requiring further investigation. © 2015 Crown in the Right of Canada.

40 CFR 180.636 - 1,3-dichloropropene; tolerances for residues.

Code of Federal Regulations, 2010 CFR

2010-07-01

...) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD Specific Tolerances...-chloroacrylic acid, and cis- and trans-3-chloroallyl alcohol in or on the following commodities. Commodity Parts...

Multi-residue analysis of 26 organochlorine pesticides in Alpinia oxyphylla by GC-ECD after solid phase extraction and acid cleanup.

PubMed

Zhao, Xiangsheng; Zhou, Yakui; Kong, Weijun; Gong, Bao; Chen, Deli; Wei, Jianhe; Yang, Meihua

2016-04-01

A simple and effective multi-residue method was developed and validated for the analysis of 26 organochlorine pesticide residues in Alpinia oxyphylla by a gas chromatography with an electron capture detector (GC-ECD). The target pesticides were extracted by sonication and cleaned up with florisil solid phase extraction and sulphuric acid. Some crucial parameters, including extraction solvent and time, sorbent type, elute solvent and concentration of sulphuric acid were optimized to improve the performance of sample preparation procedure. The optimized method gave high sensitivity with detection limit ranging from 0.1 to 2.0μg/kg. Matrix-matched calibration was employed for the quantification, and a wide linear range (from 1.0 to 1000μg/kg) with r(2) values ranging from 0.9971 to 0.9998 was obtained. For the majority of the tested pesticides, the average recoveries were in acceptable range (between 70% and 110%) with relative standard deviation values below 15.0%. Matrix effect was evaluated for target compounds through the study of ratio of peak area obtained in the solvent and blank matrix. The proposed method was applied to simultaneously analyze 26 pesticides in 55 batches of Alpinia oxyphylla samples. 3 samples were found to be positive with four pesticides (α-BHC, quintozene, trans-chlordane and op'-DDD), which were confirmed by gas chromatography-mass spectrometry (GC-MS) in selective ion monitoring (SIM) mode. Copyright © 2016 Elsevier B.V. All rights reserved.

40 CFR 180.1022 - Iodine-detergent complex; exemption from the requirement of a tolerance.

Code of Federal Regulations, 2011 CFR

2011-07-01

... PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN... a tolerance. The aqueous solution of hydriodic acid and elemental iodine, including one or both of...

Novel 2,4-Dichlorophenoxyacetic Acid Degradation Genes from Oligotrophic Bradyrhizobium sp. Strain HW13 Isolated from a Pristine Environment

PubMed Central

Kitagawa, Wataru; Takami, Sachiko; Miyauchi, Keisuke; Masai, Eiji; Kamagata, Yoichi; Tiedje, James M.; Fukuda, Masao

2002-01-01

The tfd genes of Ralstonia eutropha JMP134 are the only well-characterized set of genes responsible for 2,4-dichlorophenoxyacetic acid (2,4-D) degradation among 2,4-D-degrading bacteria. A new family of 2,4-D degradation genes, cadRABKC, was cloned and characterized from Bradyrhizobium sp. strain HW13, a strain that was isolated from a buried Hawaiian soil that has never experienced anthropogenic chemicals. The cadR gene was inferred to encode an AraC/XylS type of transcriptional regulator from its deduced amino acid sequence. The cadABC genes were predicted to encode 2,4-D oxygenase subunits from their deduced amino acid sequences that showed 46, 44, and 37% identities with the TftA and TftB subunits of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) oxygenase of Burkholderia cepacia AC1100 and with a putative ferredoxin, ThcC, of Rhodococcus erythropolis NI86/21, respectively. They are thoroughly different from the 2,4-D dioxygenase gene, tfdA, of R. eutropha JMP134. The cadK gene was presumed to encode a 2,4-D transport protein from its deduced amino acid sequence that showed 60% identity with the 2,4-D transporter, TfdK, of strain JMP134. Sinorhizobium meliloti Rm1021 cells containing cadRABKC transformed several phenoxyacetic acids, including 2,4-D and 2,4,5-T, to corresponding phenol derivatives. Frameshift mutations indicated that each of the cadRABC genes was essential for 2,4-D conversion in strain Rm1021 but that cadK was not. Five 2,4-D degraders, including Bradyrhizobium and Sphingomonas strains, were found to have cadA gene homologs, suggesting that these 2,4-D degraders share 2,4-D degradation genes similar to those of strain HW13 cadABC. PMID:11751829

Assisted inhibition effect of acetylcholinesterase with n-octylphosphonic acid and application in high sensitive detection of organophosphorous pesticides by matrix-assisted laser desorption/ionization Fourier transform mass spectrometry.

PubMed

Cai, Tingting; Zhang, Li; Wang, Haoyang; Zhang, Jing; Guo, Yinlong

2011-11-14

A simple and practical approach to improve the sensitivity of acetylcholinesterase (AChE)-inhibited method has been developed for monitoring organophosphorous (OP) pesticide residues. In this work, matrix-assisted laser desorption/ionization Fourier transform mass spectrometry (MALDI-FTMS) was used to detect AChE activity. Due to its good salt-tolerance and low sample consumption, MALDI-FTMS facilitates rapid and high-throughput screening of OP pesticides. Here we describe a new method to obtain low detection limits via employing external reagents. Among candidate compounds, n-octylphosphonic acid (n-Octyl-PA) displays assistant effect to enhance AChE inhibition by OP pesticides. In presence of n-Octyl-PA, the percentages of AChE inhibition still kept correlation with OP pesticide concentrations. The detection limits were improved significantly even by 10(2)-10(3) folds in comparison with conventional enzyme-inhibited methods. Different detection limits of OP pesticides with different toxicities were as low as 0.005 μg L(-1) for high toxic pesticides and 0.05 μg L(-1) for low toxic pesticides. Besides, the reliability of results from this method to analyze cowpea samples had been demonstrated by liquid-chromatography tandem mass spectrometry (LC-MS/MS). The application of this commercial available assistant agent shows great promise to detect OP compounds in complicated biological matrix and broadens the mind for high sensitivity detection of OP pesticide residues in agricultural products. Copyright © 2011 Elsevier B.V. All rights reserved.

Ground water contamination and costs of pesticide restrictions in the southeastern coastal plain

DOE Office of Scientific and Technical Information (OSTI.GOV)

Danielson, L.E.; Carlson, G.A.; Liu, S.

The project developed new methodology for estimating: (1) groundwater contamination potential (GWCP) in the Southeast Coastal Plain, and (2) the potential economic impacts of selected policies that restrict pesticide use. The potential for ground water contamination was estimated by use of a simple matrix for combining ratings for both soil leaching potential and pesticide leaching potential. Key soil variables included soil texture, soil acidity and organic matter content. Key pesticide characteristics included Koc, pesticide half-life, the rate of application and the fraction of the pesticide hitting the soil. Comparisons of pesticide use from various farmer and expert opinion surveys weremore » made for pesticide groups and for individual pesticide products. Methodology for merging the GWCP changes and lost benefits from selected herbicide cancellations was developed using corn production in the North Carolina Coastal Plain. Economic evaluations of pesticide cancellations for corn included national and Coastal Plain estimates for atrazine; metolachlor; dicamba; dicamba and atrazine; and dicamba, atrazine and metolachlor.« less

Problems and solutions of polyethylene glycol co-injection method in multiresidue pesticide analysis by gas chromatography-mass spectrometry: evaluation of instability phenomenon in type II pyrethroids and its suppression by novel analyte protectants.

PubMed

Akutsu, Kazuhiko; Kitagawa, Yoko; Yoshimitsu, Masato; Takatori, Satoshi; Fukui, Naoki; Osakada, Masakazu; Uchida, Kotaro; Azuma, Emiko; Kajimura, Keiji

2018-05-01

Polyethylene glycol 300 is commonly used as a base material for "analyte protection" in multiresidue pesticide analysis via gas chromatography-mass spectrometry. However, the disadvantage of the co-injection method using polyethylene glycol 300 is that it causes peak instability in α-cyano pyrethroids (type II pyrethroids) such as fluvalinate. In this study, we confirmed the instability phenomenon in type II pyrethroids and developed novel analyte protectants for acetone/n-hexane mixture solution to suppress the phenomenon. Our findings revealed that among the examined additive compounds, three lipophilic ascorbic acid derivatives, 3-O-ethyl-L-ascorbic acid, 6-O-palmitoyl-L-ascorbic acid, and 6-O-stearoyl-L-ascorbic acid, could effectively stabilize the type II pyrethroids in the presence of polyethylene glycol 300. A mixture of the three ascorbic acid derivatives and polyethylene glycol 300 proved to be an effective analyte protectant for multiresidue pesticide analysis. Further, we designed and evaluated a new combination of analyte protectant compounds without using polyethylene glycol or the troublesome hydrophilic compounds. Consequently, we obtained a set of 10 medium- and long-chain saturated fatty acids as an effective analyte protectant suitable for acetone/n-hexane solution that did not cause peak instability in type II pyrethroids. These analyte protectants will be useful in multiresidue pesticide analysis by gas chromatography-mass spectrometry in terms of ruggedness and reliable quantitativeness. Graphical abstract Comparison of effectiveness of the addition of lipophilic derivatives of ascorbic acid in controlling the instability phenomenon of fluvalinate with polyethylene glycol 300.

Assessment of Envi-Carb™ as a passive sampler binding phase for acid herbicides without pH adjustment.

PubMed

Seen, Andrew; Bizeau, Oceane; Sadler, Lachlan; Jordan, Timothy; Nichols, David

2014-05-01

The graphitised carbon solid phase extraction (SPE) sorbent Envi-Carb has been used to fabricate glass fibre filter- Envi-Carb "sandwich" disks for use as a passive sampler for acid herbicides. Passive sampler uptake of a suite of herbicides, including the phenoxyacetic acid herbicides 4-chloro-o-tolyloxyacetic acid (MCPA), 2,4-dichlorophenoxyacetic acid (2,4-D) and 3,6-dichloro-2-methoxybenzoic acid (Dicamba), was achieved without pH adjustment, demonstrating for the first time a suitable binding phase for passive sampling of acid herbicides at neutral pH. Passive sampling experiments with Duck River (Tasmania, Australia) water spiked at 0.5 μg L(-1) herbicide concentration over a 7 d deployment period showed that sampling rates in Duck River water decreased for seven out of eight herbicides, and in the cases of 3,6-dichloro-2-pyridinecarboxylic acid (Clopyralid) and Dicamba no accumulation of the herbicides occurred in the Envi-Carb over the deployment period. Sampling rates for 4-amino-3,5,6-trichloro-2-pyridinecarboxylic acid (Picloram), 2,4-D and MCPA decreased to approximately 30% of the sampling rates in ultrapure water, whilst sampling rates for 2-(4,6-dimethylpyrimidin-2-ylcarbamoylsulfamoyl) benzoic acid, methyl ester (Sulfometuron-methyl) and 3,5,6-Trichloro-2-pyridinyloxyacetic acid (Triclopyr) were approximately 60% of the ultrapure water sampling rate. For methyl N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-D-alaninate (Metalaxyl-M) there was little variation in sampling rate between passive sampling experiments in ultrapure water and Duck River water. SPE experiments undertaken with Envi-Carb disks using ultrapure water and filtered and unfiltered Duck River water showed that not only is adsorption onto particulate matter in Duck River water responsible for a reduction in herbicide sampling rate, but interactions of herbicides with dissolved or colloidal matter (matter able to pass through a 0.2 μm membrane filter) also reduces the herbicide sampling rate. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

Luminescence recognition of different organophosphorus pesticides by the luminescent Eu(III)-pyridine-2,6-dicarboxylic acid probe.

PubMed

Azab, Hassan A; Duerkop, Axel; Anwar, Z M; Hussein, Belal H M; Rizk, Moustafa A; Amin, Tarek

2013-01-08

Luminescence quenching of a novel long lived Eu(III)-pyridine-2,6-dicarboxylic acid probe of 1:2 stoichiometric ratio has been studied in 0.10 volume fraction ethanol-water mixture at pH 7.5 (HEPES buffer) in the presence of the organophosphorus pesticides chlorfenvinphos (P1), malathion (P2), azinphos (P3), and paraxon ethyl (P4). The luminescence intensity of Eu(III)-(PDCA)(2) probe decreases as the concentration of the pesticide increases. It was observed that the quenching due to P3 and P4 proceeds via both diffusional and static quenching processes. Direct methods for the determination of the pesticides under investigation have been developed using the luminescence quenching of Eu(III)-pyridine-2,6-dicarboxylic acid probe in solution. The linear range for determination of the selected pesticides is 1.0-35.0 μM. The detection limits were 0.24-0.55 μM for P3, P4, and P1 and 2.5 μM for P2, respectively. The binding constants (K), and thermodynamic parameters of the OPs with Eu(III)-(PDCA)(2) were evaluated. Positive and negative values of entropy (ΔS) and enthalpy (ΔH) changes for Eu(III)-(PDCA)(2)-P1 ternary complex were calculated. As the waters in this study do not contain the above mentioned OPs over the limit detectable by the method, a recovery study was carried out after the addition of the adequate amounts of the organophosphorus pesticides under investigation. Copyright © 2012 Elsevier B.V. All rights reserved.

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.

Chromatographic behaviour predicts the ability of potential nootropics to permeate the blood-brain barrier.

PubMed

Farsa, Oldřich

2013-01-01

The log BB parameter is the logarithm of the ratio of a compound's equilibrium concentrations in the brain tissue versus the blood plasma. This parameter is a useful descriptor in assessing the ability of a compound to permeate the blood-brain barrier. The aim of this study was to develop a Hansch-type linear regression QSAR model that correlates the parameter log BB and the retention time of drugs and other organic compounds on a reversed-phase HPLC containing an embedded amide moiety. The retention time was expressed by the capacity factor log k'. The second aim was to estimate the brain's absorption of 2-(azacycloalkyl)acetamidophenoxyacetic acids, which are analogues of piracetam, nefiracetam, and meclofenoxate. Notably, these acids may be novel nootropics. Two simple regression models that relate log BB and log k' were developed from an assay performed using a reversed-phase HPLC that contained an embedded amide moiety. Both the quadratic and linear models yielded statistical parameters comparable to previously published models of log BB dependence on various structural characteristics. The models predict that four members of the substituted phenoxyacetic acid series have a strong chance of permeating the barrier and being absorbed in the brain. The results of this study show that a reversed-phase HPLC system containing an embedded amide moiety is a functional in vitro surrogate of the blood-brain barrier. These results suggest that racetam-type nootropic drugs containing a carboxylic moiety could be more poorly absorbed than analogues devoid of the carboxyl group, especially if the compounds penetrate the barrier by a simple diffusion mechanism.

Comparison of questionnaire-based estimation of pesticide residue intake from fruits and vegetables with urinary concentrations of pesticide biomarkers.

PubMed

Chiu, Yu-Han; Williams, Paige L; Mínguez-Alarcón, Lidia; Gillman, Matthew; Sun, Qi; Ospina, Maria; Calafat, Antonia M; Hauser, Russ; Chavarro, Jorge E

2018-01-01

We developed a pesticide residue burden score (PRBS) based on a food frequency questionnaire and surveillance data on food pesticide residues to characterize dietary exposure over the past year. In the present study, we evaluated the association of the PRBS with urinary concentrations of pesticide biomarkers. Fruit and vegetable (FV) intake was classified as having high (PRBS≥4) or low (PRBS<4) pesticide residues for 90 men from the EARTH study. Two urine samples per man were analyzed for seven biomarkers of organophosphate and pyrethroid insecticides, and the herbicide 2,4-dichlorophenoxyacetic acid. We used generalized estimating equations to analyze the association of the PRBS with urinary concentrations of pesticide biomarkers. Urinary concentrations of pesticide biomarkers were positively related to high pesticide FV intake but inversely related to low pesticide FV intake. The molar sum of urinary concentrations of pesticide biomarkers was 21% (95% confidence interval (CI): 2%, 44%) higher for each one serving/day increase in high pesticide FV intake, and 10% (95% CI: 1%, 18%) lower for each one serving/day increase in low pesticide FV intake. Furthermore, intake of high pesticide FVs positively related to most individual urinary biomarkers. Our findings support the usefulness of the PRBS approach to characterize dietary exposure to select pesticides.

40 CFR 455.20 - Applicability; description of the organic pesticide chemicals manufacturing subcategory.

Code of Federal Regulations, 2014 CFR

2014-07-01

...; Endothall Acid; EXD (Herbisan); Gibberellic Acid; Glyphosate; Naphthalene Acetic Acid; Propargite; 1,8..., Terbutryn, Cyanazine, Atrazine, Propazine, Simazine, Terbuthylazine, Hexazinone, and Glyphosate. (b) For the...

40 CFR 455.20 - Applicability; description of the organic pesticide chemicals manufacturing subcategory.

Code of Federal Regulations, 2013 CFR

2013-07-01

...; Endothall Acid; EXD (Herbisan); Gibberellic Acid; Glyphosate; Naphthalene Acetic Acid; Propargite; 1,8..., Terbutryn, Cyanazine, Atrazine, Propazine, Simazine, Terbuthylazine, Hexazinone, and Glyphosate. (b) For the...

Fate of High Priority Pesticides During Drinking Water Treatment

EPA Science Inventory

The fate of organophosphorus (OP) pesticides in the presence of chlorinated oxidants was investigated under drinking water treatment conditions. In the presence of aqueous chlorine, intrinsic rate coefficients were found for the reaction of hypochlorous acid and hypochlorite ion ...

Occurrence of non extractable pesticide residues in physical and chemical fractions of two soils

NASA Astrophysics Data System (ADS)

Andreou, Kostas; Semple, Kirk; Jones, Kevin

2010-05-01

Soils are considered to be a significant sink for organic contaminants, including pesticides, in the environment. Understanding the distribution and localisation of aged pesticide residues in soil is of great importance for assessing the mobility and availability of these chemicals in the environment. This study aimed to characterise the distribution of radiolabeled herbicide isoproturon and the radiolabeled insecticides diazinon and cypermethrin in two organically managed soils. The soils were spiked and aged under laboratory conditions for 17 months. The labile fraction of the pesticides residues was recovered in CaCl2 (0.01M) and then subjected to physical size fractionation using sedimentation and centrifugation steps, with >20μm, 20-2μm and 2-0.1μm soil factions collected. Further, the distribution of the pesticide residues in the organic matter of the fractionated soil was investigated using a sequential alkaline extraction (0.1N NaOH) into humic and fulvic acid and humin. Soil fractions of 20-2μm and 2-0.1μm had the largest burden of the 14C-residues. Different soil constituents have different capacities to form non-extractable residues. Soil solid fractions of 20-2 µm and <2 µm had far greater affinity to the 14C-pesticide residues than the coarser fraction (>20 µm). Fulvic acid showed to play a vital role in the formation and stabilisation of non-extractable 14C-pesticide residues in most cases.Assessment of the likelihood of the pesticide residues to become available to soil biota requires an understanding of the structure of the SOM matrix and the definition of the kinetics of the pesticide residues in different SOM pools as a function of the time.

[The pyretroind pesticides lambda-cigalothrines influence on composition of free aminoacids in tissue of fish in Alazani River].

PubMed

Dzhikiia, G M; Mchedluri, T T; Nikolaĭshvili, M I; Zurabishvili, Z A; Iordanishvili, G S

2011-12-01

The aim of the research was to study toxic effect of lambda-cigalothrin, on quantitative contents of free amino acid in muscle, liver and in brain of fishes in r. Alazani. It was found that under the action of lambda-cigalothrin total amount of free amino acid in fish's tissue was increasing, contents of glycine, asparagine and glutamine acids, alanine and cysteine also increased. Increasing of glutamine and asparagines acids content in muscle and liver of fish goes with the dissimilation of other amino acids through the process of their deaminization by glutamate dehydrogenation system. Increasing the alanine content is indicative of reinforcement of transamination processes. Decrease of phenylalanine, valine, glycine and the other amino acids content is explained by reinforcement of amino acids catabolism in condition of pesticide load, as it occurs in condition of fishes' intoxication by phenols.

Fatty Acid Methyl Ester (FAME) Succession in Different Substrates as Affected by the Co-Application of Three Pesticides.

PubMed

Cardinali, Alessandra; Pizzeghello, Diego; Zanin, Giuseppe

2015-01-01

In intensive agriculture areas the use of pesticides can alter soil properties and microbial community structure with the risk of reducing soil quality. In this study the fatty acid methyl esters (FAMEs) evolution has been studied in a factorial lab experiment combining five substrates (a soil, two aged composts and their mixtures) treated with a co-application of three pesticides (azoxystrobin, chlorotoluron and epoxiconazole), with two extraction methods, and two incubation times (0 and 58 days). FAMEs extraction followed the microbial identification system (MIDI) and ester-linked method (EL). The pesticides showed high persistence, as revealed by half-life (t1/2) values ranging from 168 to 298 days, which confirms their recalcitrance to degradation. However, t1/2 values were affected by substrate and compost age down to 8 days for chlorotoluron in S and up to 453 days for epoxiconazole in 12M. Fifty-six FAMEs were detected. Analysis of variance (ANOVA) showed that the EL method detected a higher number of FAMEs and unique FAMEs than the MIDI one, whereas principal component analysis (PCA) highlighted that the monosaturated 18:1ω9c and cyclopropane 19:0ω10c/19ω6 were the most significant FAMEs grouping by extraction method. The cyclopropyl to monoenoic acids ratio evidenced higher stress conditions when pesticides were applied to compost and compost+soil than solely soil, as well as with final time. Overall, FAMEs profiles showed the importance of the extraction method for both substrate and incubation time, the t1/2 values highlighted the effectiveness of solely soil and the less mature compost in reducing the persistence of pesticides.

Fatty Acid Methyl Ester (FAME) Succession in Different Substrates as Affected by the Co-Application of Three Pesticides

PubMed Central

Cardinali, Alessandra; Pizzeghello, Diego; Zanin, Giuseppe

2015-01-01

Introduction In intensive agriculture areas the use of pesticides can alter soil properties and microbial community structure with the risk of reducing soil quality. Materials and Methods In this study the fatty acid methyl esters (FAMEs) evolution has been studied in a factorial lab experiment combining five substrates (a soil, two aged composts and their mixtures) treated with a co-application of three pesticides (azoxystrobin, chlorotoluron and epoxiconazole), with two extraction methods, and two incubation times (0 and 58 days). FAMEs extraction followed the microbial identification system (MIDI) and ester-linked method (EL). Results and Discussion The pesticides showed high persistence, as revealed by half-life (t1/2) values ranging from 168 to 298 days, which confirms their recalcitrance to degradation. However, t1/2 values were affected by substrate and compost age down to 8 days for chlorotoluron in S and up to 453 days for epoxiconazole in 12M. Fifty-six FAMEs were detected. Analysis of variance (ANOVA) showed that the EL method detected a higher number of FAMEs and unique FAMEs than the MIDI one, whereas principal component analysis (PCA) highlighted that the monosaturated 18:1ω9c and cyclopropane 19:0ω10c/19ω6 were the most significant FAMEs grouping by extraction method. The cyclopropyl to monoenoic acids ratio evidenced higher stress conditions when pesticides were applied to compost and compost+soil than solely soil, as well as with final time. Conclusion Overall, FAMEs profiles showed the importance of the extraction method for both substrate and incubation time, the t1/2 values highlighted the effectiveness of solely soil and the less mature compost in reducing the persistence of pesticides. PMID:26694029

Preservation Using Pesticides: Some Words of Caution.

ERIC Educational Resources Information Center

Davis, Mary

1985-01-01

Addresses problem of insects and other pests in library facility and material maintenance. Highlights include dangers of chemical pesticides; alternative methods for treatment of book infestations (light and temperature regulation, freezing, establishment of low oxygen atmosphere, microwaves and radiation, boric acid); and state and federal laws…

Pesticidal and pest repellency activities of rhizomes of Drynaria quercifolia (J. Smith) against Tribolium castaneum (Herbst).

PubMed

Khan, Alam; Islam, Md Hedayetul; Islam, Md Ekramul; Al-Bari, Md Abdul Alim; Parvin, Mst Shahnaj; Sayeed, Mohammed Abu; Islam, Md Nurul; Haque, Md Ekramul

2014-10-01

Tribolium castaneum (Herbst) is a harmful pest of stored grain and flour-based products in tropical and subtropical region. In the present study, rhizome of Drynaria quercifolia (J. Smith) was evaluated for pesticidal and pest repellency activities against T. castaneum, using surface film method and filter paper disc method, respectively. In addition, activity of the isolated compound 3,4-dihydroxybenzoic acid was evaluated against the pest. Chloroform soluble fraction of ethanol extract of rhizome of D. quercifolia showed significant pesticidal activity at doses 0.88 to 1.77 mg/cm(2) and significant pest repellency activity at doses 0.94 to 0.23 mg/cm(2). No pesticidal and pest repellency activity was found for petroleum ether, ethyl acetate and methanol soluble fractions of ethanol extract as well as for 3,4-dihydroxybenzoic acid. Considering our findings it can be concluded that chloroform soluble fraction of rhizome of D. quercifolia is useful in controlling T. castaneum of stored grain and flour-based products.

Correlations between chromatographic parameters and bioactivity predictors of potential herbicides.

PubMed

Janicka, Małgorzata

2014-08-01

Different liquid chromatography techniques, including reversed-phase liquid chromatography on Purosphere RP-18e, IAM.PC.DD2 and Cosmosil Cholester columns and micellar liqud chromatography with a Purosphere RP-8e column and using buffered sodium dodecyl sulfate-acetonitrile as the mobile phase, were applied to study the lipophilic properties of 15 newly synthesized phenoxyacetic and carbamic acid derivatives, which are potential herbicides. Chromatographic lipophilicity descriptors were used to extrapolate log k parameters (log kw and log km) and log k values. Partitioning lipophilicity descriptors, i.e., log P coefficients in an n-octanol-water system, were computed from the molecular structures of the tested compounds. Bioactivity descriptors, including partition coefficients in a water-plant cuticle system and water-human serum albumin and coefficients for human skin partition and permeation were calculated in silico by ACD/ADME software using the linear solvation energy relationship of Abraham. Principal component analysis was applied to describe similarities between various chromatographic and partitioning lipophilicities. Highly significant, predictive linear relationships were found between chromatographic parameters and bioactivity descriptors. © The Author [2013]. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Urine Methyl Hippuric Acid Levels in Acute Pesticide Poisoning: Estimation of Ingested Xylene Volume and Association with Clinical Outcome Parameters.

PubMed

Choi, Chi Young; Cho, NamJun; Park, Su Yeon; Park, Samel; Gil, Hyo Wook; Hong, Sae Yong

2017-12-01

To determine the relationship between the oral ingestion volume of xylene and methyl hippuric acid (MHA) in urine, we measured MHA in 11 patients whose ingested xylene volume was identified. The best-fit equation between urine MHA and ingested amount of xylene was as follows: y (ingested amount of xylene, mL/kg) = -0.052x² + 0.756x (x = MHA in urine in g/g creatinine). From this equation, we estimated the ingested xylene volume in 194 patients who had ingested pesticide of which the formulation was not available. Our results demonstrated that oxadiazole, dinitroaniline, chloroacetamide, organophosphate, and pyrethroid were xylene-containing pesticide classes, while the paraquat, glyphosate, glufosinate, synthetic auxin, fungicide, neonicotinoid, and carbamate classes were xylene-free pesticides. Sub-group univariate analysis showed a significant association between MHA levels in urine and ventilator necessity in the pyrethroid group. However, this association was not observed in the organophosphate group. Our results suggest that MHA in urine is a surrogate marker for xylene ingestion, and high urine MHA levels may be a risk factor for poor clinical outcome with some pesticide poisoning. © 2017 The Korean Academy of Medical Sciences.

Vapor-phase and particulate-associated pesticides and PCB concentrations in eastern North Dakota air samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hawthorne, S.B.; Miller, D.J.; Louie, P.K.K.

1996-05-01

Vapor-phase and suspended particulate (<50 {mu}m) samples were collected on polyurethane foam (PUF) and quartz fiber filters in rural North Dakota to determine the air concentrations of pesticides in an area where agriculture is a primary source of semivolatile pollutants. Samples were collected at two sites from 1992 to 1994 that were at least 0.4 km from the nearest farmed fields and known application of pesticides, and analyzed for 22 different organochlorine, triazine, and acid herbicide pesticides. Fourteen pesticides were found above the detection limits (typically <1 pg/m{sup 3}). Concentrations of polychlorinated biphenyl (PCB) congeners were much lower (<50 pg/m{supmore » 3} in all cases) than many of the pesticides. These results demonstrate that pesticides are among the most prevalent chlorinated semivolatile pollutants present in rural North Dakota, that significant transport of pesticides occurs both in the vapor-phase and on suspended particulate matter, and that blown soil may be a significant mechanism for introducing pesticides into surface and ground waters. 32 refs., 2 figs., 4 tabs.« less

Toxicity Assessment of Expired Pesticides to Green Algae Pseudokirchneriella subcapitata

PubMed Central

Satyavani, G.; Chandrasehar, G.; Varma, K. Krishna; Goparaju, A.; Ayyappan, S.; Reddy, P. Neelakanta; Murthy, P. Balakrishna

2012-01-01

In order to investigate the effect of expired pesticides on the yield and growth rate of green algae Pseudokirchneriella subcapitata, a study was conducted as per the Organisation for Economic Cooperation and Development (OECD) guideline number 201. Fifteen expired pesticide formulations, most commonly used in Indian agriculture, were tested in comparison with their unexpired counterparts. The expired pesticide formulations studied belonged to various class and functional groups: organophosphate, pyrethroid-based insecticides; azole-based fungicides; acetamide, propionate, acetic acid-based herbicides; fungicides mixtures containing two actives—azole and dithiocarbamate. The toxicity endpoints of yield (EyC50: 0–72 h) and growth rate (ErC50: 0–72 h) of Pseudokirchneriella subcapitata for each pesticide formulation (both expired and unexpired pesticides) were determined statistically using TOXSTAT 3.5 version software. The results pointed out that some expired pesticide formulations exhibited higher toxicity to tested algal species, as compared to the corresponding unexpired pesticides. These data thus stress the need for greater care to dispose expired pesticides to water bodies, to avoid the effects on aquatic ecospecies tested. PMID:23762633

78 FR 46265 - Complex Polymeric Polyhydroxy Acids; Exemption From the Requirement of a Tolerance

Federal Register 2010, 2011, 2012, 2013, 2014

2013-07-31

... number of analyses to determine the risks from aggregate exposure to pesticide residues. First, EPA... agricultural soils. Its major components are humic acid, fulvic acid, and tannins, and their relative...

Effects of a mixture of vegetable and essential oils and fatty acid potassium salts on Tetranychus urticae and Phytoseiulus persimilis.

PubMed

Tsolakis, H; Ragusa, S

2008-06-01

Laboratory trials were carried out to evaluate the toxicity and the influence of a commercial mixture of vegetal, essential oils, and potassium salts of fatty acids (Acaridoil 13SL) on the population growth rate (r(i)--instantaneous rate of increase) of two mite species, the phytophagous Tetranychus urticae Koch and the predator Phytoseiulus persimilis Athias-Henriot. A residue of 1.3 mg/cm(2) of pesticide solution was harmless for Ph. persimilis eggs, while a moderate mortality of eggs and of larvae from treated eggs of T. urticae, was observed (53.8%). The pesticide also caused a delay in the postembryonic development of the tetranychid. Moreover, 83.4% mortality was reported for treated females tetranychids and only 24.0% for Ph. persimilis females. The pesticide influenced negatively the population growth of T. urticae which showed a very low rate of increase (r(i)=0.07), compared to that obtained in the control (r(i)=0.68). The pesticide did not affect negatively the reproductive potential of Ph. persimilis (r(i)=0.54 and r(i)=0.57 for test and control, respectively). These results suggest a considerable acaricidal activity of potassium salts of fatty acids and caraway oil on T. urticae and a good selectivity on Ph. persimilis.

Transformation of Organophosphorus Pesticides in the Presence of Aqueous Chlorine: Kinetics, Pathways, and Structure-Activity Relationships

EPA Science Inventory

The fate of organophosphorus (OP) pesticides in the presence of aqueous chlorine was investigated under simulated drinking water treatment conditions. Intrinsic rate coefficients were found for the reaction of hypochlorous acid (kHOCl,OP) and hypochlorite ion (kOCl,OP) for eight...

78 FR 14540 - Cyromazine, Silica Silicates (Silica Dioxide and Silica Gel), Glufosinate Ammonium, Dioctyl...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-03-06

..., human health, farm worker, and agricultural advocates; the chemical industry; pesticide users; and... disproportionately high and adverse human health impacts and/or environmental effects from exposure to the pesticides... Acid (UDA) Registration Review; Draft Human Health and Ecological Risk Assessments; Notice of...

75 FR 16017 - Cloquintocet-mexyl; Pesticide Tolerances

Federal Register 2010, 2011, 2012, 2013, 2014

2010-03-31

...-quinolinoxyacetic acid) on wheat forage, wheat grain, wheat hay, and wheat straw. Arysta LifeScience North America...-5805. II. Petition for Tolerance EPA has received a petition from Arysta LifeScience North America, LLC... filing of the above-referenced pesticide petition (PP 9E7592) by Arysta LifeScience North America, LLC...

Developmental Toxicity of Perfluorinated Phosphonic Acids in Mice

EPA Science Inventory

Perfluorinated phosphonic acids (PFPAs) are a third member of the perfluoroalkyl acid (PFAA) family, and are structurally similar to the perfluoroalkyl sulfonates and perfluoroalkyl carboxylates. PFPAs are used primarily as a surfactant defoaming agent in pesticide production. Re...

Modificatory effect of vitamin C and vitamin B-complex on meiotic inhibition induced by organophosphorus pesticide in mice Mus musculus.

PubMed

Hoda, Q; Azfer, M A; Sinha, S P

1993-01-01

Administration of organophosphorous pesticide Malathion and Rogor (both @ 0.2 micrograms/kg body wt/day) upto ten days was found to decrease the division rate in the primary spermatocytes of mice. The concurrent administration of vitamin B-complex (0.3 ml of 1% polybion) or ascorbic acid (0.25 ml of 1% Redoxon) with the pesticide could nullify the meiotic inhibition caused by the pesticides. The vitamins were not found to produce any significant effect on the division rate. Possible mechanism(s) behind this vitamin mediated nullification of meiotic inhibition are discussed.

Influence of steric hindrance on enantioseparation of Dns-amino acids and pesticides on terguride based chiral selectors in capillary electrophoresis.

PubMed

Honzátko, Ales; Cvak, Jan; Vaingátová, Silvie; Flieger, Miroslav

2005-05-01

Three urea derivatives of ergoline-based chiral selectors (CSs), differing in the size of the urea side chain, i.e. dimethyl- (CSI), diethyl- (CSII), and diisopropylurea (CSIII), were used to study the effect of steric hindrance on the enantioseparation of dansyl amino acids (Dns-AAs), pesticides, and mandelic acid under condition of capillary electrophoresis (CE) in linear polyacrylamide coated capillaries. A mixture of organic modifiers (MeOH/THF, 4:1 v/v) in a BGE consisting of 100 mM beta-alanine-acetate was used to increase the solubility of CSs up to 25 mM. The capillary was filled with CS (high UV absorption), and the inlet and outlet vials contained buffer solutions only. The best enantioseparation of Dns-AAs was achieved on CSI. Increased steric hindrance of the chiral binding site led to reduction of both enantioselectivity and resolution. The opposite pattern was observed for the separation of mandelic acid enantiomers, where the best enantioseparation and resolution was obtained with CSIII. Most of the pesticides studied reached maximum selectivity on the diethylurea ergoline derivative (CSII). Enantioseparation of fenoxaprop was found to be independent of steric hindrance.

Enhanced Oxidative Bioremediation of cis-dichloroethene (cis-DCE) and Vinyl Chloride (VC) using Electron Shuttles

DTIC Science & Technology

2009-07-01

1989) Abiotic Reduction of Nitro Aromatic Pesticides in Anaerobic Laboratory Systems. J, Agric, Food Chem, 37: 248. 13 Doménech-Carbó A., Doménech-Carbó...in general. Agricultural Use Humic acids have been used for decades as soil amendments and adjuvants for pesticide formulations for various food...necessary" to support an exception tolerance for pesticide formulations (EPA 2000, Federal Register, July 18, Vol 65, Number 138). Further, materials

Removal of six pesticide residues in cowpea with alkaline electrolysed water.

PubMed

Han, Yongtao; Song, Le; An, Quanshun; Pan, Canping

2017-06-01

Reduction of six pesticide residues (isoprocarb, chlorpyrifos, bifenthrin, beta-cypermethrin, difenoconazole and azoxystrobin) in cowpea by alkaline electrolysed water (AlEW) solutions with different pH was investigated. The commonly used washing treatments in household processing were used for comparison. The residue magnitudes were determined by gas chromatography coupled with tandem mass spectrometry (GC-MS/MS). Results showed that the removal effect of AlEW solution on the six pesticides was superior to tap water, 5% sodium chloride, 5% sodium carbonate and 5% acetic acid solution. AlEW with pH 12.2 had more potential to eliminate the six pesticides in cowpeas. Moreover, the reduction of pesticide residues gradually increased with the increase of washing time. This study demonstrated that AlEW solution with pH of 12.2 could be used to reduce pesticide residues on fresh cowpea samples. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Lentic small water bodies: Variability of pesticide transport and transformation patterns.

PubMed

Ulrich, Uta; Hörmann, Georg; Unger, Malte; Pfannerstill, Matthias; Steinmann, Frank; Fohrer, Nicola

2018-03-15

Lentic small water bodies have a high ecological potential as they fulfill several ecosystem services such as the retention of water and pollutants. They serve as a hot spot of biodiversity. Due to their location in or adjacent to agricultural fields, they can be influenced by inputs of pesticides and their transformation products. Since small water bodies have rarely been part of monitorings/campaigns up to now, their current exposure and processes guiding the pesticide input are not understood, yet. This study presents results of a sampling campaign of 10 lentic small water bodies from 2015 to 2016. They were sampled once after the spring application for a pesticide target screening, before autumn application and three times after rainfall events following the application. The autumn sampling focused on the herbicides metazachlor, flufenacet and their transformation products - oxalic acid and - sulfonic acid as representatives for common pesticides in the study region. The concentrations were associated with rainfall before and after application, characteristics of the site and the water bodies, physicochemical parameters and the applied amount of pesticides. The key results of the pesticide screening in spring indicate positive detections of pesticides which have not been applied for years to the single fields. The autumn sampling showed frequent occurrences of the transformation products, which are formed in soil, from 39% to 94% of all samples (n=71). Discharge patterns were observed for metazachlor with highest concentrations in the first sample after application and then decreasing, but not for flufenacet. The concentrations of the transformation products increased over time and revealed highest values mainly in the last sample. Besides rainfall patterns right after application, the spatial and temporal dissemination of the pesticides to the water bodies seems to play a major role to understand the exposure of lentic small water bodies. Copyright © 2017 Elsevier B.V. All rights reserved.

Pesticide Chemical Research in Toxicology: Lessons from Nature.

PubMed

Casida, John E; Durkin, Kathleen A

2017-01-17

Pesticide researchers are students of nature, and each new compound and mechanism turns a page in the ever-expanding encyclopedia of life. Pesticides are both probes to learn about life processes and tools for pest management to facilitate food production and enhance health. In contrast to some household and industrial chemicals, pesticides are assumed to be hazardous to health and the environment until proven otherwise. About a thousand current pesticides working by more than 100 different mechanisms have helped understand many processes and coupled events. Pesticide chemical research is a major source of toxicology information on new natural products, novel targets or modes of action, resistance mechanisms, xenobiotic metabolism, selective toxicity, safety evaluations, and recommendations for safe and effective pest management. Target binding site models help define the effect of substituent changes and predict modifications for enhanced potency and safety and circumvention of resistance. The contribution of pesticide chemical research in toxicology is illustrated here with two each of the newer or most important insecticides, herbicides, and fungicides. The insecticides are imidacloprid and chlorantraniliprole acting on the nicotinic acetylcholine receptor and the ryanodine receptor Ca 2+ channel, respectively. The herbicides are glyphosate that inhibits aromatic amino acid biosynthesis and mesotrione that prevents plastoquinone and carotenoid formation. The fungicides are azoxystrobin inhibiting the Q o site of the cytochrome bc 1 complex and prothioconazole inhibiting the 14α-demethylase in ergosterol biosynthesis. The two target sites involved for each type of pesticide account for 27-40% of worldwide sales for all insecticides, herbicides, and fungicides. In each case, selection for resistance involving a single amino acid change in the binding site or detoxifying enzyme circumvents the pesticide chemists's structure optimization and guarantees survival of the pest and a continuing job for the design chemist. These lessons from nature are a continuing part of pest management and maintaining human and environmental health.

Prenatal exposure to glycol ethers and cryptorchidism and hypospadias: a nested case-control study.

PubMed

Warembourg, Charline; Botton, Jérémie; Lelong, Nathalie; Rouget, Florence; Khoshnood, Babak; Le Gléau, Florent; Monfort, Christine; Labat, Laurence; Pierre, Fabrice; Heude, Barbara; Slama, Rémy; Multigner, Luc; Charles, Marie-Aline; Cordier, Sylvaine; Garlantézec, Ronan

2018-01-01

Glycol ethers (GE) are oxygenated solvents frequently found in occupational and consumer products. Some of them are well-known testicular and developmental animal toxicants. This study aims to evaluate the risk of male genital anomalies in association with prenatal exposure to GE using urinary biomarkers of exposure. We conducted a case-control study nested in two joint mother-child cohorts (5303 pregnant women). Cases of cryptorchidism and hypospadias were identified at birth and confirmed during a 2-year follow-up period (n=14 cryptorchidism and n=15 hypospadias). Each case was matched to three randomly selected controls within the cohorts for region of inclusion and gestational age at urine sampling. Concentrations of five GE acidic metabolites were measured in spot maternal urine samples collected during pregnancy. ORs were estimated with multivariate conditional logistic regressions including a Firth's penalisation. Detection rates of urinary GE metabolites ranged from 8% to 93% and only two were sufficiently detected (>33%) in each cohort to be studied: methoxyacetic acid (MAA) and phenoxyacetic acid (PhAA). A significantly higher risk of hypospadias was associated with the highest tertile of exposure to MAA: OR (95% CI) 4.5(1.4 to 23.4). No association were observed with urinary concentration of PhAA, nor with the risk of cryptorchidism. In view of the toxicological plausibility of our results, this study, despite its small sample size, raises concern about the potential developmental toxicity of MAA on the male genital system and calls for thorough identification of current sources of exposure to MAA. © Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2018. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

Chromatographic Behaviour Predicts the Ability of Potential Nootropics to Permeate the Blood-Brain Barrier

PubMed Central

Farsa, Oldřich

2013-01-01

The log BB parameter is the logarithm of the ratio of a compound’s equilibrium concentrations in the brain tissue versus the blood plasma. This parameter is a useful descriptor in assessing the ability of a compound to permeate the blood-brain barrier. The aim of this study was to develop a Hansch-type linear regression QSAR model that correlates the parameter log BB and the retention time of drugs and other organic compounds on a reversed-phase HPLC containing an embedded amide moiety. The retention time was expressed by the capacity factor log k′. The second aim was to estimate the brain’s absorption of 2-(azacycloalkyl)acetamidophenoxyacetic acids, which are analogues of piracetam, nefiracetam, and meclofenoxate. Notably, these acids may be novel nootropics. Two simple regression models that relate log BB and log k′ were developed from an assay performed using a reversed-phase HPLC that contained an embedded amide moiety. Both the quadratic and linear models yielded statistical parameters comparable to previously published models of log BB dependence on various structural characteristics. The models predict that four members of the substituted phenoxyacetic acid series have a strong chance of permeating the barrier and being absorbed in the brain. The results of this study show that a reversed-phase HPLC system containing an embedded amide moiety is a functional in vitro surrogate of the blood-brain barrier. These results suggest that racetam-type nootropic drugs containing a carboxylic moiety could be more poorly absorbed than analogues devoid of the carboxyl group, especially if the compounds penetrate the barrier by a simple diffusion mechanism. PMID:23641330

The evaluation of different sorbents for the preconcentration of phenoxyacetic acid herbicides and their metabolites from soils.

PubMed

Moret, Sònia; Sánchez, Juan M; Salvadó, Victòria; Hidalgo, Manuela

2005-12-16

A procedure using alkaline extraction, solid-phase extraction (SPE) and HPLC is developed to analyze the polar herbicides 2,4-dichlorophenoxyacetic acid (2,4-D) and 4-chloro-2-methylphenoxyacetic acid (MCPA) together with their main metabolites in soils. An ion-pairing HPLC method is used for the determination as it permits the baseline separation of these highly polar herbicides and their main metabolites. The use of a highly cross-linked polystyrene-divinylbenzene sorbent (PS-DVB) gives the best results for the analysis of these compounds. This sorbent allows the direct preconcentration of the analytes at the high pH values obtained after quantitative alkaline extraction of the herbicides from soil samples. Different parameters are evaluated for the SPE preconcentration step. The high polarity of the main analytes of interest (2,4-D and MCPA) makes it necessary to work at low flow rates (< or =0.5 mL min(-1)) in order for these compounds to be retained by the PS-DVB sorbent. A two stage desorption from the SPE sorbent is required to obtain the analytes in solvents that are appropriate for HPLC determination. A first desorption with a 50:50 methanol:water mixture elutes the most polar analytes (2,4-D, MCPA and 2CP). The second elution step with methanol permits the analysis of the other phenol derivatives. The humic and fulvic substances present in the soil are not efficiently retained by PS-DVB sorbents at alkaline pH's and so do not interfere in the analysis. This method has been successfully applied in the analysis of soil samples from a golf course treated with a commercial product containing esters of 2,4-D and MCPA as the active components.

76 FR 5805 - Pesticide Products; Registration Applications

Federal Register 2010, 2011, 2012, 2013, 2014

2011-02-02

... Seed Treatment. Active ingredient: Plant growth regulator, Salicylic Acid, at 0.04%. Proposed... Treatment. Active ingredient: Plant growth regulator, Salicylic Acid, at 0.0067%. Proposed classification... Pyxis Consulting, Inc., 4110 136th St., NW., Gig Harbor, WA 98332. Product name: Salicylic Acid...

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

This interim notice covers the following: extractable organic halides in solids, total organic halides, analysis by gas chromatography/Fourier transform-infrared spectroscopy, hexadecane extracts for volatile organic compounds, GC/MS analysis of VOCs, GC/MS analysis of methanol extracts of cryogenic vapor samples, screening of semivolatile organic extracts, GPC cleanup for semivolatiles, sample preparation for GC/MS for semi-VOCs, analysis for pesticides/PCBs by GC with electron capture detection, sample preparation for pesticides/PCBs in water and soil sediment, report preparation, Florisil column cleanup for pesticide/PCBs, silica gel and acid-base partition cleanup of samples for semi-VOCs, concentrate acid wash cleanup, carbon determination in solids using Coulometrics` CO{submore » 2} coulometer, determination of total carbon/total organic carbon/total inorganic carbon in radioactive liquids/soils/sludges by hot persulfate method, analysis of solids for carbonates using Coulometrics` Model 5011 coulometer, and soxhlet extraction.« less

The use of constructed wetlands for removal of pesticides from agricultural runoff and drainage: a review.

PubMed

Vymazal, Jan; Březinová, Tereza

2015-02-01

Pesticides are used in modern agriculture to increase crop yields, but they may pose a serious threat to aquatic ecosystems. Pesticides may enter water bodies through diffuse and point sources, but diffuse sources are probably the most important. Among diffuse pollution, surface runoff and erosion, leaching and drainage represent the major pathways. The most commonly used mitigation techniques to prevent pesticide input into water bodies include edge-of-field and riparian buffer strips, vegetated ditches and constructed wetlands. The first attempts to use wetland macrophytes for pesticide removal were carried out as early as the 1970s, but only in the last decade have constructed wetlands for pesticide mitigation become widespread. The paper summarizes 47 studies in which removal of 87 pesticides was monitored. The survey revealed that constructed wetlands with free water surface are the most commonly used type. Also, it has been identified that removal of pesticides is highly variable. The results of the survey revealed that the highest pesticide removal was achieved for pesticides of the organochlorine, strobilurin/strobin, organosphosphate and pyrethroid groups while the lowest removals were observed for pesticides of the triazinone, aryloxyalkanoic acid and urea groups. The removal of pesticides generally increases with increasing value of KOC but the relationship is not strong. Copyright © 2014 Elsevier Ltd. All rights reserved.

Anaerobic biotransformation of organoarsenical pesticides monomethylarsonic acid and dimethylarsinic acid

USGS Publications Warehouse

Sierra-Alvarez, R.; Yenal, U.; Feld, J.A.; Kopplin, M.; Gandolfi, A.J.; Garbarino, J.R.

2006-01-01

Monomethylarsonic acid (MMAV) and dimethylarsinic acid (DMAV) are extensively utilized as pesticides, introducing large quantities of arsenic into the environment. Once released into the environment, these organoarsenicals are subject to microbial reactions. Aerobic biodegradation of MMAV and DMAV has been evaluated, but little is known about their fate in anaerobic environments. The objective of this study was to evaluate the biotransformation of MMAV and DMAV in anaerobic sludge. Biologically mediated conversion occurred under methanogenic or sulfate-reducing conditions but not in the presence of nitrate. Monomethylarsonous acid (MMAIII) was consistently observed as an important metabolite of MMAV degradation, and it was recovered in molar yields ranging from 5 to 47%. The main biotransformation product identified from DMAV metabolism was MMAV, which was recovered in molar yields ranging from 8 to 65%. The metabolites indicate that reduction and demethylation are important steps in the anaerobic bioconversion of MMAV and DMAV, respectively. ?? 2006 American Chemical Society.

Broad-specificity immunoassay for O,O-diethyl organophosphorus pesticides: Application of molecular modeling to improve assay sensitivity and study antibody recognition

USDA-ARS?s Scientific Manuscript database

A monoclonal antibody (MAb) against 4-(diethoxyphosphorothioyloxy)benzoic acid (hapten 1) was raised and used to develop a broad-specificity competitive indirect enzyme-linked immunosorbent assay (ciELISA) for 14 O,O-diethyl organophosphorus pesticides (OPs). Computer-assisted molecular modeling was...

EVALUATION OF INTERSPECIES DIFFERENCES IN PHARMACOKINETICS (PK) USING A PBPK MODEL FOR THE PESTICIDE DIMETHYLARSINIC ACID (DMAV)

EPA Science Inventory

DMAV is an organoarsenical pesticide registered for use on certain citrus crops and as a cotton defoliant. In lifetime oral route studies in rodents, DMAV causes statistically significant increases in bladder tumors in rats, but not in mice. We have developed a PBPK model for D...

75 FR 35796 - Busan 74 (2-hydroxypropyl methanethiosulfonate); Chlorine Gas; and Dichromic Acid, et al...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-06-23

... disproportionately high and adverse human health impacts or environmental effects from exposure to the pesticide(s... without unreasonable adverse effects on human health or the environment. Registration review dockets... its effects on human health and the environment. DATES: Comments must be received on or before August...

21 CFR 172.710 - Adjuvants for pesticide use dilutions.

Code of Federal Regulations, 2011 CFR

2011-04-01

... fatty acids. α-[p-(1,1,3,3-Tetramethylbutyl) phenyl]-omega-hydroxypoly(oxyethylene) produced by the...-Tetramethylbutyl) phenyl]-omega-hydroxypoly(oxyethylene) produced by the condensation of 1 mole of p-(1,1,3,3... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Adjuvants for pesticide use dilutions. 172.710...

21 CFR 172.710 - Adjuvants for pesticide use dilutions.

Code of Federal Regulations, 2010 CFR

2010-04-01

... fatty acids. α-[p-(1,1,3,3-Tetramethylbutyl) phenyl]-omega-hydroxypoly(oxyethylene) produced by the...-Tetramethylbutyl) phenyl]-omega-hydroxypoly(oxyethylene) produced by the condensation of 1 mole of p-(1,1,3,3... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Adjuvants for pesticide use dilutions. 172.710...

76 FR 53372 - Receipt of Several Pesticide Petitions Filed for Residues of Pesticide Chemicals in or on Various...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-08-26

... requirement of a tolerance for residues of 2- propanoic acid, 2-methyl-, polymer with methyl 2-methyl-2... of a tolerance for residues of Nonylphenol Ethoxylate Phosphate and Sulfate Derivatives (NPEPSD...-49-1). NPE Sulfate Derivatives (NPESD): [alpha]-(p-nonylphenol)-[omega]- hydroxypoly(oxyethylene...

The occurrence of glyphosate, atrazine, and other pesticides in vernal pools and adjacent streams in Washington, DC, Maryland, Iowa, and Wyoming, 2005-2006

USGS Publications Warehouse

Battaglin, William A.; Rice, Karen C.; Focazio, Michael J.; Salmons, Sue; Barry, Robert X.

2009-01-01

Vernal pools are sensitive environments that provide critical habitat for many species, including amphibians. These small water bodies are not always protected by pesticide label requirements for no-spray buffer zones, and the occurrence of pesticides in them is poorly documented. In this study, we investigated the occurrence of glyphosate, its primary degradation product aminomethylphosphonic acid, and additional pesticides in vernal pools and adjacent flowing waters. Most sampling sites were chosen to be in areas where glyphosate was being used either in production agriculture or for nonindigenous plant control. The four site locations were in otherwise protected areas (e.g., in a National Park). When possible, water samples were collected both before and after glyphosate application in 2005 and 2006. Twenty-eight pesticides or pesticide degradation products were detected in the study, and as many as 11 were identified in individual samples. Atrazine was detected most frequently and concentrations exceeded the freshwater aquatic life standard of 1.8 micrograms per liter (μg/l) in samples from Rands Ditch and Browns Ditch in DeSoto National Wildlife Refuge. Glyphosate was measured at the highest concentration (328 μg/l) in a sample from Riley Spring Pond in Rock Creek National Park. This concentration exceeded the freshwater aquatic life standard for glyphosate of 65 μg/l. Aminomethylphosphonic acid, triclopyr, and nicosulfuron also were detected at concentrations greater than 3.0 μg/l.

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).

Urinary biomarkers of exposure to insecticides, herbicides, and one insect repellent among pregnant women in Puerto Rico.

PubMed

Lewis, Ryan C; Cantonwine, David E; Anzalota Del Toro, Liza V; Calafat, Antonia M; Valentin-Blasini, Liza; Davis, Mark D; Baker, Samuel E; Alshawabkeh, Akram N; Cordero, José F; Meeker, John D

2014-11-19

There are potential adverse health risks to the mother and fetus from exposure to pesticides. Thus, studies of exposure to pesticides among pregnant women are of interest as they will assist with understanding the potential burden of exposure globally, identifying sources of exposure, and designing epidemiology studies. We measured urinary concentrations of the insect repellent N-N-diethyl-meta-toluamide (DEET) and two of its metabolites [3-diethyl-carbamoyl benzoic acid (DCBA) and N,N-diethyl-3-hydroxymethylbenzamide (DHMB)], four pyrethroid insecticide metabolites [4-fluoro-3-phenoxybenzoic acid (4-F-3-PBA); 3-phenoxybenzoic acid (3-PBA); trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane carboxylic acid (trans-DCCA); and cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane carboxylic acid (cis-DBCA)], and two chlorophenoxy herbicides [2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T)] in 54 pregnant women from Puerto Rico at three separate time points (20 ± 2 weeks, 24 ± 2 weeks, and 28 ± 2 weeks of gestation). We calculated the distributions of the biomarker concentrations and compared them to those of women of reproductive age from the general U.S. population where available, and estimated the within-subject temporal variability of these repeated measurements. We also collected questionnaire data on demographics, consumption of select fruits, vegetables, and legumes in the past 48-hr, and pest-related issues, and associations between these variables and biomarker concentrations were examined. We found that 95th percentile urinary concentrations of DEET, 3-PBA, trans-DCCA, and 2,4-D were lower than women of reproductive age on the U.S. mainland, whereas 95th percentile urinary concentrations of 4-F-3-PBA, cis-DBCA, and 2,4,5-T were similar. DCBA, the only urinary biomarker detected in >50% of the samples, showed fair to good reproducibility across pregnancy (intraclass correlation coefficient: 0.60). Women were more likely (p <0.05) to have greater urinary concentrations of pesticide biomarkers if they were less educated (DCBA and trans-DCCA), unemployed (DHMB), or married (2,4-D), had consumed collards or spinach in past 48-hr (2,4-D) or had been using insect repellent since becoming pregnant (DCBA), or were involved with residential applications of pesticides (trans-DCCA). We identified concentrations and predictors of several pesticides among pregnant women in Puerto Rico. Further research is needed to understand what aspects of the predictors identified lead to greater exposure, and whether exposure during pregnancy is associated with adverse health.

Pesticides in soils and ground water in selected irrigated agricultural areas near Havre, Ronan, and Huntley, Montana

USGS Publications Warehouse

Clark, D.W.

1990-01-01

Three areas in Montana representing a range of agricultural practices and applied pesticides, were studied to document whether agricultural pesticides are being transported into the soil and shallow groundwater in irrigated areas. Analytical scans for triazine herbicides, organic-acid herbicides, and carbamate insecticides were performed on soil and shallow groundwater samples. The results indicate pesticide residue in both types of samples. The concentrations of pesticides in the groundwater were less than Federal health-advisory limits. At the Havre Agricultural Experiment Station, eight wells were installed at two sites. All four soil samples and two of four water samples collected after application of pesticides contained detectable concentrations of atrazine or dicamba. In an area where seed potatoes are grown near Ronan, eight wells were installed at two sites. Pesticides were not detected after initial application of pesticides and irrigation water. The site was resampled after irrigation water was reapplied, and aldicarb metabolities were detected in four of five soil samples and one of five water samples. At the Huntley Agricultural Experiment Station, five wells were installed in a no-tillage corn field where atrazine was applied in 1987. Soil and water samples were collected in June and July 1988; pesticides were not detected in any samples. Results indicate residue of two pesticides in soil samples and three soluble pesticides in groundwater samples. Therefore, irrigated agricultural areas in Montana might be susceptible to transport of soluble pesticides through permeable soil to the shallow groundwater system. (USGS)

Study on the interaction of catalase with pesticides by flow injection chemiluminescence and molecular docking.

PubMed

Tan, Xijuan; Wang, Zhuming; Chen, Donghua; Luo, Kai; Xiong, Xunyu; Song, Zhenghua

2014-08-01

The interaction mechanisms of catalase (CAT) with pesticides (including organophosphates: disulfoton, isofenphos-methyl, malathion, isocarbophos, dimethoate, dipterex, methamidophos and acephate; carbamates: carbaryl and methomyl; pyrethroids: fenvalerate and deltamethrin) were first investigated by flow injection (FI) chemiluminescence (CL) analysis and molecular docking. By homemade FI-CL model of lg[(I0-I)/I]=lgK+nlg[D], it was found that the binding processes of pesticides to CAT were spontaneous with the apparent binding constants K of 10(3)-10(5) L mol(-1) and the numbers of binding sites about 1.0. The binding abilities of pesticides to CAT followed the order: fenvalerate>deltamethrin>disulfoton>isofenphos-methyl>carbaryl>malathion>isocarbophos>dimethoate>dipterex>acephate>methomyl>methamidophos, which was generally similar to the order of determination sensitivity of pesticides. The thermodynamic parameters revealed that CAT bound with hydrophobic pesticides by hydrophobic interaction force, and with hydrophilic pesticides by hydrogen bond and van der Waals force. The pesticides to CAT molecular docking study showed that pesticides could enter into the cavity locating among the four subdomains of CAT, giving the specific amino acid residues and hydrogen bonds involved in CAT-pesticides interaction. It was also found that the lgK values of pesticides to CAT increased regularly with increasing lgP, Mr, MR and MV, suggesting that the hydrophobicity and steric property of pesticide played essential roles in its binding to CAT. Copyright © 2014 Elsevier Ltd. All rights reserved.

Combined Prenatal Pesticide Exposure and Folic Acid Intake in Relation to Autism Spectrum Disorder.

PubMed

Schmidt, Rebecca J; Kogan, Vladimir; Shelton, Janie F; Delwiche, Lora; Hansen, Robin L; Ozonoff, Sally; Ma, Claudia C; McCanlies, Erin C; Bennett, Deborah H; Hertz-Picciotto, Irva; Tancredi, Daniel J; Volk, Heather E

2017-09-08

Maternal folic acid (FA) protects against developmental toxicity from certain environmental chemicals. We examined combined exposures to maternal FA and pesticides in relation to autism spectrum disorder (ASD). Participants were California children born from 2000-2007 who were enrolled in the Childhood Autism Risks from Genetics and the Environment (CHARGE) case-control study at age 2-5 y, were clinically confirmed to have ASD (n=296) or typical development (n=220), and had information on maternal supplemental FA and pesticide exposures. Maternal supplemental FA and household pesticide product use were retrospectively collected in telephone interviews from 2003-2011. High vs. low daily FA intake was dichotomized at 800μg (median). Mothers' addresses were linked to a statewide database of commercial applications to estimate agricultural pesticide exposure. High FA intake (≥800μg) during the first pregnancy month and no known pesticide exposure was the reference group for all analyses. Compared with this group, ASD was increased in association with <800μg FA and any indoor pesticide exposure {adjusted odds ratio [OR]=2.5 [95% confidence interval (CI): 1.3, 4.7]} compared with low FA [OR=1.2 (95% CI: 0.7, 2.2)] or indoor pesticides [OR=1.7 (95% CI: 1.1, 2.8)] alone. ORs for the combination of low FA and regular pregnancy exposure (≥6 mo) to pet pesticides or to outdoor sprays and foggers were 3.9 (95% CI: 1.4, 11.5) and 4.1 (95% CI: 1.7, 10.1), respectively. ORs for low maternal FA and agricultural pesticide exposure 3 mo before or after conception were 2.2 (95% CI: 0.7, 6.5) for chlorpyrifos, 2.3 (95% CI: 0.98, 5.3) for organophosphates, 2.1 (95% CI: 0.9, 4.8) for pyrethroids, and 1.5 (95% CI: 0.5, 4.8) for carbamates. Except for carbamates, these ORs were approximately two times greater than those for either exposure alone or for the expected ORs for combined exposures under multiplicative or additive models. In this study population, associations between pesticide exposures and ASD were attenuated among those with high versus low FA intake during the first month of pregnancy. Confirmatory and mechanistic studies are needed. https://doi.org/10.1289/EHP604.

Combined Prenatal Pesticide Exposure and Folic Acid Intake in Relation to Autism Spectrum Disorder

PubMed Central

Kogan, Vladimir; Shelton, Janie F.; Delwiche, Lora; Hansen, Robin L.; Ozonoff, Sally; Ma, Claudia C.; McCanlies, Erin C.; Bennett, Deborah H.; Hertz-Picciotto, Irva; Tancredi, Daniel J.; Volk, Heather E.

2017-01-01

Background: Maternal folic acid (FA) protects against developmental toxicity from certain environmental chemicals. Objective: We examined combined exposures to maternal FA and pesticides in relation to autism spectrum disorder (ASD). Methods: Participants were California children born from 2000–2007 who were enrolled in the Childhood Autism Risks from Genetics and the Environment (CHARGE) case–control study at age 2–5 y, were clinically confirmed to have ASD (n=296) or typical development (n=220), and had information on maternal supplemental FA and pesticide exposures. Maternal supplemental FA and household pesticide product use were retrospectively collected in telephone interviews from 2003–2011. High vs. low daily FA intake was dichotomized at 800μg (median). Mothers’ addresses were linked to a statewide database of commercial applications to estimate agricultural pesticide exposure. Results: High FA intake (≥800μg) during the first pregnancy month and no known pesticide exposure was the reference group for all analyses. Compared with this group, ASD was increased in association with <800μg FA and any indoor pesticide exposure {adjusted odds ratio [OR]=2.5 [95% confidence interval (CI): 1.3, 4.7]} compared with low FA [OR=1.2 (95% CI: 0.7, 2.2)] or indoor pesticides [OR=1.7 (95% CI: 1.1, 2.8)] alone. ORs for the combination of low FA and regular pregnancy exposure (≥6 mo) to pet pesticides or to outdoor sprays and foggers were 3.9 (95% CI: 1.4, 11.5) and 4.1 (95% CI: 1.7, 10.1), respectively. ORs for low maternal FA and agricultural pesticide exposure 3 mo before or after conception were 2.2 (95% CI: 0.7, 6.5) for chlorpyrifos, 2.3 (95% CI: 0.98, 5.3) for organophosphates, 2.1 (95% CI: 0.9, 4.8) for pyrethroids, and 1.5 (95% CI: 0.5, 4.8) for carbamates. Except for carbamates, these ORs were approximately two times greater than those for either exposure alone or for the expected ORs for combined exposures under multiplicative or additive models. Conclusions: In this study population, associations between pesticide exposures and ASD were attenuated among those with high versus low FA intake during the first month of pregnancy. Confirmatory and mechanistic studies are needed. https://doi.org/10.1289/EHP604 PMID:28934093

Atmospheric Photooxidation Products and Chemistry of Current-use Pesticides

NASA Astrophysics Data System (ADS)

Murschell, T.; Farmer, D.

2017-12-01

Pesticides are widely used in agricultural, commercial, and residential applications across the United States. Pesticides can volatilize off targets and travel long distances, with atmospheric lifetimes determined by both physical and chemical loss processes. In particular, oxidation by the hydroxyl radical (OH) can reduce the lifetime and thus atmospheric transport of pesticides, though the rates and oxidation products of atmospheric pesticide oxidation are poorly understood. Here, we investigate reactions of current-use pesticides with OH. MCPA, triclopyr, and fluroxypyr are herbicides that are often formulated together to target broadleaf weeds. We detect these species in the gas-phase using real-time high resolution chemical ionization mass spectrometry (CIMS) with both acetate and iodide reagent ions. We used an Oxidative Flow Reactor to explore OH radical oxidation and photolysis of these compounds, simulating up to 5 equivalent days of atmospheric aging by OH. Use of two ionization schemes allowed for the more complete representation of the OH radical oxidation of the three pesticides. The high resolution mass spectra allows us to deduce structures of the oxidation products and identify multi-generational chemistry. In addition, we observe nitrogen oxides, as well as isocyanic acid (HNCO), from some nitrogen-containing pesticides. We present yields of species of atmospheric importance, including NOx and halogen species and consider their impact on air quality following pesticide application.

Interaction of pesticides with natural and synthetic solids. Evaluation in dynamic and equilibrium conditions.

PubMed

Otalvaro, Julián Ortiz; Brigante, Maximiliano

2018-03-01

Interactions between pesticides (paraquat, glyphosate, 2,4-D, atrazine, and metsulfuron methyl) and soil organic and inorganic components have been studied in batch experiments by performing adsorption, dissolution, and chemical and photochemical degradation under different conditions. The obtained results confirm that the affinity of a pesticide to the solid surface depends on the nature of both and shows that each reactant strongly affects the mobility of the other one, e.g., anionic pesticides promote the dissolution of the solid humic acid but if this last is retained into the inorganic matrix enhances the adsorption of a cationic pesticide. Adsorption also seems to protect the bonded specie to be chemical degraded, such as shown in two pesticide/clay systems at constant pH. The use of mesoporous silicas could result in a good alternative for pesticide remediation. In fact, the solid shows high adsorption capacity towards paraquat and its modification with TiO 2 nanoparticles increases not only the pesticide adsorption but also seems to catalyze its degradation under UV light to less-toxic metabolites. UV-VIS spectroscopy was relevant and novel in such sense. Electrostatic interactions, hydrogen and coordinative bonds formations, surface complexations and hydrophobic associations play a key role in the fate of mentioned pesticides on soil and ground/surface water environments.

Effects of pesticides and antibiotics on penaeid shrimp with special emphases on behavioral and biomarker responses.

PubMed

Tu, Huynh Thi; Silvestre, Frederic; Phuong, Nguyen Thanh; Kestemont, Patrick

2010-04-01

The purpose of the present study is to provide information on the current state of knowledge regarding the effects of pesticides and antibiotics used in aquaculture on penaeid shrimp, one of the most common aquatic products for human consumption, with a special emphasis on the use of behavioral, physiological, and biochemical response. These include behavior; feeding rate changes; respiration rate, oxygen consumption, and osmoregulation alterations; nucleic acids, protein, and glycogen synthesis; cholinesterase activity inhibition; ATPase activity; and oxidative stress responses. This paper also deals with residues of antibiotics and pesticides in penaeid shrimp. Antibiotics and pesticides used in aquaculture may have adverse effects on treated animals and human consumers health if they are not correctly used. As a complement to the measurement of antibiotic and pesticide residues in tissues, the use of behavioral and biomarker responses can provide more relevant biological information on the potential adverse effects of antibiotics and pesticides on penaeid shrimp health. (c) 2009 SETAC.

Population-Based Biomonitoring of Exposure to Organophosphate and Pyrethroid Pesticides in New York City

PubMed Central

Jacobson, J. Bryan; Kass, Daniel; Barr, Dana Boyd; Davis, Mark; Calafat, Antonia M.; Aldous, Kenneth M.

2013-01-01

Background: Organophosphates and pyrethroids are the most common classes of insecticides used in the United States. Widespread use of these compounds to control building infestations in New York City (NYC) may have caused higher exposure than in less-urban settings. Objectives: The objectives of our study were to estimate pesticide exposure reference values for NYC and identify demographic and behavioral characteristics that predict exposures. Methods: The NYC Health and Nutrition Examination Survey was a population-based, cross-sectional study conducted in 2004 among adults ≥ 20 years of age. It measured urinary concentrations of organophosphate metabolites [dimethylphosphate (DMP), dimethylthiophosphate (DMTP), dimethyldithiophosphate, diethylphosphate, diethylthiophosphate, and diethyldithiophosphate] in 883 participants, and pyrethroid metabolites [3-phenoxybenzoic acid (3-PBA), trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid (trans-DCCA), 4-fluoro-3-phenoxybenzoic acid, and cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid] in 1,452 participants. We used multivariable linear regression to estimate least-squares geometric mean total dialkylphospate (ΣDAP) and 3-PBA concentrations across categories of predictors. Results: The dimethyl organophosphate metabolites had the highest 95th percentile concentrations (87.4 μg/L and 74.7 μg/L for DMP and DMTP, respectively). The highest 95th percentiles among pyrethroid metabolites were measured for 3-PBA and trans-DCCA (5.23 μg/L and 5.94 μg/L, respectively). Concentrations of ΣDAP increased with increasing age, non-Hispanic white or black compared with Hispanic race/ethnicity, professional pesticide use, and increasing frequency of fruit consumption; they decreased with non-green vegetable consumption. Absolute differences in geometric mean urinary 3-PBA concentrations across categories of predictors were too small to be meaningful. Conclusion: Estimates of exposure to pyrethroids and dimethyl organophosphates were higher in NYC than in the United States overall, underscoring the importance of considering pest and pesticide burdens in cities when formulating pesticide use regulations. Citation: McKelvey W, Jacobson JB, Kass D, Barr DB, Davis M, Calafat AM, Aldous KM. 2013. Population-based biomonitoring of exposure to organophosphate and pyrethroid pesticides in New York City. Environ Health Perspect 121:1349–1356; http://dx.doi.org/10.1289/ehp.1206015 PMID:24076605

Organic compounds in concrete from demolition works.

PubMed

Van Praagh, M; Modin, H; Trygg, J

2015-11-01

This study aims to verify the effect of physically removing the outer surface of contaminated concrete on total contents and on potential mobility of pollutants by means of leaching tests. Reclaimed concrete from 3 industrial sites in Sweden were included: A tar impregnated military storage, a military tar track-depot, as well as concrete constructions used for disposing of pesticide production surplus and residues. Solid materials and leachates from batch and column leaching tests were analysed for metals, Cl, F, SO4, DOC and contents of suspected organic compounds (polycyclic aromatic hydrocarbons, PAH, and pesticides/substances for pesticide production such as phenoxy acids, chlorophenols and chlorocresols, respectively). In case of PAH contaminated concrete, results indicate that removing 1 or 5 mm of the surface lead to total concentrations below the Swedish guidelines for recycling of aggregates and soil in groundwork constructions. 3 out of 4 concrete samples contaminated with pesticides fulfilled Swedish guidelines for contaminated soil. Results from batch and column leaching tests indicated, however, that concentrations above environmental quality standards for certain PAH and phenoxy acids, respectively, might occur at site when the crushed concrete is recycled in groundwork constructions. As leaching tests engaged in the study deviated from leaching test standards with a limited number of samples, the potential impact of the leaching tests' equipment on measured PAH and pesticide leachate concentrations has to be evaluated in future work. Copyright © 2015. Published by Elsevier Ltd.

Evaluation and prevention of the negative matrix effect of terpenoids on pesticides in apples quantification by gas chromatography-tandem mass spectrometry.

PubMed

Giacinti, Géraldine; Raynaud, Christine; Capblancq, Sophie; Simon, Valérie

2016-12-21

The sample matrix can enhance the gas chromatography signal of pesticide residues relative to that obtained with the same concentration of pesticide in solvent. This paper is related to negative matrix effects observed in coupled gas chromatography-mass spectrometry ion trap (GC/MS 2 ) quantification of pesticides in concentrated extracts of apple peel prepared by the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) method. It is focused on the pesticides most frequently used on the apple varieties studied, throughout the crop cycle, right up to harvest, to combat pests and diseases and to improve fruit storage properties. Extracts from the fleshy receptacle (flesh), the epiderm (peel) and fruit of three apple varieties were studied by high-performance thin-layer chromatography hyphenated with UV-vis light detection (HPTLC/UV visible). The peel extracts had high concentrations of triterpenic acids (oleanolic and ursolic acids), reaching 25mgkg -1 , whereas these compounds were not detected in the flesh extracts (<0.05mgkg -1 ). A significant relationship has been found between the levels of these molecules and negative matrix effects in GC/MS 2 . The differences in the behavior of pesticides with respect to matrix effects can be accounted for by the physicochemical characteristics of the molecules (lone pairs, labile hydrogen, conjugation). The HPTLC/UV visible method developed here for the characterization of QuEChERS extracts acts as a complementary clean-up method, aimed to decrease the negative matrix effects of such extracts. Copyright © 2016 Elsevier B.V. All rights reserved.

Comparison of three pesticide fate models based on lysimeter data of chloridazon and s-metolachlor from the Wagna test site, Austria

NASA Astrophysics Data System (ADS)

Brückner, Lisa; Klammler, Gernot; Schuhmann, Andrea; Kupfersberger, Hans; Fank, Johann

2017-04-01

A lysimeter experiment was conducted at the agricultural test site in Wagna, Austria, where clayey-sandy cambisol are predominant. The pesticides chloridazon and s-metolachlor were applied between 2010 and 2014 and the concentration of the active ingredients and their metabolites were measured regularly in the soil and the leachate in different depths (Schuhmann et al. 2016). During the lysimeter experiment maize, pumpkin and triticale were cultivated, which are the main field crops in that region. Beside this data, precise measurements of the soil hydrology parameters as well as meteorological data are available. Average annual precipitation at this site is 972 mm, mean annual groundwater recharge is 358 mm (2005-2014). Based on this data and the different breakthrough curves a comparison of the three different pesticide fate models PEARL, PELMO and MACRO is carried out for the pesticides s-metolachlor and chloridazon and their metabolites metolachlor oxanilic acid, metolachlor ethane sulfonic acid, desphenyl-chloridazon and methyl-desphenyl-chloridazon. The results of the modeling of the water movement and pesticide fate are evaluated and discussed. This work will contribute to a better understanding of the performance of this pesticide fate models for the above mentioned soil and hydrologic conditions. Schuhmann, A; Gans, O; Weiss, S; Fank, J; Klammler, G; Haberhauer, G; Gerzabek, MH (2016): A long-term lysimeter experiment to investigate the environmental dispersion of the herbicide chloridazon and its metabolites - comparison of lysimeter types. J SOIL SEDIMENT. 2016; 16(3): 1032-1045

Evaluation and prevention of the negative matrix effect of terpenoids on pesticides in apples quantification by gas chromatography-tandem mass spectrometry.

PubMed

Giacinti, Géraldine; Raynaud, Christine; Capblancq, Sophie; Simon, Valérie

2017-02-03

The sample matrix can enhance the gas chromatography signal of pesticide residues relative to that obtained with the same concentration of pesticide in solvent. This paper is related to negative matrix effects observed in coupled gas chromatography-mass spectrometry ion trap (GC/MS 2 ) quantification of pesticides in concentrated extracts of apple peel prepared by the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) method. It is focused on the pesticides most frequently used on the apple varieties studied, throughout the crop cycle, right up to harvest, to combat pests and diseases and to improve fruit storage properties. Extracts from the fleshy receptacle (flesh), the epiderm (peel) and fruit of three apple varieties were studied by high-performance thin-layer chromatography hyphenated with UV-vis light detection (HPTLC/UV visible). The peel extracts had high concentrations of triterpenic acids (oleanolic and ursolic acids), reaching 25mgkg -1 , whereas these compounds were not detected in the flesh extracts (<0.05mgkg -1 ). A significant relationship has been found between the levels of these molecules and negative matrix effects in GC/MS 2 . The differences in the behavior of pesticides with respect to matrix effects can be accounted for by the physicochemical characteristics of the molecules (lone pairs, labile hydrogen, conjugation). The HPTLC/UV visible method developed here for the characterization of QuEChERS extracts acts as a complementary clean-up method, aimed to decrease the negative matrix effects of such extracts. Copyright © 2016 Elsevier B.V. All rights reserved.

PURIFICATION AND PARTIAL CHARACTERIZATION OF AN ACID PHOSPHATASE FROM SPIRODELA OLIGORRHIZA AND ITS AFFINITY FOR SELECTED ORGANOPHOSPHATE PESTICIDES

EPA Science Inventory

An acid phosphatase from the aquatic plant Spirodela oligorrhiza (duckweed) was isolated by fast protein liquid chromatography (FPLC) and partially characterized. The enzyme was purified 1871-fold with a total yield of 40%. SDS-PAGE electrophoresis of the pure acid phosphatase ...

Enantioselective environmental toxicology of chiral pesticides.

PubMed

Ye, Jing; Zhao, Meirong; Niu, Lili; Liu, Weiping

2015-03-16

The enantioselective environmental toxic effect of chiral pesticides is becoming more important. As the industry develops, increasing numbers of chiral insecticides and herbicides will be introduced into use, potentially posing toxic effects on nontarget living beings. Chiral pesticides, including herbicides such as acylanilides, phenoxypropanoic acids, and imidazolinones, and insecticides such as synthetic pyrethroids, organophosphates, and DDT often behave enantioselectively during agricultural use. These compounds also pose unpredictable enantioselective ecological threats to nontarget living beings and/or humans, affecting the food chain and entire ecosystems. Thus, to investigate the enantioselective toxic effects of chiral insecticides and herbicides is necessary during environmental protection. The environmental toxicology of chiral pesticides, especially the findings obtained from studies conducted in our laboratory during the past 10 years, is reviewed.

The greening of pesticide-environment interactions: some personal observations.

PubMed

Casida, John E

2012-04-01

Pesticide-environment interactions are bidirectional. The environment alters pesticides by metabolism and photodegradation, and pesticides in turn change the environment through nontarget or secondary effects. Approximately 900 currently used commercial pesticides of widely diverse structures act by nearly a hundred mechanisms to control insects, weeds, and fungi, usually with minimal disruption of nature's equilibrium. Here I consider some aspects of the discovery, development, and use of ecofriendly or green pesticides (i.e., pesticides that are safe, effective, and biodegradable with minimal adverse secondary effects on the environment). Emphasis is given to research in my laboratory. The need for understanding and improving pesticide-environment interactions began with production of the first major insecticide approximately 150 years ago: The arsenical poison Paris Green was green in color but definitely not ecofriendly. Development and use of other pesticides has led to a variety of problems. Topics considered here include the need for high purity [e.g., hexachlorocyclohexane and polychloroborane isomers and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T)], environmental degradation and the bioactivity of resulting photoproducts and metabolites, pesticide photochemistry (including the use of structural optimization, photostabilizers, and photosensitizers to achieve suitable persistence), the presence of multiple active ingredients in botanical insecticides, the need to consider compounds with common mechanisms of action, issues related to primary and secondary targets, and chemically induced or genetically modified changes in plant biochemistry. Many insecticides are bird, fish, and honeybee toxicants, whereas herbicides and fungicides pose fewer environmental problems. Six factors have contributed to the greening of pesticide-environment interactions: advances in pesticide chemistry and toxicology, banning of many chlorinated hydrocarbons, the development of new biochemical targets, increased reliance on genetically modified crops that reduce the amount and variety of pesticides applied, emphasis on biodegradability and environmental protection, and integrated pest- and pesticide-management systems.

Production and characterization of a broad-specificity polyclonal antibody for O,O-diethyl organophosphorus pesticides and a quantitative structure-activity relationship study of antibody recognition

USDA-ARS?s Scientific Manuscript database

Polyclonal antibody (PAb) with broad-specificity for O,O-diethyl organophosphorus pesticides (OPs) against a generic hapten, 4-(diethoxyphosphoro thioyloxy) benzoic acid, was produced. The obtained PAb showed high sensitivity to seven commonly used O,O-diethyl OPs in a competitive indirect enzyme-l...

[Simultaneous determination of 6 pesticides in drinking water by high performance liquid chromatography-tandem mass spectrometry with solid phase extraction].

PubMed

Liu, Hua-liang; Wang, Lian-hong

2013-05-01

To develop an analytical method for simultaneous determination of 6 pesticides, namely bentazone, 2,4-dichlorophenoxyacetic acid,carbofuran, carbaryl, atrazine and pentachlorophenol, in drinking water by high performance liquid chromatography-tandem mass spectrometry, and thereby to provide a reference to revise the Health Standards for Drinking Water (GB/T 5750-2006). Meanwhile, to evaluate the content of the above 6 pesticides in the drinking water samples supplied by 12 centralized water plants in Jiangsu province. The 10 ml water sample was acidized by hydrochloric acid to pH ≤ 2, and then concentrated by solid phase extraction cartridge and eluted with acetone. The solvent was changed into methanol after drying by nitrogen blow. The target compounds were separated by C18 column using methanol/water as mobile phase, and detected by mass spectrometry with multi-reaction-monitoring(MRM) mode. The repeatability and sensitivity of the assay were evaluated. The drinking water samples from the 12 water plants were then detected. In this experimental method, the minimum detectable concentration were around 0.02-0.41 µg/L, with the recovery rate at 75%-115%, and the RSD between 2% and 10%. Under the experimental condition, there were no pesticides detected in the drinking water samples from the 12 centralized water plants. The method is efficient and environment-friendly, with little discharge of effluent, which could meet the requirement of the drinking water monitor.

Atmospheric transport of organophosphate pesticides from California's Central Valley to the Sierra Nevada Mountains

USGS Publications Warehouse

Zabik, John M.; Seiber, James N.

1993-01-01

Atmospheric transport of organophosphate pesticides from California's Central Valley to the Sierra Nevada mountains was assessed by collecting air- and wet-deposition samples during December, January, February, and March, 1990 to 1991. Large-scale spraying of these pesticides occurs during December and January to control insect infestations in valley orchards. Sampling sites were placed at 114- (base of the foothills), 533-, and 1920-m elevations. Samples acquired at these sites contained chlorpyrifos [phosphorothioic acid; 0,0-diethyl 0-(3,5,6-trichloro-2-pyridinyl) ester], parathion [phosphorothioic acid, 0-0-diethylo-(4-nitrophenyl) ester], diazinon {phosphorothioic acid, 0,0-diethyl 0-[6-methyl-2-(1-methylethyl)-4-pyrimidinyl] ester} diazinonoxon {phosphoric acid, 0,0-diethyl 0-[6-methyl-2-(1-methylethyl)-4-pyrimidinyl] ester}, and paraoxon [phosphoric acid, 0,0-diethyl 0-(4-nitrophenyl) ester] in both air and wet deposition samples. Air concentrations of chloropyrifos, diazinon and parathion ranged from 13 to 13 000 pg/m3 at the base of the foothills. At 533-m air concentrations were below the limit of quantification (1.4 pg/m3) to 83 pg/m3 and at 1920 m concentrations were below the limit of quantification. Concentrations in wet deposition varied with distance and elevation from the Central Valley. Rainwater concentrations at the base of the foot hills ranged from 16 to 7600 pg/mL. At 533-m rain and snow water concentrations ranged from below the limit of quantification (1.3 pg/mL) to 140 pg/mL and at 1920 m concentrations ranged from below the limit of quantification to 48 pg/mL. These findings indicate that atmospheric transport of pesticides applied in the valley to the Sierra Nevada mountains is occurring, but the levels decrease as distance and elevation increase from the valley floor.

Liquid chromatography-tandem mass spectrometry method for simultaneous quantification of azoxystrobin and its metabolites, azoxystrobin free acid and 2-hydroxybenzonitrile, in greenhouse-grown lettuce.

PubMed

Gautam, Maheswor; Fomsgaard, Inge S

2017-12-01

Lettuce is an important part of the diet in Europe. The permitted levels of pesticides in lettuce are strictly regulated and there is growing urge among food safety authorities to analyse pesticide metabolites as well. Azoxystrobin is one of pesticides that is frequently detected in lettuce. Although there are several analytical methods for the determination of azoxystrobin in lettuce, a sensitive method for the determination of its metabolites in lettuce is lacking. This study aimed at developing an extraction and LC-MS/MS method for the simultaneous determination of azoxystrobin, and its metabolites azoxystrobin free acid and 2-hydroxybenzonitrile in lettuce. Accelerated solvent extraction, QuEChERS extraction, and shaking extraction were compared using various solvents. The final method consisted of shaking freeze-dried sample in 0.1% formic acid in 80% aqueous acetonitrile. The selected method was validated by spiking each analyte at 125 ng/g and 500 ng/g. The method resulted in acceptable recovery for 2-hydroxybenzonitrile, azoxystrobin free acid, and azoxystrobin, with a RSD of <10%. The matrix-matched calibration curve for each analyte was linear over the range of quantification, with a correlation coefficient ≥0.98. The method was sensitive for the determination of 2-hydroxybenzonitrile, azoxystrobin free acid, and azoxystrobin, with limits of quantification of 0.36, 0.48, and 0.68 ng/g dry weight, respectively. The method was successfully applied to quantify 2-hydroxybenzonitrile, azoxystrobin free acid, and azoxystrobin in greenhouse-grown lettuce.

Application of acid modified polyurethane foam surface for detection and removing of organochlorine pesticides from wastewater.

PubMed

Moawed, E A; Radwan, A M

2017-02-15

The commercial polyurethane foam was acid modified to get an inexpensive adsorbent (AM-PUF) has highly surface polarity and sorption capacity. The elemental analysis, scanning electron microscopy, thermal analysis, ultraviolet/visible/infrared spectroscopies and X-ray diffraction were used for characterization of AM-PUF. The surface of AM-PUF has amorphous character (broadband at 2θ, 21.75°) and contains several active sites e.g. NH, OH, CO, CC and COC groups. The electrical conductivity (σ), iodine value and methylene blue index of AM-PUF are 1.7×10 -5 Ω -1 m -1 , 208mg/g and 107mg/g. The AM-PUF has a high efficiency for completely removing (99-100%) of Aldrin, DDT, Endrin, Heptachlor, Heptachlor epoxide and Lindane pesticides in both acidic and alkaline solutions. The removing rates of the organochlorine pesticides from wastewater are very rapid (t 1/2 =22s). The negative value of ΔG (-10.9kJ/mol) for removing of OCPs using AM-PUF showed that the feasibility of the removing process and its spontaneous nature. Copyright © 2017 Elsevier B.V. All rights reserved.

Direct surface analysis of pesticides on soil, leaves, grass, and stainless steel by static secondary ion mass spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ingram, J.C.; Groenewold, G.S.; Appelhans, A.D.

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 analysismore » 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.« less

Barrage fishponds: Reduction of pesticide concentration peaks and associated risk of adverse ecological effects in headwater streams.

PubMed

Gaillard, Juliette; Thomas, Marielle; Iuretig, Alain; Pallez, Christelle; Feidt, Cyril; Dauchy, Xavier; Banas, Damien

2016-03-15

Constructed wetlands have been suggested as pesticide risk mitigation measures. Yet, in many agricultural areas, ponds or shallow lakes are already present and may contribute to the control of non-point source contamination by pesticides. In order to test this hypothesis, we investigated the influence of extensively managed barrage fishponds (n = 3) on the dissolved concentrations of 100 pesticides in headwater streams over the course of a year. Among the 100 pesticides, 50 different substances were detected upstream and 48 downstream. Highest measured concentration upstream was 26.5 μg/L (2-methyl-4-chlorophenoxyacetic acid, MCPA) and 5.19 μg/L (isoproturon) downstream. Fishponds were found to reduce peak exposure levels as high pesticide concentrations (defined here as ≥ 1 μg/L) generally decreased by more than 90% between upstream and downstream sampling sites. The measured concentrations in the investigated streams were compared to laboratory toxicity data for standard test organisms (algae, invertebrates and fish) using the toxic unit approach. When considering the threshold levels set by the European Union within the first tier risk assessment procedure for pesticide registration (commission regulation (EU) N° 546/2011), regulatory threshold exceedances were observed for 22 pesticides upstream from fishponds and for 9 pesticides downstream. Therefore, the investigated barrage fishponds contributed to the reduction of pesticide peak concentrations and potential risk of adverse effects for downstream ecosystems. Copyright © 2016 Elsevier Ltd. All rights reserved.

40 CFR 180.1178 - Formic acid; exemption from the requirement of a tolerance.

Code of Federal Regulations, 2013 CFR

2013-07-01

... pesticide formic acid is exempted from the requirement of a tolerance in or on honey and honeycomb when used to control tracheal mites and suppress varroa mites in bee colonies, and applied in accordance with...

40 CFR 180.1178 - Formic acid; exemption from the requirement of a tolerance.

Code of Federal Regulations, 2012 CFR

2012-07-01

... pesticide formic acid is exempted from the requirement of a tolerance in or on honey and honeycomb when used to control tracheal mites and suppress varroa mites in bee colonies, and applied in accordance with...

40 CFR 180.1178 - Formic acid; exemption from the requirement of a tolerance.

Code of Federal Regulations, 2011 CFR

2011-07-01

... pesticide formic acid is exempted from the requirement of a tolerance in or on honey and honeycomb when used to control tracheal mites and suppress varroa mites in bee colonies, and applied in accordance with...

40 CFR 180.1178 - Formic acid; exemption from the requirement of a tolerance.

Code of Federal Regulations, 2010 CFR

2010-07-01

... pesticide formic acid is exempted from the requirement of a tolerance in or on honey and honeycomb when used to control tracheal mites and suppress varroa mites in bee colonies, and applied in accordance with...

40 CFR 180.1178 - Formic acid; exemption from the requirement of a tolerance.

Code of Federal Regulations, 2014 CFR

2014-07-01

... pesticide formic acid is exempted from the requirement of a tolerance in or on honey and honeycomb when used to control tracheal mites and suppress varroa mites in bee colonies, and applied in accordance with...

[Simultaneous determination of seven high risk pesticide residues in royal jelly by high performance liquid chromatography-tandem mass spectrometry].

PubMed

Li, Yinghong; Zhou, Ping; Xu, Quanhua; Zhao, Huan; Shao, Qiaoyun

2018-02-08

A method was developed for the simultaneous determination of seven high risk pesticides in the royal jelly, eg. tau-fluvalinate, triadimenol, coumaphos, haloxyfop, carbendazim, thiophanate-ethyl and thiophanate-methyl by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). First, the royal jelly samples were extracted with acetonitrile under alkaline conditions. After dehydration by anhydrous sodium sulfate, the extracts were enriched and purified through solid-phase extraction (SPE) with Oasis HLB cartridges. Finally, the pesticides were detected by HPLC-MS/MS method. The separation was carried out on a Venusil MP C18 column with gradient elution. Methanol (containing 0.1% (v/v) formic acid) and 0.5 mmol/L ammonium acetate aqueous solution (containing 0.1% (v/v) formic acid) were used as the mobile phases. The detection was achieved using electrospray ionization in positive ion (ESI + ) mode and multiple reaction monitoring (MRM) mode for data collection. Quantification was carried out using internal standard method. The results showed that the seven high risk pesticides were linear in the range of 5-100 μg/kg. The linear correlation coefficients ( r 2 ) were 0.9921-0.9996. The limits of detection (LODs) and limits of quantification (LOQs) of the seven high risk pesticides were 0.5-2.0 μg/kg and 1.0-5.0 μg/kg, respectively. The average recoveries at the three spiked levels were 80.5%-101.3%, and the relative standard deviations were 3.6%-9.4% ( n =3). This method is simple, effective and sensitive, and is suitable for the determination of the pesticide residues in royal jelly.

Assessment of serum biomarkers in rats after exposure to pesticides of different chemical classes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moser, Virginia C., E-mail: Moser.ginger@epa.gov; Stewart, Nicholas; Freeborn, Danielle L.

There is increasing emphasis on the use of biomarkers of adverse outcomes in safety assessment and translational research. We evaluated serum biomarkers and targeted metabolite profiles after exposure to pesticides (permethrin, deltamethrin, imidacloprid, carbaryl, triadimefon, fipronil) with different neurotoxic actions. Adult male Long–Evans rats were evaluated after single exposure to vehicle or one of two doses of each pesticide at the time of peak effect. The doses were selected to produce similar magnitude of behavioral effects across chemicals. Serum or plasma was analyzed using commercial cytokine/protein panels and targeted metabolomics. Additional studies of fipronil used lower doses (lacking behavioral effects),more » singly or for 14 days, and included additional markers of exposure and biological activity. Biomarker profiles varied in the number of altered analytes and patterns of change across pesticide classes, and discriminant analysis could separate treatment groups from control. Low doses of fipronil produced greater effects when given for 14 days compared to a single dose. Changes in thyroid hormones and relative amounts of fipronil and its sulfone metabolite also differed between the dosing regimens. Most cytokine changes reflected alterations in inflammatory responses, hormone levels, and products of phospholipid, fatty acid, and amino acid metabolism. These findings demonstrate distinct blood-based analyte profiles across pesticide classes, dose levels, and exposure duration. These results show promise for detailed analyses of these biomarkers and their linkages to biological pathways. - Highlights: • Pesticides typical of different classes produced distinct patterns of change in biomarker panels. • Based on the panels used, alterations suggest impacts on immune, metabolism, and homeostasis functions. • Some changes may reflect actions on neurotransmitter systems involved in immune modulation. • Fipronil effects on thyroid and kinetics differed with acute and repeated administration.« less

Agricultural effluent treatment in biobed systems using novel substrates from southeastern Mexico: the relationship with physicochemical parameters of biomixtures.

PubMed

Góngora-Echeverría, Virgilio René; Martin-Laurent, Fabrice; Quintal-Franco, Carlos; Giácoman-Vallejos, German; Ponce-Caballero, Carmen

2017-04-01

Misuse of pesticides in farming activities leads to contamination of drinking water sources and is responsible for animal and human health problems. The biobeds are practicable option to minimize contamination by pesticides during preparation, use and washing of equipment for pesticide treatments. This research aimed at testing substrate mixtures to optimize biobed efficiency to remove pesticides under the climate of the Yucatan (México). Agricultural soil and 11 mixtures adding vegetable compost, sisal pulp, corn stover and seaweed were tested under controlled conditions. Each biomixture was exposed to a mixture of five pesticides (2,4-diclorophenoxyacetic acid "2,4-D" [1.08 mg cm -3 ], atrazine [2.50 mg cm -3 ], carbofuran [0.23 mg cm -3 ], diazinon [0.34 mg cm -3 ], and glyphosate [0.36 mg cm -3 ]) in a period of 41 days. Monitoring of the dissipation of pesticide residues showed that pesticides were quickly dissipated in soil at microcosm level experiment, while at two critical times of 20 and 41 days, all mixtures of substrates (biomixtures) were efficient in dissipation of high concentrations of pesticide in a short time (>99%). Time, biomixture and type of pesticide were shown to be the main parameters influencing pesticide dissipation (P < 0.05). Several other physicochemical parameters of the biomixtures, such as organic matter (OM), lignin, water holding capacity (WHC), and pH, were also significant on pesticide dissipation (P < 0.05), being pH the most significant.

The sorption properties of polymers with molecular imprints of chlorine-containing pesticides

NASA Astrophysics Data System (ADS)

Popov, S. A.; Dmitrienko, S. G.; Chumichkina, Yu. A.; Zolotov, Yu. A.

2009-04-01

Polymers with molecular imprints of 2,4-dichlorophenoxyacetic acid (2,4-D), 3,6-dichloro-2-methoxybenzoic acid (dicamba), and (RS)-1- p-chlorophenyl-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl) pentan-3-ol and the corresponding blank polymers were synthesized using acrylamide as a functional monomer. The specific surface area of the resulting materials was estimated and their sorption properties were studied. It was found that the sorption characteristics of the polymers with molecular imprints of chlorine-containing pesticides depended on the nature of template molecules, functional monomer: template ratio in the polymerization mixture, and nature and content of solvents varied at the synthesis stage. According to the sorption isotherms, the difference in the sorption behavior of molecularly imprinted and blank polymers was observed over a wide range of chlorine-containing pesticide concentrations. The selectivity of the adsorbent with 2,4-D imprints was estimated for the example of structurally related compounds.

Preparation, Characterization and Intracellular Imaging of 2,4-Dichlorophenoxyacetic Acid Conjugated Gold Nanorods.

PubMed

Jia, Jin-Liang; Jin, Xiao-Yong; Liu, Qing-Le; Liang, Wen-Long; Lin, Miao-Shan; Xu, Han-Hong

2016-05-01

Visualizing the biodistribution of pesticides inside living cells is great importance for enhancing targeting of pesticides. Here we reported for the first time that gold nanorods (Au NRs) with size of 39.4 nm x 11.3 nm could be used as a fluorescent tracer to examine the distribution of a typical herbicide, 2,4-dichlorophenoxyacetic acid (2,4-D), in tobacco bright yellow 2 (BY-2) cells. The nanostructures of hybrid materials were analyzed by using Raman spectra and X-ray photoelectron spectroscopy (XPS), including spectra assignments and electronic property. These data revealed 2,4-D has successfully conjugated MP-Au NRs according to Raman and XPS. The biodistribution of the conjugates inside BY-2 cells was directly examined at 12 and 24 h by the two-photon microscopy. The intensity of two-photon luminescence (TPL) inside cells demonstrated that the conjugates could be localized and excluded by BY-2 cells. Thus, this labeling approach opens up new avenues to the facile and efficient labeling of pesticides.

Determination of eight pesticides in Lycium barbarum by LC-MS/MS and dietary risk assessment.

PubMed

Fu, Yan; Yang, Ting; Zhao, Jian; Zhang, Liang; Chen, Ruoxia; Wu, Yinliang

2017-03-01

A LC-MS/MS method for determination of eight pesticides (triadimefon, sulfoxaflor, flusilazole, tebuconazole, difenoconazole, amitraz, azoxystrobin, and thiophanate-methyl) in Lycium barbarum was established. The samples were extracted with acetonitrile, and then cleaned up by primary secondary amine. The extracts were diluted with 0.1% formic acid in water. The results showed that at the fortified levels of 0.01-10mg/kg, the average recoveries of these pesticides ranged from 82.1% to 96.2% with the relative standard deviations lower than 7%. The half-lives of eight pesticides were 1.3-5.0days in Lycium barbarum fruits. The pre-harvest interval of all pesticides mentioned above were investigated. Tebuconazole (14days), sulfoxaflor (14days) and flusilazole (28days) have longer pre-harvest interval than the others which have 7days. The dietary risks, assessed as hazard quotients, were far below 100%. The results showed that the eight pesticides applied to Lycium barbarum were comparably safe for the consumer. Copyright © 2016 Elsevier Ltd. All rights reserved.

Modeling water infiltration and pesticides transport in unsaturated zone of a sedimentary aquifer

NASA Astrophysics Data System (ADS)

Sidoli, Pauline; Angulo-Jaramillo, Rafael; Baran, Nicole; Lassabatère, Laurent

2015-04-01

Groundwater quality monitoring has become an important environmental, economic and community issue since increasing needs drinking water at the same time with high anthropic pressure on aquifers. Leaching of various contaminants as pesticide into the groundwater is closely bound to water infiltration in the unsaturated zone which whom solute transport can occur. Knowledge's about mechanisms involved in the transfer of pesticides in the deep unsaturated zone are lacking today. This study aims to evaluate and to model leaching of pesticides and metabolites in the unsaturated zone, very heterogeneous, of a fluvio-glacial aquifer, in the South-East of France, where contamination of groundwater resources by pesticides is frequently observed as a consequence of intensive agricultural activities. Water flow and pesticide transport were evaluated from column tests under unsaturated conditions and from adsorption batch experiments onto the predominant lithofacies collected, composed of a mixture of sand and gravel. A maize herbicide, S-metolachlor, applied on the study site and worldwide and its two major degradation products (metolachlor ethanesulfonic acid and metolachlor oxanilic acid) were studied here. A conservative tracer, bromide ion, was used to determine water dispersive parameters of porous media. Elution curves were obtained from pesticide concentrations analyzed by an ultra-performance liquid chromatography system interfaced to a triple quadrupole mass spectrometer and from bromide concentrations measured by ionic chromatography system. Experimental data were implemented into Hydrus to model flow and solute transfer through a 1D profile in the vadose zone. Nonequilibrium solute transport model based on dual-porosity model with mobile and immobile water is fitting correctly elution curves. Water dispersive parameters show flow pattern realized in the mobile phase. Exchanges between mobile and immobile water are very limited. Because of low adsorptions onto fluvio-glacial deposits, retention of S-metolachlor and its ionic metabolites is low in column tests and high mobility was observed meaning these molecules are prone to reach groundwater.

Pesticide and transformation product detections and age-dating relations from till and sand deposits

USGS Publications Warehouse

Warner, K.L.; Morrow, W.S.

2007-01-01

Pesticide and transformation product concentrations and frequencies in ground water from areas of similar crop and pesticide applications may vary substantially with differing lithologies. Pesticide analysis data for atrazine, metolachlor, alachlor, acetochlor, and cyanazine and their pesticide transformation products were collected at 69 monitoring wells in Illinois and northern Indiana to document occurrence of pesticides and their transformation products in two agricultural areas of differing lithologies, till, and sand. The till is primarily tile drained and has preferential fractured flow, whereas the sand primarily has surface water drainage and primary porosity flow. Transformation products represent most of the agricultural pesticides in ground water regardless of aquifer material - till or sand. Transformation products were detected more frequently than parent pesticides in both the till and sand, with metolachlor ethane sulfonic acid being most frequently detected. Estimated ground-water recharge dates for the sand were based on chlorofluorocarbon analyses. These age-dating data indicate that ground water recharged prior to 1990 is more likely to have a detection of a pesticide or pesticide transformation product. Detections were twice as frequent in ground water recharged prior to 1990 (82%) than in ground water recharged on or after 1990 (33%). The highest concentrations of atrazine, alachlor, metolachlor, and their transformation products, also were detected in samples from ground water recharged prior to 1990. These age/pesticide detection relations are opposite of what would normally be expected, and may be the result of preferential flow and/or ground-water mixing between aquifers and aquitards as evident by the detection of acetochlor transformation products in samples with estimated ground-water ages predating initial pesticide application. ?? 2007 American Water Resources Association.

78 FR 20029 - Castor Oil, Polymer With Adipic Acid, Linoleic Acid, Oleic Acid and Ricinoleic Acid; Tolerance...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-04-03

... of pesticide use in residential settings. If EPA is able to determine that a finite tolerance is not... environment. 2. The polymer does contain as an integral part of its composition the atomic elements carbon... impurities, any element other than those listed in 40 CFR 723.250(d)(2)(ii). 4. The polymer is neither...

Analysis and occurrence of pharmaceuticals, estrogens, progestogens and polar pesticides in sewage treatment plant effluents, river water and drinking water in the Llobregat river basin (Barcelona, Spain)

NASA Astrophysics Data System (ADS)

Kuster, Marina; López de Alda, Maria José; Hernando, Maria Dolores; Petrovic, Mira; Martín-Alonso, Jordi; Barceló, Damià

2008-08-01

SummaryThis work investigated the presence of 21 emerging contaminants of various chemical groups (7 estrogens, 3 progestogens, 6 pharmaceuticals and personal care products (PPCPs), and 5 acidic pesticides) in the Llobregat river basin (NE Spain). Waters from the outlet of various sewage treatment plants (STP) and waterworks located along the river basin, as well as water samples from the river or its tributaries upstream and downstream of these plants were analysed in two pilot monitoring studies. Chemical analyses were performed by means of on-line or off-line solid-phase extraction followed by liquid chromatography-electrospray-tandem mass spectrometry. Methods detection limits (in ng/L) were ⩽0.85 for estrogens, ⩽3.94 for progestogens, ⩽30 for PPCPs, and ⩽0.99 for pesticides. Of the estrogens and progestogens analysed, only estrone-3-sulfate, estrone, estriol and progesterone were found to be present in the low nanogram per liter range in some of the samples investigated. Except for atenolol, all PPCPs studied (ibuprofen, diclofenac, clofibric acid, salicylic acid, and triclosan) could be identified at levels usually lower than 250 ng/L and up to 1200 ng/l (diclofenac). Of the various pesticides investigated (2,4-D, bentazone; MCPA, mecoprop and propanil) MCPA and 2,4-D were the most ubiquitous and abundant and bentazone the only one not detected. Individual concentrations were most often below 100 ng/L and never surpassed the EU limits.

Suitability of hardwood treated with phenoxy and pyridine herbicides for firewood use

Treesearch

P.B. Bush; D.G. Neary; Charles K. McMahon; J.W. Taylor

1987-01-01

Abstract. Potential exposure to pesticide residues resulting from burning wood treated with phenoxyand pyridine herbicides was assessed. Wood samples from trees treated with 2,4-D [2,4-dichlo-rophenoxy acetic acid], dicamba [3,6-dichloro-o-anisic acid], dichlorprop [2-(2,4-dichlorphenoxy) propionic acid], picloram [4-amino-3,5,dtrichloropico-linic...

Runoff of pyrethroid insecticides from concrete surfaces following simulated and natural rainfalls.

PubMed

Jiang, Weiying; Haver, Darren; Rust, Michael; Gan, Jay

2012-03-01

Intensive residential use of insecticides has resulted in their ubiquitous presence as contaminants in urban surface streams. For pest eradication, urban hard surfaces such as concrete are often directly treated with pesticides, and wind/water can also carry pesticides onto hard surfaces from surrounding areas. This study expanded on previous bench-scale studies by considering pesticide runoff caused by irrigation under dry weather conditions and rain during the wet season, and evaluated the effects of pesticide residence time on concrete, single versus recurring precipitations, precipitation intensity, and concrete surface conditions, on pesticide transferability to runoff water. Runoff from concrete 1 d after pesticide treatment contained high levels of bifenthrin (82 μg/L) and permethrin (5143 μg/L for cis and 5518 μg/L for trans), indicating the importance of preventing water contact on concrete after pesticide treatments. Although the runoff transferability quickly decreased as the pesticide residence time on concrete increased, detectable residues were still found in runoff water after 3 months (89 d) exposure to hot and dry summer conditions. ANOVA analysis showed that precipitation intensities and concrete surface conditions (i.e., acid wash, silicone seal, stamping, and addition of microsilica) did not significantly affect the pesticide transferability to runoff. For concrete slabs subjected to natural rainfalls during the winter wet season, pesticide levels in the runoff decreased as the time interval between pesticide application and the rain event increased. However, bifenthrin and permethrin were still detected at 0.15-0.17 and 0.75-1.15 μg/L in the rain runoff after 7 months (221 d) from the initial treatment. In addition, pesticide concentrations showed no decrease between the two rainfall events, suggesting that concrete surfaces contaminated by pesticides may act as a reservoir for pesticide residues, leading to sustained urban runoff contamination. Copyright © 2011 Elsevier Ltd. All rights reserved.

Effects of wastewater irrigation and sewage sludge application on soil residues of chiral fungicide benalaxyl.

PubMed

Jing, Xu; Yao, Guojun; Liu, Donghui; Liang, Yiran; Luo, Mai; Zhou, Zhiqiang; Wang, Peng

2017-05-01

The effects of wastewater irrigation and sewage sludge on the dissipation behavior of the fungicide benalaxyl and its primary metabolite benalaxyl acid in soil were studied on an enantiomeric level during a 148-day exposure experiment. Chiral separation and analysis of the two pairs of enantiomers were achieved using HPLC-MS/MS with a chiralpak IC chiral column. Benalaxyl decreased with half-life of 16.1 days in soil under tap water irrigation with preferential residue of S-benalaxyl. Benalaxyl acid was formed with great preference of R-enantiomer before 21 days while enriched in S-enantiomer afterwards. The degradation of benalaxyl was restrained by both wastewater and treated wastewater irrigation, but the enantioselectivity in S-benalaxyl residue was enhanced. Benalaxyl acid was also formed with similar enantioselectivity as in tap water irrigation. Sewage sludge could accelerate benalaxyl degradation with shorter half-life. Surprisingly, the enantioselectivity with preference degradation of S-enantiomer in sewage sludge was opposite to that in soil. More benalaxyl acid was generated with EF values always lower than 0.5 and remained longer in sewage sludge than in soil. A sterilization experiment indicated that the conversion of benalaxyl to benalaxyl acid and the enantioselectivity were determined by the microorganisms in soil or sewage sludge. Farming practices like wastewater irrigation and sewage sludge application might not only influence the fate of pesticide, but also the enantioselectivity of chiral pesticide enantiomers and thus the risks of pesticide residues posed to the environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Matrix Effects and Interferences of Different Citrus Fruit Coextractives in Pesticide Residue Analysis Using Ultrahigh-Performance Liquid Chromatography-High-Resolution Mass Spectrometry.

PubMed

Besil, Natalia; Cesio, Verónica; Heinzen, Horacio; Fernandez-Alba, Amadeo R

2017-06-14

The matrix effects of ethyl acetate extracts from seven different citrus fruits on the determination of 80 pesticide residues using liquid chromatography coupled to high-resolution time-of-flight mass spectrometry (UHPLC-(ESI)-HR-TOF) at 4 GHz resolution mode were studied. Only 20% of the evaluated pesticides showed noticeable matrix effects (ME) due to coelution with natural products between t R = 3 and 11 min. Principal component analysis (PCA) of the detected coextractives grouped the mandarins and the orange varieties, but separated lemon, oranges, and mandarins from each other. Matrix effects were different among species but similar between varieties, forcing the determination of pesticide residues through matrix-matched calibration curves with the same fruit. Twenty-three natural products (synephrine, naringin, poncirin, glycosides of hesperitin, limonin, nomilin, and a few fatty acids, among others) were identified in the analyzed extracts. Twelve of the identified compounds coeluted with 28 of the pesticides under study, causing different matrix effects.

75 FR 770 - Acrylic acid-benzyl methacrylate-1-propanesulfonic acid, 2-methyl-2-[(1-oxo-2-propenyl)amino...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-01-06

....960. Akzo Nobel Surface Chemistry LLC submitted a petition to EPA under the Federal Food, Drug, and... the receipt of a pesticide petition (PP 9E7599) filed by Akzo Nobel Surface Chemistry LLC. The...

40 CFR Table 1 to Part 455 - List of Organic Pesticide Active Ingredients

Code of Federal Regulations, 2013 CFR

2013-07-01

...) 00534-52-1 45 101101 Metribuzin 21087-64-9 46 19401 CPA (4-chlorophenoxyacetic acid) 00122-88-3 46 (1) CPA Salts and Esters (1) 47 19201 MCPB [4-(2-Methyl-4-chlorophenoxy)butyric acid] 00094-81-5 47 (1...

40 CFR Table 1 to Part 455 - List of Organic Pesticide Active Ingredients

Code of Federal Regulations, 2011 CFR

2011-07-01

...) 00534-52-1 45 101101 Metribuzin 21087-64-9 46 19401 CPA (4-chlorophenoxyacetic acid) 00122-88-3 46 (1) CPA Salts and Esters (1) 47 19201 MCPB [4-(2-Methyl-4-chlorophenoxy)butyric acid] 00094-81-5 47 (1...

40 CFR Table 1 to Part 455 - List of Organic Pesticide Active Ingredients

Code of Federal Regulations, 2014 CFR

2014-07-01

...) 00534-52-1 45 101101 Metribuzin 21087-64-9 46 19401 CPA (4-chlorophenoxyacetic acid) 00122-88-3 46 (1) CPA Salts and Esters (1) 47 19201 MCPB [4-(2-Methyl-4-chlorophenoxy)butyric acid] 00094-81-5 47 (1...

40 CFR Table 1 to Part 455 - List of Organic Pesticide Active Ingredients

Code of Federal Regulations, 2010 CFR

2010-07-01

...) 00534-52-1 45 101101 Metribuzin 21087-64-9 46 19401 CPA (4-chlorophenoxyacetic acid) 00122-88-3 46 (1) CPA Salts and Esters (1) 47 19201 MCPB [4-(2-Methyl-4-chlorophenoxy)butyric acid] 00094-81-5 47 (1...

40 CFR Table 1 to Part 455 - List of Organic Pesticide Active Ingredients

Code of Federal Regulations, 2012 CFR

2012-07-01

...) 00534-52-1 45 101101 Metribuzin 21087-64-9 46 19401 CPA (4-chlorophenoxyacetic acid) 00122-88-3 46 (1) CPA Salts and Esters (1) 47 19201 MCPB [4-(2-Methyl-4-chlorophenoxy)butyric acid] 00094-81-5 47 (1...

Role of induced glutathione-S-transferase from Helicoverpa armigera (Lepidoptera: Noctuidae) HaGST-8 in detoxification of pesticides.

PubMed

Labade, Chaitali P; Jadhav, Abhilash R; Ahire, Mehul; Zinjarde, Smita S; Tamhane, Vaijayanti A

2018-01-01

The present study deals with glutathione-S-transferase (GST) based detoxification of pesticides in Helicoverpa armigera and its potential application in eliminating pesticides from the environment. Dietary exposure of a pesticide mixture (organophosphates - chlorpyrifos and dichlorvos, pyrethroid - cypermethrin; 2-15ppm each) to H. armigera larvae resulted in a dose dependant up-regulation of GST activity and gene expression. A variant GST from H. armigera (HaGST-8) was isolated from larvae fed with 10ppm pesticide mixture and it was recombinantly expressed in yeast (Pichia pastoris HaGST-8). HaGST-8 had a molecular mass of 29kDa and was most active at pH 9 at 30°C. GC-MS and LC-HRMS analysis validated that HaGST-8 was effective in eliminating organophosphate type of pesticides and partially reduced the cypermethrin content (53%) from aqueous solutions. Unlike the untransformed yeast, P. pastoris HaGST-8 grew efficiently in media supplemented with pesticide mixtures (200 and 400ppm each pesticide) signifying the detoxification ability of HaGST-8. The amino acid sequence of HaGST-8 and the already reported sequence of HaGST-7 had just 2 mismatches. The studies on molecular interaction strengths revealed that HaGST-8 had stronger binding affinities with organophosphate, pyrethroid, organochloride, carbamate and neonicotinoid type of pesticides. The abilities of recombinant HaGST-8 to eliminate pesticides and P. pastoris HaGST-8 to grow profusely in the presence of high level of pesticide content can be applied for removal of such residues from food, water resources and bioremediation. Copyright © 2017 Elsevier Inc. All rights reserved.

Screening for estrogen and androgen receptor activities in 200 pesticides by in vitro reporter gene assays using Chinese hamster ovary cells.

PubMed Central

Kojima, Hiroyuki; Katsura, Eiji; Takeuchi, Shinji; Niiyama, Kazuhito; Kobayashi, Kunihiko

2004-01-01

We tested 200 pesticides, including some of their isomers and metabolites, for agonism and antagonism to two human estrogen receptor (hER) subtypes, hERalpha and hERbeta, and a human androgen receptor (hAR) by highly sensitive transactivation assays using Chinese hamster ovary cells. The test compounds were classified into nine groups: organochlorines, diphenyl ethers, organophosphorus pesticides, pyrethroids, carbamates, acid amides, triazines, ureas, and others. These pesticides were tested at concentrations < 10-5 M. Of the 200 pesticides tested, 47 and 33 showed hER- and hERbeta-mediated estrogenic activities, respectively. Among them, 29 pesticides had both hERalpha and hERbeta agonistic activities, and the effects of the organochlorine insecticides beta-benzene hexachloride (BHC) and delta-BHC and the carbamate insecticide methiocarb were predominantly hERbeta rather than hERalpha agonistic. Weak antagonistic effects toward hERalpha and hERbeta were shown in five and two pesticides, respectively. On the other hand, none of tested pesticides showed hAR-mediated androgenic activity, but 66 of 200 pesticides exhibited inhibitory activity against the transcriptional activity induced by 5alpha-dihydrotestosterone. In particular, the antiandrogenic activities of two diphenyl ether herbicides, chlornitrofen and chlomethoxyfen, were higher than those of vinclozolin and p,p -dichlorodiphenyl dichloroethylene, known AR antagonists. The results of our ER and AR assays show that 34 pesticides possessed both estrogenic and antiandrogenic activities, indicating pleiotropic effects on hER and hAR. We also discussed chemical structures related to these activities. Taken together, our findings suggest that a variety of pesticides have estrogenic and/or antiandrogenic potential via ER and/or AR, and that numerous other manmade chemicals may also possess such estrogenic and antiandrogenic activities. PMID:15064155

Urinary Concentrations of Insecticide and Herbicide Metabolites among Pregnant Women in Rural Ghana: A Pilot Study.

PubMed

Wylie, Blair J; Ae-Ngibise, Kenneth A; Boamah, Ellen A; Mujtaba, Mohammed; Messerlian, Carmen; Hauser, Russ; Coull, Brent; Calafat, Antonia M; Jack, Darby; Kinney, Patrick L; Whyatt, Robin; Owusu-Agyei, Seth; Asante, Kwaku P

2017-03-29

Use of pesticides by households in rural Ghana is common for residential pest control, agricultural use, and for the reduction of vectors carrying disease. However, few data are available about exposure to pesticides among this population. Our objective was to quantify urinary concentrations of metabolites of organophosphate (OP), pyrethroid, and select herbicides during pregnancy, and to explore exposure determinants. In 2014, 17 pregnant women from rural Ghana were surveyed about household pesticide use and provided weekly first morning urine voids during three visits ( n = 51 samples). A total of 90.1% (46/51) of samples had detectable OP metabolites [geometric mean, GM (95% CI): 3,5,6-trichloro-2-pyridinol 0.54 µg/L (0.36-0.81), para-nitrophenol 0.71 µg/L (0.51-1.00)], 75.5% (37/49) had detectable pyrethroid metabolites [GM: 3-phenoxybenzoic acid 0.23 µg/L (0.17, 0.32)], and 70.5% (36/51) had detectable 2,4-dichlorophenoxyacetic acid levels, a herbicide [GM: 0.46 µg/L (0.29-0.73)]. Concentrations of para-nitrophenol and 2,4-dichlorophenoxyacetic acid in Ghanaian pregnant women appear higher when compared to nonpregnant reproductive-aged women in a reference U.S. Larger studies are necessary to more fully explore predictors of exposure in this population.

Currently used pesticides and their mixtures affect the function of sex hormone receptors and aromatase enzyme activity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kjeldsen, Lisbeth Stigaard; Ghisari, Mandana; Bonefeld-Jørgensen, Eva Cecilie, E-mail: ebj@mil.au.dk

The endocrine-disrupting potential of pesticides is of health concern, since they are found ubiquitously in the environment and in food items. We investigated in vitro effects on estrogen receptor (ER) and androgen receptor (AR) transactivity, and aromatase enzyme activity, of the following pesticides: 2-methyl-4-chlorophenoxyacetic acid (MCPA), terbuthylazine, iodosulfuron-methyl-sodium, mesosulfuron-methyl, metsulfuron-methyl, chlormequat chloride, bitertanol, propiconazole, prothioconazole, mancozeb, cypermethrin, tau fluvalinate, malathion and the metabolite ethylene thiourea (ETU). The pesticides were analyzed alone and in selected mixtures. Effects of the pesticides on ER and AR function were assessed in human breast carcinoma MVLN cells and hamster ovary CHO-K1 cells, respectively, using luciferasemore » reporter gene assays. Effects on aromatase enzyme activity were analyzed in human choriocarcinoma JEG-3 cells, employing the classical [{sup 3}H]{sub 2}O method. Five pesticides (terbuthylazine, propiconazole, prothioconazole, cypermethrin and malathion) weakly induced the ER transactivity, and three pesticides (bitertanol, propiconazole and mancozeb) antagonized the AR activity in a concentration-dependent manner. Three pesticides (terbuthylazine, propiconazole and prothioconazole) weakly induced the aromatase activity. In addition, two mixtures, consisting of three pesticides (bitertanol, propiconazole, cypermethrin) and five pesticides (terbuthylazine, bitertanol, propiconazole, cypermethrin, malathion), respectively, induced the ER transactivity and aromatase activity, and additively antagonized the AR transactivity. In conclusion, our data suggest that currently used pesticides possess endocrine-disrupting potential in vitro which can be mediated via ER, AR and aromatase activities. The observed mixture effects emphasize the importance of considering the combined action of pesticides in order to assure proper estimations of related health effect risks. - Highlights: • Currently used pesticides possess endocrine-disrupting (ED) potential in vitro. • ED effects can be mediated via sex hormone receptors and/or the aromatase enzyme. • Additive mixture effects on androgen receptor transactivity were observed.« less

TRACE ANALYSIS OF FLUORESCEIN-DERIVATIZED PHENOXY ACID HERBICIDES BY MICELLAR ELECTROKINETIC CHROMATOGRAPHY WITH LASER-INDUCTED FLUORESCENCE DETECTION

EPA Science Inventory

Micellar electrokinetic chromatography (MEKC) with laser-induced fluorescence (LIF) detection was used for the trace analysis of phenoxy acid herbicides. Capillary electrophoresis (CE) with LIF detection, which has not previously been used for pesticide analysis, overcomes the po...

Predictors of urinary levels of 2,4-dichlorophenoxyacetic acid, 3,5,6-trichloro-2-pyridinol, 3-phenoxybenzoic acid, and pentachlorophenol in 121 adults in Ohio

EPA Science Inventory

Limited data exist on the driving factors that influence the non-occupational exposures of adults to pesticides using urinary biomonitoring. In this work, the objectives were to quantify the urinary levels of 2,4-dichlorophenoxyacetic acid (2,4-D), 3,5,6-trichloro-2-pyridinol (TC...

Botanical pesticides effect from shells of bean’s cashew nut on biological agents of trichoderma sp. and gliocladium sp.

NASA Astrophysics Data System (ADS)

Bande, L. O. S.; Mariadi; Gusnawaty, HS; Nuriadi; Trisulpa, L.; Rahmania

2018-02-01

A shell of cashew nut (Anacardium occidentanle) has contained Cashew Nut Shell Liquid (CNSL) that is used as botanical pesticides. CNSL oil consists of active substance such as anacardat acid, cardol and cardanol. Utilization of the pesticides from shells of cashew nut to control pests and diseases of plants would be affected on biological agents. The objective of this research was to investigate pesticides inhibition on the increase of mycelium Trichoderma sp. and Gliocladium sp. by in vitro method. The tested concentration sample consisted of 0.0% (control), 2.5%, 7.5% and 10.0% in PDA media. The results of this research showed that 2.5% botanical pesticides concentration could minimize mycelium of Trichoderma sp. and Gliocladium sp. 22.73% and 21.04% respectively and also the increase shells of cashew extract could be affected the increase of mycelium inhibition. The extract with 2.5% concentration was the recommended concentration to control of fruit rot diseases and if concentration was 10.0% then its inhibition become 54.98% and 49.35%, respectively. The results proved that uncontrolled utilization of the pesticides could be affected on decrease of Trichoderma sp. and Gliocladium sp. growth.

Health effect of agricultural pesticide use in China: implications for the development of GM crops

PubMed Central

Zhang, Chao; Hu, Ruifa; Huang, Jikun; Huang, Xusheng; Shi, Guanming; Li, Yifan; Yin, Yanhong; Chen, Zhaohui

2016-01-01

It is notable that the adoption of GM glyphosate-tolerant crops increases glyphosate use but reduces non-glyphosate herbicide use; and adoption of GM insect-resistant crops significantly reduces insecticide use. While the health hazard of pesticide use has been well documented, little literature evaluates the health effects of different pesticides related to GM crops in an integrated framework. This study aims to associate the uses of different pesticides related to GM crops with the blood chemistry panel and peripheral nerve conduction of Chinese farmers. Pesticides used by farmers were recorded and classified as glyphosate, non-glyphosate herbicides, chemical lepidopteran insecticides, biological lepidopteran insecticides, non-lepidopteran insecticides and fungicides. The multivariate regression results show that none of the examined 35 health indicators was associated with glyphosate use, while the use of non-glyphosate herbicides was likely to induce renal dysfunction and decrease of serum folic acid. The use of chemical lepidopteran insecticides might be associated with hepatic dysfunction, serum glucose elevation, inflammation and even severe nerve damage. In this context, if GM crops are adopted, the alterations in pesticide use may benefit farmer health in China and globe, which has positive implications for the development of GM crops. PMID:27721390

Effect of Humic Acids and pesticides on Agricultural Soil Structure and Stability and Its Implication on Soil Quality

NASA Astrophysics Data System (ADS)

Gaonkar, O. D.; Nambi, I. M.; G, S. K.

2016-12-01

The functional and morphological aspects of soil structure determine the soil quality. The dispersion of colloidal soil particles, especially the clay fraction and rupture of soil aggregates, both of which play an important role in soil structure development, lead to degradation of soil quality. The main objective of this work was to determine the effect of behaviour of soil colloids on the agricultural soil structure and quality. The effect of commercial humic acid, organophosphate pesticides and soil natural organic matter on the electrical and structural properties of the soil colloids was also studied. Agricultural soil, belonging to the sandy loam texture class from northern part of India was considered in this study. In order to understand the changes in the soil quality in the presence and absence of humic acids, the soil fabric and structure was analyzed by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR) Spectroscopy and Scanning Electron Microscopy (SEM). Electrical properties of natural soil colloids in aqueous suspensions were assessed by zeta potential measurements at varying pH values with and without the presence of humic acids and pesticides. The influence of natural organic matter was analyzed by oxidizing the natural soil organic matter with hydrogen peroxide. The zeta potential of the soil colloids was found to be negative in the pH range studied. The results indicated that hydrogen peroxide treatment lead to deflocculation of colloidal soil particles. In addition, the humic acids undergoes effective adsorption onto the soil surface imparting more negative zeta potential to the colloidal soil particles. The soil hydrophilicity decreased in the presence of humic acids which was confirmed by surface free energy determination. Thus, it can be concluded that the presence of humic acids altered the soil fabric and structure, thereby affecting the soil quality. This study assumes significance in understanding the soil aggregation and the interactions at soil solid-liquid interface.

Evaluation of urinary speciated arsenic in NHANES: Issues in interpretation in the context of potential inorganic arsenic exposure

EPA Science Inventory

Urinary dimethylarsinic acid (DMA) and monomethylarsonic acid (MMA) are among the commonly used biomarkers for inorganic arsenic (iAs) exposure, but may also arise from seafood consumption and organoarsenical pesticide applications. We examined speciated urinary arsenic data from...

A PHYSIOLOGICALLY BASED PHARMACOKINETIC (PBPK) MODEL FOR THE PESTICIDE MONOMETHYLARSONIC ACID (MMA)

EPA Science Inventory

The monosodium salt of monomethylarsonic acid [MMA(V)] is a widely used organoarsenical herbicide. In lifetime feeding studies with MMA(V), the large intestine (focal muscosal ulceration) was the primary target organ in both male and female mice and rats and no treatment-related...

Predictors of urinary levels of 2,4-dichlorophenoxyacetic acid, 3,5,6-trichloro-2-pyridinol, 3-phenoxybenzoic acid, and pentachlorophenol in 121 adults in Ohio.

PubMed

Morgan, Marsha K

2015-07-01

Limited data exist on the driving factors that influence the non-occupational exposures of adults to pesticides using urinary biomonitoring. In this work, the objectives were to quantify the urinary levels of 2,4-dichlorophenoxyacetic acid (2,4-D), 3,5,6-trichloro-2-pyridinol (TCP), 3-phenoxybenzoic acid (3-PBA), and pentachlorophenol (PCP) in 121 adults over a 48-h monitoring period and to examine the associations between selected sociodemographic and lifestyle factors and urinary levels of each pesticide biomarker. Adults, ages 20-49 years old, were recruited from six counties in Ohio (OH) in 2001. The participants collected 4-6 spot urine samples and completed questionnaires and diaries at home over a 48-h monitoring period. Urine samples were analyzed for 2,4-D, TCP, 3-PBA, and PCP by gas chromatography/mass spectrometry. Multiple regression modeling was used to determine the impact of selected sociodemographic and lifestyle factors on the log-transformed (ln) levels of each pesticide biomarker in adults. The pesticide biomarkers were detected in ≥ 89% of the urine samples, except for 3-PBA (66%). Median urinary levels of 2,4-D, TCP, 3-PBA, and PCP were 0.7, 3.4, 0.3, and 0.5 ng/mL, respectively. Results showed that 48-h sweet/salty snack consumption, 48-h time spend outside at home, and ln(creatinine) levels were significant predictors (p < 0.05), and race was a marginally significant predictor (p = 0.093) of the adults' ln(urinary 2,4-D) concentrations. Strong predictors (p < 0.05) of the adults' ln(urinary TCP) concentrations were urbanicity, employment status, sampling season, and ln(creatinine) levels. For 3-PBA, sampling season, pet ownership and removal of shoes before entering the home were significant predictors (p < 0.05) of the adults' ln(urinary 3-PBA) levels. Finally for PCP, removal of shoes before entering the home and ln(creatinine) levels were significant predictors (p < 0.05), and pet ownership was a marginally significant predictor (p = 0.056) of the adults' ln(urinary PCP) concentrations. In conclusion, specific sociodemographic and lifestyle factors were identified that increased the exposures of these adults to several different pesticides in their daily environments. Published by Elsevier GmbH.

A review of currently used pesticides (CUPs) in Canadian air and precipitation. Part 2: Regional information and perspectives

NASA Astrophysics Data System (ADS)

Tuduri, Ludovic; Harner, Tom; Blanchard, Pierrette; Li, Yi-Fan; Poissant, Laurier; Waite, Don T.; Murphy, Clair; Belzer, Wayne

This paper, and its companion (that dealt with lindane and endosulfan) review available data on the presence of currently used pesticides (CUPs) in air and precipitation in Canada, since the late 1980s. Pesticides usage/sales are also given when available. Data from local studies/initiatives, region-wide monitoring networks and remote locations are compiled to summarize atmospheric levels of different CUP classes (e.g. acid herbicides, organophosphates, "new" organochlorines, triazines, etc.) and how this varies among regions and with time. Based on this information, and other parameters not specific to Canada, knowledge gaps are identified and ideas for further research work are proposed.

Evaluation of various soaking agents as a novel tool for pesticide residues mitigation from cauliflower (Brassica oleracea var. botrytis).

PubMed

Abdullah; Randhawa, Muhammad Atif; Asghar, Ali; Pasha, Imran; Usman, Rabia; Shamoon, Muhammad; Bhatti, Muhammad Arslan; Irshad, Muhammad Asim; Ahmad, Naveed

2016-08-01

The increasing use of pesticides for boosting the yield of agricultural crops also impart toxic residues which ultimately extend to numerous physiological disorders upon consumption. The present study was designed as an effort to assess the reduction potential of various chemical solutions and to minimize the pesticide residues in cauliflower ( Brassica oleracea var. botrytis ). The samples were soaked in various solutions along with tap water to mitigate pesticide residues. Afterwards, the extracted supernatant was passed through column containing anhydrous sodium sulfate trailed by activated carbon for clean-up. Eluents were first evaporated and then completely dried under gentle stream of Nitrogen. Finally, the residues were determined using gas chromatography equipped with electron capture detector (GC-ECD). Results revealed the highest reduction of endosulfan, bifenthrin and cypermethrin residues with acetic acid (10 %) was 1.133 ± 0.007 (41 %), 0.870 ± 0.022 (60 %) and 0.403 ± 0.003 (75 %), respectively among the tested solutions. However, simple tap water treatment also resulted in 0.990 ± 0.02 (12 %), 1.323 ± 0.015 (14 %) and 1.274 ± 0.002 (21 %) elimination of endosulfan, bifenthrin and cypermethrin residues, respectively. Moreover, among various solutions, acetic acid depicted maximum reduction potential followed by citric acid, hydrogen peroxide, sodium chloride and sodium carbonate solutions. The percent reduction by various solutions ranged from 12 to 41, 14 to 60 and 21 to 75 % for the elimination of endosulfan, bifenthrin and cypermethrin residues, respectively.

Photodegradation of lambda-cyhalothrin and cypermethrin in aqueous solution as affected by humic acid and/or copper: intermediates and degradation pathways.

PubMed

Xie, Jimin; Wang, Pingli; Liu, Jun; Lv, Xiaomeng; Jiang, Deli; Sun, Cheng

2011-11-01

The influence of coexisting humic acids (HA) or Cu²⁺ on the photodegradation of pesticides lambda-cyhalothrin (λ-CHT) and cypermethrin (CPM) in aqueous solution was studied under xenon lamp irradiation. The removal efficiency of pesticides λ-CHT and CPM were enhanced in the presence of either Cu²⁺ or HA but restrained in the presence of both Cu²⁺ and HA. The photodegradation of λ-CHT and CPM followed first-order reaction kinetics. The photodegradation intermediates of λ-CHT and CPM were determined using gas chromatography/mass spectrometry. Possible photodegradation pathways included decarboxylation, ester bond cleavage, dechlorination, and phenyl group removal. Copyright © 2011 SETAC.

Emerging contaminants (pharmaceuticals, personal care products, a food additive and pesticides) in waters of Sydney estuary, Australia.

PubMed

Birch, G F; Drage, D S; Thompson, K; Eaglesham, G; Mueller, J F

2015-08-15

The current investigation of marine water from 30 sites adjacent to stormwater outlets across the entire Sydney estuary is the first such research in Australia. The number of analytes detected were: 8/59 pharmaceutical compounds (codeine, paracetamol, tramadol, venlafaxine, propranolol, fluoxetine, iopromide and carbamazepine), 7/38 of the pesticides (2,4-dichlorophenoxyacetic acid (2,4-D), 3,4-dichloroaniline, carbaryl, diuron, 2-methyl-4-chlorophenoxyacetic acid (MCPA), mecoprop and simazine) and 0/3 of the personal care products (PCPs) analysed. An artificial sweetener (acesulfame) was detected, however none of the nine antibiotics analysed were identified. Sewage water is not discharged to this estuary, except infrequently as overflow during high-precipitation events. The presence of acesulfame (a recognised marker of domestic wastewater) and pharmaceuticals in water from all parts of the estuary after a dry period, suggests sewage water is leaking into the stormwater system in this catchment. The pesticides are applied to the environment and were discharged via stormwater to the estuary. Copyright © 2015 Elsevier Ltd. All rights reserved.

Degradation of 2,4-dichlorophenoxyacetic acid by a halotolerant strain of Penicillium chrysogenum: antibiotic production.

PubMed

Ferreira-Guedes, Sumaya; Mendes, Benilde; Leitão, Ana Lúcia

2012-01-01

The extensive use of pesticides in agriculture has prompted intensive research on chemical and biological methods in order to protect contamination of water and soil resources. In this paper the degradation of the pesticide 2,4-dichlorophenoxyacetic acid by a Penicillium chrysogenum strain previously isolated from a salt mine was studied in batch cultures. Co-degradation of 2,4-dichlorophenoxyacetic acid with additives such as sugar and intermediates of pesticide metabolism was also investigated. Penicillium chrysogenum in solid medium was able to grow at concentrations up to 1000 mg/L of 2,4-dichlorophenoxyacetic acid (2,4-D) with sucrose. Meanwhile, supplementation of the solid medium with glucose and lactose led to fungal growth at concentrations up to 500 mg/L of herbicide. Batch cultures of 2,4-D at 100 mg/L were developed under aerobic conditions with the addition of glucose, lactose and sucrose, showing sucrose as the best additional carbon source. The 2,4-D removal was quantified by liquid chromatography. The fungus was able to use 2,4-D as the sole carbon and energy source under 0%, 2% and 5.9% NaCl. The greatest 2,4-D degradation efficiency was found using alpha-ketoglutarate and ascorbic acid as co-substrates under 2% NaCl at pH 7. Penicillin production was evaluated in submerged cultures by bioassay, and higher amounts of beta-lactam antibiotic were produced when the herbicide was alone. Taking into account the ability of P. chrysogenum CLONA2 to degrade aromatic compounds, this strain could be an interesting tool for 2,4-D herbicide remediation in saline environments.

Improvement of pesticide adsorption capacity of cellulose fibre by high-energy irradiation-initiated grafting of glycidyl methacrylate

NASA Astrophysics Data System (ADS)

Takács, Erzsébet; Wojnárovits, László; Koczog Horváth, Éva; Fekete, Tamás; Borsa, Judit

2012-09-01

Cellulose as a renewable raw material was used for preparation of adsorbent of organic impurities in wastewater treatment. Hydrophobic surface of cellulose substrate was developed by grafting glycidyl methacrylate in simultaneous grafting using gamma irradiation initiation. Water uptake of cellulose significantly decreased while adsorption of phenol and a pesticide molecule (2,4-dichlorophenoxyacetic acid: 2,4-D) increased upon grafting. Adsorption equilibrium data fitted the Freundlich isotherm for both solutes.

Screening of 439 Pesticide Residues in Fruits and Vegetables by Gas Chromatography-Quadrupole-Time-of-Flight Mass Spectrometry Based on TOF Accurate Mass Database and Q-TOF Spectrum Library.

PubMed

Li, Jian-Xun; Li, Xiao-Ying; Chang, Qiao-Ying; Li, Yan; Jin, Ling-He; Pang, Guo-Fang; Fan, Chun-Lin

2018-05-03

Because of its unique characteristics of accurate mass full-spectrum acquisition, high resolution, and fast acquisition rates, GC-quadrupole-time-of-flight MS (GC-Q-TOF/MS) has become a powerful tool for pesticide residue analysis. In this study, a TOF accurate mass database and Q-TOF spectrum library of 439 pesticides were established, and the parameters of the TOF database were optimized. Through solid-phase extraction (SPE), whereby pesticides are extracted from fruit and vegetable substrates by using 40 mL 1% acetic acid in acetonitrile (v/v), purified by the Carbon/NH₂ SPE cartridge, and finally detected by GC-Q-TOF/MS, the rapid analysis of 439 pesticides in fruits and vegetables can be achieved. The methodology verification results show that more than 70 and 91% of pesticides, spiked in fruits and vegetables with concentrations of 10 and 100 μg/kg, respectively, saw recoveries that conform to the European Commission's criterion of between 70 and 120% with RSD ≤20%. Eighty-one percent of pesticides have screening detection limits lower than 10 μg/kg, which makes this a reliable analysis technology for the monitoring of pesticide residues in fruits and vegetables. This technology was further validated for its characteristics of high precision, high speed, and high throughput through successful detection of 9817 samples during 2013-2015.

Application of diethanolamide surfactant derived from palm oil to improve the performance of biopesticide from neem oil

NASA Astrophysics Data System (ADS)

Nisya, F. N.; Prijono, D.; Nurkania, A.

2017-05-01

The purpose of this research was to improve the performance of organic pesticide derived from neem plant using diethanolamide surfactant (DEA) derived from palm oil in controlling armyworms. The pesticide was made of neem oil. Neem oil is a neem plant product containing several active components, i.e. azadirachtin, salanin, nimbin, and meliantriol which act as a pesticide. DEA surfactant acts as a wetting, dispersing and spreading agent in neem oil pesticide. The neem oil was obtained by pressing neem seeds using a screw press machine and a hydraulic press machine. DEA surfactant was synthesized from methyl esters of palm oil olein. Pesticide formulation was conducted by stirring the ingredients by using a homogenizer at 5,000 rpm for 30 minutes. Surfactant was added to the formulation by up to 5%. Glycerol, as an emulsifier, was added in to pesticide formulations of neem oil. The efficacy of the pesticides in controlling armyworms fed soybean leaves in laboratory was measured at six concentrations, i.e. 10, 13, 16, 19, 22, and 25 ml/L. Results showed that the neem oil used in this study had a density of 0.91 g/cm3, viscosity of 58.94 cPoise, refractive index of 1.4695, surface tension of 40.69 dyne/cm, azadirachtin content of 343.82-1.604 ppm. Meanwhile, the azadirachtin content of neem seed cake was 242.20 ppm. It was also found that palmitic (31.4%) and oleic (22.5%) acids were the main fatty acids contained in neem oil. As the additive material used in neem oil in this study, diethanolamide surfactant had a pH of 10.6, density of 0.9930 g/cm3, viscosity of 708.20 cP, and surface tension of 25.37 dyne/cm. Results of CMC, contact angle, and droplet size analyzes showed that diethanolamide surfactant could be added into insecticide formulation by 5%. Results of LC tests showed that on Spodoptera litura the LC50 and LC95 values were 13 and 22 ml/L, respectively. Neem oil was found to inhibit the development of Spodoptera litura and its larval molting process.

Pesticides in Surface Drinking-Water Supplies of the Northern Great Plains

PubMed Central

Donald, David B.; Cessna, Allan J.; Sverko, Ed; Glozier, Nancy E.

2007-01-01

Background Human health anomalies have been associated with pesticide exposure for people living in rural landscapes in the northern Great Plains of North America. Objective The objective of this study was to investigate the occurrence of 45 pesticides in drinking water from reservoirs in this area that received water primarily from snowmelt and rainfall runoff from agricultural crop lands. Methods Water from 15 reservoirs was sampled frequently during the spring pesticide application period (early May to mid-August) and less frequently for the remainder of the year. Drinking water was sampled in early July. Sample extracts were analyzed for pesticide content using mass spectrometric detection. Results We detected two insecticides and 27 herbicides in reservoir water. Consistent detection of a subset of 7 herbicides suggested that atmospheric deposition, either directly or in rain, was the principal pathway from fields to the reservoirs. However, the highest concentrations and number of herbicides in drinking water were associated with runoff from a localized 133-mm rainfall over 15 days toward the end of spring herbicide application. Water treatment removed from 14 to 86% of individual herbicides. Drinking water contained 3–15 herbicides (average, 6.4). Conclusions We estimated the mean annual calculated concentration of herbicides in drinking water to be 75 ng/L (2,4-dichlorophenoxy)acetic acid, 31 ng/L (2-chloro-4-methylphenoxy)acetic acid, 24 ng/L clopyralid, 11 ng/L dichlorprop, 4 ng/L dicamba, 3 ng/L mecoprop, and 1 ng/L bro-moxynil. The maximum total concentration of herbicides in drinking water was 2,423 ng/L. For the seven herbicides with established drinking water guidelines, all concentrations of the individual chemicals were well below their respective guideline. However, guidelines have not been established for the majority of the herbicides found in drinking water or for mixtures of pesticides. PMID:17687445

COMPARISON OF GENE EXPRESSION IN KIDNEY AND URINARY BLADDER FROM RATS TREATED WITH DIMETHYLARSINIC ACID

EPA Science Inventory

Arsenic is widespread in the environment and a human carcinogen. A major metabolite of inorganic arsenic (iAs) in most species, including humans, is dimethylarsinic acid (DMA), which is also used as a pesticide. Unlike iAs, DMA induces urinary bladder tumors in rats. DMA is belie...

Impact of Pesticide Resistance on Toxicity and Tolerance of Hostplant Phytochemicals in Amyelois Transitella (Lepidoptera: Pyralidae)

PubMed Central

Bagchi, Vikram A.; Siegel, Joel P.; Demkovich, Mark R.; Zehr, Luke N.; Berenbaum, May R.

2016-01-01

For some polyphagous insects, adaptation to phytochemically novel plants can enhance resistance to certain pesticides, but whether pesticide resistance expands tolerance to phytochemicals has not been examined. Amyelois transitella Walker (navel orangeworm) is an important polyphagous pest of nut and fruit tree crops in California. Bifenthrin resistance, partially attributable to enhanced cytochrome P450 (P450)-mediated detoxification, has been reported in an almond-infesting population exposed to intense pesticide selection. We compared the toxicity of bifenthrin and three phytochemicals–chlorogenic acid, and the furanocoumarins xanthotoxin and bergapten–to three strains of A. transitella: pyrethroid-resistant R347 (maintained in the laboratory for ∼10 generations), fig-derived FIG (in the laboratory for ∼25 generations), and CPQ–a laboratory strain derived from almonds ∼40 years ago). Whereas both Ficus carica (fig) and Prunus dulcis (almond) contain chlorogenic acid, furanocoumarins occur only in figs. Both R347 and FIG exhibited 2-fold greater resistance to the three phytochemicals compared with CPQ; surprisingly, bifenthrin resistance was highest in FIG. Piperonyl butoxide, a P450 synergist, increased toxicity of all three phytochemicals only in CPQ, implicating alternate tolerance mechanisms in R347 and FIG. To test the ability of the strains to utilize novel hostplants directly, we compared survival on diets containing seeds of Wisteria sinensis and Prosopis pallida, two non-host Fabaceae species; survival of FIG was highest and survival of R347 was lowest. Our results suggest that, while P450-mediated pesticide resistance enhances tolerance of certain phytochemicals in this species, it is only one of multiple biochemical adaptations associated with acquiring novel hostplants. PMID:27620560

Cloning of a Novel Arylamidase Gene from Paracoccus sp. Strain FLN-7 That Hydrolyzes Amide Pesticides

PubMed Central

Zhang, Jun; Yin, Jin-Gang; Hang, Bao-Jian; Cai, Shu; Li, Shun-Peng

2012-01-01

The bacterial isolate Paracoccus sp. strain FLN-7 hydrolyzes amide pesticides such as diflubenzuron, propanil, chlorpropham, and dimethoate through amide bond cleavage. A gene, ampA, encoding a novel arylamidase that catalyzes the amide bond cleavage in the amide pesticides was cloned from the strain. ampA contains a 1,395-bp open reading frame that encodes a 465-amino-acid protein. AmpA was expressed in Escherichia coli BL21 and homogenously purified using Ni-nitrilotriacetic acid affinity chromatography. AmpA is a homodimer with an isoelectric point of 5.4. AmpA displays maximum enzymatic activity at 40°C and a pH of between 7.5 and 8.0, and it is very stable at pHs ranging from 5.5 to 10.0 and at temperatures up to 50°C. AmpA efficiently hydrolyzes a variety of secondary amine compounds such as propanil, 4-acetaminophenol, propham, chlorpropham, dimethoate, and omethoate. The most suitable substrate is propanil, with Km and kcat values of 29.5 μM and 49.2 s−1, respectively. The benzoylurea insecticides (diflubenzuron and hexaflumuron) are also hydrolyzed but at low efficiencies. No cofactor is needed for the hydrolysis activity. AmpA shares low identities with reported arylamidases (less than 23%), forms a distinct lineage from closely related arylamidases in the phylogenetic tree, and has different biochemical characteristics and catalytic kinetics with related arylamidases. The results in the present study suggest that AmpA is a good candidate for the study of the mechanism for amide pesticide hydrolysis, genetic engineering of amide herbicide-resistant crops, and bioremediation of amide pesticide-contaminated environments. PMID:22544249

Effect of Pesticide Inoculation, Duration of Composting, and Degradation Time on the Content of Compost Fatty Acids, Quantified Using Two Methods ▿ †

PubMed Central

Cardinali, Alessandra; Otto, Stefan; Vischetti, Costantino; Brown, Colin; Zanin, Giuseppe

2010-01-01

Compost biobeds can promote biodegradation of pesticides. The microbial community structure changes during the composting process, and simple methods can potentially be used to follow these changes. In this study the microbial identification (MIDI) and ester-linked (EL) procedures were used to determine the composition of fatty acid methyl esters (FAMEs) in composts aged 3 and 12 months, inoculated with 3 recalcitrant pesticides (azoxystrobin, chlorotoluron, and epoxyconazole and a coapplication of all three) after 0, 56, and 125 days of degradation. Pesticide persistence was high, and after 125 days the residue was 22 to 70% of the applied amount depending mostly on the composting age. Seventy-one FAMEs belonging to nine groups were detected. The EL method provided three times as many detections as did the MIDI method and was more sensitive for all FAME groups except alcohol. Thirty-six and five FAMEs were unique to the EL and MIDI methods, respectively. The extraction method was of importance. The EL method provided a higher number of detections for 57 FAMEs, and the MIDI method provided a higher number for 9 FAMEs, while the two methods were equal for 5 FAMEs; thus, the EL method provided a more uniform overall FAME profile. Effects of the other factors were not always clear. Inoculation with pesticide did not influence the FAME profile with the MIDI method, while it influenced cyclopropane and monounsaturated content with the EL method. Composting age and degradation time had an effect on some groups of FAMEs, and this effect was greater with the EL method. The use of some FAMEs as biomarkers to follow microbial community succession was likely influenced by the type of compost and other factors. PMID:20693445

Impact of Pesticide Resistance on Toxicity and Tolerance of Hostplant Phytochemicals in Amyelois Transitella (Lepidoptera: Pyralidae).

PubMed

Bagchi, Vikram A; Siegel, Joel P; Demkovich, Mark R; Zehr, Luke N; Berenbaum, May R

2016-01-01

For some polyphagous insects, adaptation to phytochemically novel plants can enhance resistance to certain pesticides, but whether pesticide resistance expands tolerance to phytochemicals has not been examined. Amyelois transitella Walker (navel orangeworm) is an important polyphagous pest of nut and fruit tree crops in California. Bifenthrin resistance, partially attributable to enhanced cytochrome P450 (P450)-mediated detoxification, has been reported in an almond-infesting population exposed to intense pesticide selection. We compared the toxicity of bifenthrin and three phytochemicals-chlorogenic acid, and the furanocoumarins xanthotoxin and bergapten-to three strains of A. transitella: pyrethroid-resistant R347 (maintained in the laboratory for ∼10 generations), fig-derived FIG (in the laboratory for ∼25 generations), and CPQ-a laboratory strain derived from almonds ∼40 years ago). Whereas both Ficus carica (fig) and Prunus dulcis (almond) contain chlorogenic acid, furanocoumarins occur only in figs. Both R347 and FIG exhibited 2-fold greater resistance to the three phytochemicals compared with CPQ; surprisingly, bifenthrin resistance was highest in FIG. Piperonyl butoxide, a P450 synergist, increased toxicity of all three phytochemicals only in CPQ, implicating alternate tolerance mechanisms in R347 and FIG. To test the ability of the strains to utilize novel hostplants directly, we compared survival on diets containing seeds of Wisteria sinensis and Prosopis pallida, two non-host Fabaceae species; survival of FIG was highest and survival of R347 was lowest. Our results suggest that, while P450-mediated pesticide resistance enhances tolerance of certain phytochemicals in this species, it is only one of multiple biochemical adaptations associated with acquiring novel hostplants. © The Author 2016. Published by Oxford University Press on behalf of the Entomological Society of America. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

NAWQA, National Water-Quality Assessment Program; Allegheny-Monongahela River Basin

USGS Publications Warehouse

McAuley, Steven D.; Brown, Juliane B.; Sams, James I.

1997-01-01

Surface-water and ground-water quality and aquatic life can be significantly affected by the following principal issues identified in the Allegheny-Monongahela River Basin:Contaminants common to surface and under-ground coal mine discharge such as acidity, iron, aluminum, manganese, and sulfate.Volatile organic compounds (VOC’s), pesti-cides, and nutrients from increased urbanization.Runoff and loading of nutrients and pesticides to streams from nonpoint and point sources such as agricultural land uses.Radon in ground water.

Decision Document for the Storm Water Outfalls/Industrial Wastewater Treatment Plant, Pesticide Rinse Area, Old Fire Fighting Training Pit, Illicit PCB Dump Site, and the Battery Acid Pit Fort Lewis, Washington

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cantrell, Kirk J; Liikala, Terry L; Strenge, Dennis L

PNNL conducted independent site evaluations for four sites at Fort Lewis, Washington, to determine their suitability for closure on behalf of the installation. These sites were recommended for ''No Further Action'' by previous investigators and included the Storm Water Outfalls/Industrial Waste Water Treatment Plant (IWTP), the Pesticide Rinse Area, the Old Fire Fighting Training Pit, and the Illicit PCB Dump Site.

Decision Document for the Storm Water Outfalls/Industrial Wastewater Treatment Plant, Pesticide Rinse Area, Old Fire Fighting Training Pit, Illicit PCB Dump Site, and the Battery Acid Pit Fort Lewis, Washington

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cantrell, Kirk J.; Liikala, Terry L.; Strenge, Dennis L.

PNNL conducted independent site evaluations for four sites at Fort Lewis, Washington, to determine their suitability for closure on behalf of the installation. These sites were recommended for "No Further Action" by previous invesitgators and included the Storm Water Outfalls/Industrial Waste Water Treatment Plant (IWTP), the Pesticide Rinse Area, the Old Fire Fighting Training Pit, and the Illicit PCB Dump Site.

Occurrence of fungicides and other pesticides in surface water, groundwater, and sediment from three targeted-use areas in the United States, 2009

USGS Publications Warehouse

Orlando, James L.; Smalling, Kelly L.; Reilly, Timothy J.; Boehlke, Adam; Meyer, Michael T.; Kuivila, Kathryn

2013-01-01

Surface-water, groundwater, and suspended- and bedsediment samples were collected in three targeted-use areas in the United States where potatoes were grown during 2009 and analyzed for an extensive suite of fungicides and other pesticides by gas chromatograph/mass spectrometry and liquid chromatography with tandem mass spectrometry. Fungicides were detected in all environmental matrices sampled during the study. The most frequently detected fungicides were azoxystrobin, boscalid, chlorothalonil, and pyraclostrobin. Other pesticides that were detected frequently included amino phosphonic acid (AMPA), atrazine, metolaclor, and the organochlorine insecticide p,p’-DDT and its degradates p,p’-DDD and p,p’-DDE. A greater number of pesticides were detected in surface water relative to the other environmental matrices sampled, and at least one pesticide was detected in 62 of the 63 surfacewater samples. The greatest numbers of pesticides and the maximum observed concentrations for most pesticides were measured in surface-water samples from Idaho. In eight surface- water samples (six from Idaho and two from Wisconsin), concentrations of bifenthrin, metolachlor, or malathion exceeded U.S. Environmental Protection Agency freshwater aquatic-life benchmarks for chronic toxicity to invertebrates. Thirteen pesticides, including seven fungicides, were detected in groundwater samples. Shallow groundwater samples collected beneath recently harvested potato fields contained more pesticides and had higher concentrations of pesticides than samples collected from other groundwater sources sampled during the study. Generally, pesticide concentrations were lower in groundwater samples than in surfacewater or sediment samples, with the exception of the fungicide boscalid, which was found to have its highest concentration in a shallow groundwater sample collected in Wisconsin. Thirteen pesticides, including four fungicides, were detected in suspended-sediment samples. The most frequently detected compounds were the fungicides boscalid, pyraclostrobin, and zoxamide, and the degradates p,p’-DDD and p,p’-DDE. Twenty pesticides, including six fungicides, were detected in bed-sediment samples. The most frequently detected compounds were pyraclostrobin, p,p’-DDT, p,p’-DDD, and p,p’-DDE.

Compensation for matrix effects in the gas chromatography-mass spectrometry analysis of 186 pesticides in tea matrices using analyte protectants.

PubMed

Li, Yan; Chen, Xi; Fan, Chunlin; Pang, Guofang

2012-11-30

A gas chromatography-mass spectrometry (GC-MS) analytical method was developed for simultaneously determining 186 pesticides in tea matrices using analyte protectants to counteract the matrix-induced effect. The matrix effects were evaluated for green, oolong and black tea, representing unfermented, partially fermented and completely fermented teas respectively and depending on the type of tea, 72%, 94% and 94% of the pesticides presented strong response enhancement effect. Several analyte protectants as well as certain combinations of these protectants were evaluated to check their compensation effects. A mixture of triglycerol and d-ribonic acid-γ-lactone (both at 2mg/mL in the injected samples) was found to be the most effective in improving the chromatographic behavior of the 186 pesticides. More than 96% of the 186 pesticides achieved recoveries within the range of 70-120% when using the selected mixture of analyte protectants. The simple addition of analyte protectants offers a more convenient solution to overcome matrix effects, results in less active sites compared to matrix-matched standardization and can be an effective approach to compensate for matrix effects in the GC-MS analysis of pesticide residues. Copyright © 2012 Elsevier B.V. All rights reserved.

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. Copyright © 2014 Elsevier Ltd. All rights reserved.

Simulation of the fate of Boscalid and its transformation product 4-Chlorobenzoic acid in a vineyard-terraces catchment

NASA Astrophysics Data System (ADS)

Vollert, Dieter; Gassmann, Matthias; Olsson, Oliver; Kümmerer, Klaus

2017-04-01

In the viniculture fungicides are commonly applied foliar on the plant surface, resulting in high concentrations in runoff water. The fungicide Boscalid occurred frequently and in high concentrations in runoff water in the Loechernbach catchment, a 180 ha vineyard catchment in south-west Germany, during rainfall-runoff events in 2016. The catchment is characterized by a typical terraces structure and the connection of a dense road network. The washing off from drift-depositions on the streets is expected to be a major pathway for pesticides. The main objective of this study was the provision of a catchment model to simulate the transport and transformation processes of Boscalid. Based on this model, source areas of Boscalid residue pollution and its export pathways will be identified and provide urgently needed information for the development of water pollution control strategies. The distributed, process-based, reactive transport catchment model ZIN-AgriTra was used for the evaluation of the pesticide mobilization and the export processes. The hydrological model was successfully calibrated for a 6-month high-resolution time series of discharge data. Pesticide modelling was calibrated for single rainfall events after Boscalid application. Additionally, the transformation product 4-Chlorobenzoic acid has been simulated using literature substance parameters, in order to gain information about anticipated environmental concentrations. The pathways for the discharge of Boscalid were characterized and the streets were confirmed as major pathway for the pesticide discharge in the catchment. The main Boscalid loss occured during the first flush after a storm event containing concentrations up to 10 µg/l. The results show that storage on surfaces without sorption contributes significantly to the export of pesticides through the first flush. Therefore, the mobilization process affects a combination of both sorptive (e.g. at the soil) and non-sorptive (e.g. on the surface) storages at the roads. Furthermore, measurements and simulation results show that there are background pesticide concentrations, an order of magnitude lower than the first flush concentration, for the whole simulation period. Additionally, almost half of the applied Boscalid still remains as residue in the soil at the end of the simulated 6-month period, because of slow degradation rates of Boscalid. The transformation product 4-Chlorobenzoic acid was simulated to have concentrations in the range of 0.1 µg/l. The model assumes that subsurface flow is the major loss pathway for this substance. Concluding, the introduced catchment model is an applicable tool to simulate the individual processes of the Boscalid fate in the vineyard catchment. It was confirmed that roads receiving pesticide drift are the major loss areas of Boscalid in the Loechernbach catchment.

Identification of microbial species present in a pesticide dissipation process in biobed systems using typical substrates from southeastern Mexico as a biomixture at a laboratory scale.

PubMed

Góngora-Echeverría, Virgilio R; Quintal-Franco, Carlos; Arena-Ortiz, María Leticia; Giácoman-Vallejos, Germán; Ponce-Caballero, Carmen

2018-07-01

Biobed systems are an important option to control point pollution in agricultural areas. Substrates used and microbial diversity present in a biomixture perform an essential function in pesticide dissipation. In this study, the effects of soil (50% of volume/volume [V/V] proportion for all biomixtures) and four soil-based biomixtures (miniaturized biobeds; addition of novel substrates from southeastern Mexico) on dissipation of high concentrations of 2,4-dichlorophenoxyacetic acid (2,4-D), atrazine, carbofuran, diazinon, and glyphosate and on microbial diversity in biomixtures were evaluated. Small residual amounts of all pesticides at 20 (<2%) and 41 (<1%) days were observed; however, the lowest efficiency rates were observed in soil. Glyphosate was the only pesticide that completely dissipated in soil and biomixtures. Archaea, bacteria, and fungi were identified in biobeds, with bacteria being the most diverse microorganisms according to the identified species. The presence of white-rot fungi (normally related to pesticide degradation in biomixtures) was observed. Effects of the pesticide type and of biomixtures on pesticide dissipation were significant (P<0.05); however, only the effect of biomixtures on microbial diversity was significant (P<0.05); microbial diversity and richness had a significant effect on the residual amount of pesticides (P<0.05). Microbial diversity in terms of phyla was directly related to physicochemical parameters such as organic matter, lignin, water-holding capacity, and pH of soil and biomixtures. Copyright © 2018 Elsevier B.V. All rights reserved.

Anthelmintic efficacy of cinnamaldehyde and cinnamic acid from cortex cinnamon essential oil against Dactylogyrus intermedius.

PubMed

Ling, Fei; Jiang, Chao; Liu, Guanglu; Li, Mingshuang; Wang, Gaoxue

2015-12-01

Utilization of chemical pesticide to control monogenean diseases is often restricted in many countries due to the development of pesticide resistance and concerns of chemical residues and environmental contamination. Thus, the use of antiparasitic agents from plants has been explored as a possible way for controlling monogenean infections. Extracts from Cinnamomum cassia were investigated under in vivo conditions against Dactylogyrus intermedius in goldfish. The two bioactive compounds, cinnamaldehyde and cinnamic acid, were identified using nuclear magnetic resonance and electrospray ionization mass spectrometry. The 48 h median effective concentrations (EC(50)) for these compounds against D. intermedius were 0·57 and 6·32 mg L(-1), respectively. The LD(50) of cinnamaldehyde and cinnamic acid were 13·34 and 59·66 mg L(-1) to goldfish in 48 h acute toxicity tests, respectively. These data confirm that cinnamaldehyde is effective against D. intermedius, and the cinnamaldehyde exhibits potential for the development of a candidate antiparasitic agent.

Gas Chromatography

NASA Astrophysics Data System (ADS)

Qian, Michael C.

Gas chromatography (GC) has many applications in the analysis of food products. GC has been used for the determination of fatty acids, triglycerides, cholesterol, gases, water, alcohols, pesticides, flavor compounds, and many more. While GC has been used for other food components such as sugars, oligosaccharides, amino acids, peptides, and vitamins, these substances are more suited to analysis by high performance liquid chromatography. GC is ideally suited to the analysis of volatile substances that are thermally stable. Substances such as pesticides and flavor compounds that meet these criteria can be isolated from a food and directly injected into the GC. For compounds that are thermally unstable, too low in volatility, or yield poor chromatographic separation due to polarity, a derivatization step must be done before GC analysis. The two parts of the experiment described here include the analysis of alcohols that requires no derivatization step, and the analysis of fatty acids which requires derivatization. The experiments specify the use of capillary columns, but the first experiment includes conditions for a packed column.

Organochloride pesticides modulated gut microbiota and influenced bile acid metabolism in mice.

PubMed

Liu, Qian; Shao, Wentao; Zhang, Chunlan; Xu, Cheng; Wang, Qihan; Liu, Hui; Sun, Haidong; Jiang, Zhaoyan; Gu, Aihua

2017-07-01

Organochlorine pesticides (OCPs) can persistently accumulate in body and threaten human health. Bile acids and intestinal microbial metabolism have emerged as important signaling molecules in the host. However, knowledge on which intestinal microbiota and bile acids are modified by OCPs remains unclear. In this study, adult male C57BL/6 mice were exposed to p, p'-dichlorodiphenyldichloroethylene (p, p'-DDE) and β-hexachlorocyclohexane (β-HCH) for 8 weeks. The relative abundance and composition of various bacterial species were analyzed by 16S rRNA gene sequencing. Bile acid composition was analyzed by metabolomic analysis using UPLC-MS. The expression of genes involved in hepatic and enteric bile acids metabolism was measured by real-time PCR. Expression of genes in bile acids synthesis and transportation were measured in HepG2 cells incubated with p, p'-DDE and β-HCH. Our findings showed OCPs changed relative abundance and composition of intestinal microbiota, especially in enhanced Lactobacillus with bile salt hydrolase (BSH) activity. OCPs affected bile acid composition, enhanced hydrophobicity, decreased expression of genes on bile acid reabsorption in the terminal ileum and compensatory increased expression of genes on synthesis of bile acids in the liver. We demonstrated that chronic exposure of OCPs could impair intestinal microbiota; as a result, hepatic and enteric bile acid profiles and metabolism were influenced. The findings in this study draw our attention to the hazards of chronic OCPs exposure in modulating bile acid metabolism that might cause metabolic disorders and their potential to cause related diseases in human. Copyright © 2017 Elsevier Ltd. All rights reserved.

Analysis of metolachlor ethane sulfonic acid chirality in groundwater: A tool for dating groundwater movement in agricultural settings

USDA-ARS?s Scientific Manuscript database

Chemical chirality of pesticides can be a useful tool for studying environmental processes. The chiral forms of metolachlor ethane sulfonic acid (MESA), an abundant metabolite of metolachlor, and metolachlor were examined over a 6 year period in groundwater and a groundwater-fed stream in a riparia...

Inert Reassessment Document for Poly(oxyethylene)(5) sorbitan monooleate

EPA Pesticide Factsheets

The sorbitan fatty acid esters and polysorbates are inert ingredients used as surfactants, related adjuvants of surfactants, emulsifiers, buffering agents, and corrosion inhibitors in a variety of pesticide products.

Photodegradation of chlorpyrifos with humic acid-bound suspended matter.

PubMed

Amarathunga, A A D; Kazama, F

2014-09-15

Land exploitation in several developing countries, including tropical areas, has caused a rapid change of the landscape, from forest to farms. This has led to an increase of pesticide use and concentration of suspended matter in river waters, which may cause soil erosion of these areas. Humic acid (HA), one of the main components in the soil particulate organic matter, has a positive effect on the photodegradation of organic matter in water; however, the efficiency of HA-bound suspended matter (HABSM) for pesticide photodegradation is not known. The aim of this study is to clarify the effect of HABSM on the photodegradation of chlorpyrifos employed in artificial soil particulate covered with HA. Experiments were carried out in liquid HA phase, with/without HABSM phase and HABSM with additional LHA phase under light. The adsorption procedure of the pesticide on HABSM was also studied. Our results reveal that adsorption takes place within a short time period on HABSM and that photodegradation is successfully achieved. The additional LHA+HABSM phase have not demonstrated any significant effect of HA concentration to photodegradation of chlorpyrifos. For instance, when 2.0mg/L chlorpyrifos was used in the experiments, concentration reductions caused by adsorption, photodegradation under suspended matter and HABSM were found to be 19.3, 17.7, and 61.7% respectively. This finding suggests that HABSM can be considered as a potential catalyst for pesticide photodegradation under sunlight. Copyright © 2014 Elsevier B.V. All rights reserved.

Microwave assisted solvent extraction and coupled-column reversed-phase liquid chromatography with UV detection use of an analytical restricted-access-medium column for the efficient multi-residue analysis of acidic pesticides in soils.

PubMed

Hogendoom, E A; Huls, R; Dijkman, E; Hoogerbrugge, R

2001-12-14

A screening method has been developed for the determination of acidic pesticides in various types of soils. Methodology is based on the use of microwave assisted solvent extraction (MASE) for fast and efficient extraction of the analytes from the soils and coupled-column reversed-phase liquid chromatography (LC-LC) with UV detection at 228 nm for the instrumental analysis of uncleaned extracts. Four types of soils, including sand, clay and peat, with a range in organic matter content of 0.3-13% and ten acidic pesticides of different chemical families (bentazone, bromoxynil, metsulfuron-methyl, 2,4-D, MCPA, MCPP, 2,4-DP, 2,4,5-T, 2,4-DB and MCPB) were selected as matrices and analytes, respectively. The method developed included the selection of suitable MASE and LC-LC conditions. The latter consisted of the selection of a 5-microm GFF-II internal surface reversed-phase (ISRP, Pinkerton) analytical column (50 x 4.6 mm, I.D.) as the first column in the RAM-C18 configuration in combination with an optimised linear gradient elution including on-line cleanup of sample extracts and reconditioning of the columns. The method was validated with the analysis of freshly spiked samples and samples with aged residues (120 days). The four types of soils were spiked with the ten acidic pesticides at levels between 20 and 200 microg/kg. Weighted regression of the recovery data showed for most analyte-matrix combinations, including freshly spiked samples and aged residues, that the method provides overall recoveries between 60 and 90% with relative standard deviations of the intra-laboratory reproducibility's between 5 and 25%; LODs were obtained between 5 and 50 microg/kg. Evaluation of the data set with principal component analysis revealed that the parameters (i) increase of organic matter content of the soil samples and (ii) aged residues negatively effect the recovery of the analytes.

Effectiveness of dishwashing liquids in removing chlorothalonil and chlorpyrifos residues from cherry tomatoes.

PubMed

Wang, Zhiwei; Huang, Jiexun; Chen, Jinyuan; Li, Feili

2013-08-01

Washing is the most practical way to remove pesticide residues in fruits and vegetables. Two commonly used kitchen dishwashing liquids (detergents) in Chinese market were tested for enhanced removal of chlorpyrifos (CHP) and chlorothalonil (CHT) in cherry tomatoes by soaking the cherry tomatoes in the detergent solutions. The critical micelle concentrations of detergent A and detergent B were about 250 mg L(-1) and 444 mg L(-1), respectively. Detergent A had a higher solubilizing ability for pesticides and hence washing effectiveness than detergent B. The apparent solubility of CHP increased with increasing detergent concentration, while that of CHT remained comparatively invariant independent of detergent concentration within the tested range. The apparent solubility of CHP was also consistently higher in solutions of both detergents as compared to CHT. Due probably to its lower logKow value, CHT was more readily washed off cherry tomatoes than CHP. In terms of washing, a duration of 10-20 min was sufficient for removal of pesticides on cherry tomatoes in distilled water and detergent solutions. The effectiveness of removing pesticides increased with increasing detergent concentration from 50 mg L(-1) to 5 g L(-1), with up to 80% CHT and 42% CHP removed. Multiple washing further increased pesticide removal. Adding 10% acetic acid to lower pH or increasing washing temperature favored pesticide removal, but 10% NaCl produced the shielding effect and substantially reduced the effectiveness of detergent A for pesticide removal. Copyright © 2013 Elsevier Ltd. All rights reserved.

Activity-Based Protein Profiling of Organophosphorus and Thiocarbamate Pesticides Reveals Multiple Serine Hydrolase Targets in Mouse Brain

PubMed Central

NOMURA, DANIEL K.; CASIDA, JOHN E.

2010-01-01

Organophosphorus (OP) and thiocarbamate (TC) agrochemicals are used worldwide as insecticides, herbicides, and fungicides, but their safety assessment in terms of potential off-targets remains incomplete. In this study, we used a chemoproteomic platform, termed activity-based protein profiling, to broadly define serine hydrolase targets in mouse brain of a panel of 29 OP and TC pesticides. Among the secondary targets identified, enzymes involved in degradation of endocannabinoid signaling lipids, monoacylglycerol lipase and fatty acid amide hydrolase, were inhibited by several OP and TC pesticides. Blockade of these two enzymes led to elevations in brain endocannabinoid levels and dysregulated brain arachidonate metabolism. Other secondary targets include enzymes thought to also play important roles in the nervous system and unannotated proteins. This study reveals a multitude of secondary targets for OP and TC pesticides and underscores the utility of chemoproteomic platforms in gaining insights into biochemical pathways that are perturbed by these toxicants. PMID:21341672

Application of electrokinetic soil flushing to four herbicides: A comparison.

PubMed

dos Santos, E Vieira; Souza, F; Saez, C; Cañizares, P; Lanza, M R V; Martinez-Huitle, C A; Rodrigo, M A

2016-06-01

In this work, four bench-scale plants containing soil spiked with four herbicides (2,4-Dichlorophenoxyacetic acid (2,4-D), oxyfluorfen, chlorsulfuron and atrazine) undergo treatment consisting of an electrokinetic soil flushing (EKSF). Results clearly demonstrate that efficiency of EKSF depends on the chemical characteristic of the pesticide used. The amount of pesticide collected in the anode well is more significant than that collected in the cathode wells, indicating that the electromigration is much more important than drainage by electro-osmotic flux for this application. After 15 d of treatment, the 2,4-D is the pesticide most efficiently removed (95% of removal), while chlorsulfuron is the pesticide more resilient to the treatment. Additionally, volatilization was found to be a process of the major significance in the application of electrokinetic techniques to soil polluted with herbicides and because of that it should always be taken into account in the future design of full-scale processes. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

Partitioning of the pesticide trifluralin between dissolved organic matter and water using automated SPME-GC/MS.

PubMed

Caupos, Emilie; Touffet, Arnaud; Mazellier, Patrick; Croue, Jean-Philippe

2015-03-01

Solid-phase microextraction (SPME) was used to determine the equilibrium association constant for a pesticide, trifluralin (TFR), with dissolved organic matter (DOM). After optimization of the SPME method for the analysis of TFR, partition coefficients (K DOM) with three different sources of DOM were determined in buffered solutions at pH 7. Commercial humic acids and DOM fractions isolated from two surface waters were used. The values of log K DOM varied from 4.3 to 5.8, depending on the nature of the organic material. A good correlation was established between log K DOM and DOM properties (as measured with the H/O atomic ratio and UV absorbance), in agreement with literature data. This is consistent with the effect of polarity and aromaticity for governing DOM-pollutant associations, regardless of the origin of DOM. This association phenomenon is relevant to better understand the behavior of pesticides in the environment since it controls part of pesticide leaching and fate in aquatic systems.

The Greening of Pesticide–Environment Interactions: Some Personal Observations

PubMed Central

2012-01-01

Background: Pesticide–environment interactions are bidirectional. The environment alters pesticides by metabolism and photodegradation, and pesticides in turn change the environment through nontarget or secondary effects. Objectives: Approximately 900 currently used commercial pesticides of widely diverse structures act by nearly a hundred mechanisms to control insects, weeds, and fungi, usually with minimal disruption of nature’s equilibrium. Here I consider some aspects of the discovery, development, and use of ecofriendly or green pesticides (i.e., pesticides that are safe, effective, and biodegradable with minimal adverse secondary effects on the environment). Emphasis is given to research in my laboratory. Discussion: The need for understanding and improving pesticide–environment interactions began with production of the first major insecticide approximately 150 years ago: The arsenical poison Paris Green was green in color but definitely not ecofriendly. Development and use of other pesticides has led to a variety of problems. Topics considered here include the need for high purity [e.g., hexachlorocyclohexane and polychloroborane isomers and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T)], environmental degradation and the bioactivity of resulting photoproducts and metabolites, pesticide photochemistry (including the use of structural optimization, photostabilizers, and photosensitizers to achieve suitable persistence), the presence of multiple active ingredients in botanical insecticides, the need to consider compounds with common mechanisms of action, issues related to primary and secondary targets, and chemically induced or genetically modified changes in plant biochemistry. Many insecticides are bird, fish, and honeybee toxicants, whereas herbicides and fungicides pose fewer environmental problems. Conclusion: Six factors have contributed to the greening of pesticide–environment interactions: advances in pesticide chemistry and toxicology, banning of many chlorinated hydrocarbons, the development of new biochemical targets, increased reliance on genetically modified crops that reduce the amount and variety of pesticides applied, emphasis on biodegradability and environmental protection, and integrated pest- and pesticide-management systems. PMID:22472325

Four-year advanced monitoring program of polar pesticides in groundwater of Catalonia (NE-Spain).

PubMed

Köck-Schulmeyer, Marianne; Ginebreda, Antoni; Postigo, Cristina; Garrido, Teresa; Fraile, Josep; López de Alda, Miren; Barceló, Damià

2014-02-01

Pesticide contamination of groundwater is of paramount importance because it is the most sensitive and the largest body of freshwater in the European Union. In this paper, an isotopic dilution method based on on-line solid phase extraction-liquid chromatography (electrospray)-tandem mass spectrometry (SPE-LC(ESI)-MS/MS) was used for the analysis of 22 pesticides in groundwater. Results were evaluated from monitoring 112 wells and piezometers coming from 29 different aquifers located in 18 ground water bodies (GWBs), from Catalonia, Spain, for 4 years as part of the surveillance and operational monitoring programs conducted by the Catalan Water Agency. The analytical method developed allows the determination of the target pesticides (6 triazines, 4 phenylureas, 4 organophosphorous, 1 anilide, 2 chloroacetanilides, 1 thiocarbamate, and 4 acid herbicides) in groundwater with good sensitivity (limits of detection <5 ng/L), accuracy (relative recoveries between 85 and 116%, except for molinate), and repeatability (RSD<23%), and in a fully automated way. The most ubiquitous compounds were simazine, atrazine, desethylatrazine and diuron. Direct relation between frequency of detection of each target compound and Groundwater Ubiquity Score index (GUS index) is observed. Desethylatrazine and deisopropylatrazine, metabolites of atrazine and simazine, respectively, presented the highest mean concentrations. Compounds detected in less than 5% of the samples were cyanazine, molinate, fenitrothion and mecoprop. According to the Directive 2006/118/EC, 13 pesticides have individual values above the requested limits (desethylatrazine, atrazine and terbuthylazine lead the list) and 14 samples have total pesticide levels above 500 ng/L. The GWB with the highest levels of total pesticides is located in Lleida (NE-Spain), with 9 samples showing total pesticide levels above 500 ng/L. Several factors such as regulation of the use of pesticides, type of activities in the area, and irrigation were discussed in relation to the observed levels of pesticides. © 2013.

Conditions Optimizing and Application of Laccase-mediator System (LMS) for the Laccase-catalyzed Pesticide Degradation

PubMed Central

Jin, Xiaoting; Yu, Xiangyang; Zhu, Guangyan; Zheng, Zuntao; Feng, Fayun; Zhang, Zhiyong

2016-01-01

A high capacity of laccase from Trametes versicolor capable of degrading pesticides has been revealed. The conditions for degrading of five selected pesticides including chlorpyrifos, chlorothalonil, pyrimethanil, atrazine and isoproturon with the purified laccases from Trametes versicolor were optimized. The results showed that the optimum conditions for the highest activity were pH at 5.0 and temperature at 25 °C. The best mediators were violuric acid for pyrimethanil and isoproturon, vanillin for chlorpyrifos, and acetosyringone and HBT for chlorothalonil and atrazine, respectively. The laccase was found to be stable at a pH range from 5.0 to 7.0 and temperature from 25 to 30 °C. It was observed that each pesticide required a different laccase mediator concentration typically between 4.0–6.0 mmol/L. In the experiment, the degradation rates of pyrimethanil and isoproturon were significantly faster than those of chlorpyrifos, chlorothalonil and atrazine. For example, it was observed that pyrimethanil and isoproturon degraded up to nearly 100% after 24 hours while the other three pesticides just reached up 90% of degradation after 8 days of incubation. PMID:27775052

Conditions Optimizing and Application of Laccase-mediator System (LMS) for the Laccase-catalyzed Pesticide Degradation.

PubMed

Jin, Xiaoting; Yu, Xiangyang; Zhu, Guangyan; Zheng, Zuntao; Feng, Fayun; Zhang, Zhiyong

2016-10-24

A high capacity of laccase from Trametes versicolor capable of degrading pesticides has been revealed. The conditions for degrading of five selected pesticides including chlorpyrifos, chlorothalonil, pyrimethanil, atrazine and isoproturon with the purified laccases from Trametes versicolor were optimized. The results showed that the optimum conditions for the highest activity were pH at 5.0 and temperature at 25 °C. The best mediators were violuric acid for pyrimethanil and isoproturon, vanillin for chlorpyrifos, and acetosyringone and HBT for chlorothalonil and atrazine, respectively. The laccase was found to be stable at a pH range from 5.0 to 7.0 and temperature from 25 to 30 °C. It was observed that each pesticide required a different laccase mediator concentration typically between 4.0-6.0 mmol/L. In the experiment, the degradation rates of pyrimethanil and isoproturon were significantly faster than those of chlorpyrifos, chlorothalonil and atrazine. For example, it was observed that pyrimethanil and isoproturon degraded up to nearly 100% after 24 hours while the other three pesticides just reached up 90% of degradation after 8 days of incubation.

Conditions Optimizing and Application of Laccase-mediator System (LMS) for the Laccase-catalyzed Pesticide Degradation

NASA Astrophysics Data System (ADS)

Jin, Xiaoting; Yu, Xiangyang; Zhu, Guangyan; Zheng, Zuntao; Feng, Fayun; Zhang, Zhiyong

2016-10-01

A high capacity of laccase from Trametes versicolor capable of degrading pesticides has been revealed. The conditions for degrading of five selected pesticides including chlorpyrifos, chlorothalonil, pyrimethanil, atrazine and isoproturon with the purified laccases from Trametes versicolor were optimized. The results showed that the optimum conditions for the highest activity were pH at 5.0 and temperature at 25 °C. The best mediators were violuric acid for pyrimethanil and isoproturon, vanillin for chlorpyrifos, and acetosyringone and HBT for chlorothalonil and atrazine, respectively. The laccase was found to be stable at a pH range from 5.0 to 7.0 and temperature from 25 to 30 °C. It was observed that each pesticide required a different laccase mediator concentration typically between 4.0-6.0 mmol/L. In the experiment, the degradation rates of pyrimethanil and isoproturon were significantly faster than those of chlorpyrifos, chlorothalonil and atrazine. For example, it was observed that pyrimethanil and isoproturon degraded up to nearly 100% after 24 hours while the other three pesticides just reached up 90% of degradation after 8 days of incubation.

Formation of 2,4-D bound residues in soils: New insights into microbial metabolism.

PubMed

Botero, Liliana Rocío; Mougin, Chistian; Peñuela, Gustavo; Barriuso, Enrique

2017-04-15

The microbial contribution to the formation of bound residues in soils is studied by characterizing the metabolic activity of three microorganisms (Trametes versicolor, Fusarium solani and Ralstonia eutropha) on 14 C-2,4-dichlorophenoxyacetic acid (2,4-D) during incubation in synthetic liquid media and soil. A fractionation protocol was applied to quantify the 14 C-2,4-D that was incorporated into the biomass among biomolecular-like fractions. Successive fractionation of microbial biomass was implemented to break up and quantify the methanol/dichloromethane fraction (corresponding to the 14 C-lipid-like fraction), the trichloroacetic acid fraction (or hydrolysed 14 C-polysaccharide-like fraction) and the acid hydrolysable fraction (or the hydrolysed 14 C-protein-like fraction). Relevant differences in the 2,4-D degradation and biomass radioactivity distribution among the three microorganisms were found. The 14 C-protein-like fraction was the most consistent biomass fraction for reflecting the pesticide use capacity of the microorganisms under liquid and soil conditions. 2,4-D and its metabolite 4-chlorophenol were detected in methanol/dichloromethane and trichloroacetic acid fractions of the biomass of microorganisms exhibiting a low capacity to mineralize 2,4-D, thus proving that the microbial participation in the formation of bound residues while conserving the initial pesticide structure under natural soil conditions may be intimately associated with the lipid- and polysaccharide-like constituents. The fractionation protocol differentiates between 14 C that is incorporated into biomass as a biomolecular constituent and the pesticide or its metabolites that accumulate in the biomass and thus correspond to the stricto sensu definition of bound residues. Copyright © 2017 Elsevier B.V. All rights reserved.

Mobility and dissipation of chlorpyriphos and quinalphos in sandy clay loam in an agroecosystem-a laboratory-based soil column study.

PubMed

G P, Bindumol; C C, Harilal

2017-09-15

Leaching potential of pesticides, apart from climatological factors, depends on soil physical properties, soil-pesticide interaction and chemical nature of the molecule. Recent investigations have revealed the presence of various organophosphate pesticides in various agroecosystems. The present study investigated the soil transport mechanism of commonly used organophosphate pesticides in acidic sandy clay loam soils of Kerala State, India. Packed soil column experiment was undertaken under laboratory condition for 30 days. Unsaturated flow was carried out using distilled water/0.01 M CaCl 2 solution after applying chlorpyriphos and quinalphos at the rate of 0.04% a.i.ha -1 and 0.025% a.i.ha -1 , respectively. The study revealed the retention of residues of chlorpyriphos and quinalphos in the top 5-cm layer. Irrespective of the applied concentration of chlorpyriphos and quinalphos, the relative concentration of the pesticides in soil was similar. About 56% of the applied chemicals were dissipated in 30 days of unsaturated flow. A new dissipation compound iron, tricarbonyl [N-(phenyl-2-pyridinylmethyene) benzenamine-N, N'], was detected in GCMS analysis of soil extract from distilled water percolated soil. The dissipation of chlorpyriphos and quinalphos was faster in 0.01 M CaCl 2 -treated soil column. Among the pesticides analysed, the residue of quinalphos was detected in leachate.

Bioactive Paper Sensor Based on the Acetylcholinesterase for the Rapid Detection of Organophosphate and Carbamate Pesticides

PubMed Central

Badawy, Mohamed E. I.; El-Aswad, Ahmed F.

2014-01-01

In many countries, people are becoming more concerned about pesticide residues which are present in or on food and feed products. For this reason, several methods have been developed to monitor the pesticide residue levels in food samples. In this study, a bioactive paper-based sensor was developed for detection of acetylcholinesterase (AChE) inhibitors including organophosphate and carbamate pesticides. Based on the Ellman colorimetric assay, the assay strip is composed of a paper support (1 × 10 cm), onto which a biopolymer chitosan gel immobilized in crosslinking by glutaraldehyde with AChE and 5,5′-dithiobis(2-nitrobenzoic) acid (DTNB) and uses acetylthiocholine iodide (ATChI) as an outside reagent. The assay protocol involves introducing the sample to sensing zone via dipping of a pesticide-containing solution. Following an incubation period, the paper is placed into ATChI solution to initiate enzyme catalyzed hydrolysis of the substrate, causing a yellow color change. The absence or decrease of the yellow color indicates the levels of the AChE inhibitors. The biosensor is able to detect organophosphate and carbamate pesticides with good detection limits (methomyl = 6.16 × 10−4 mM and profenofos = 0.27 mM) and rapid response times (~5 min). The results show that the paper-based biosensor is rapid, sensitive, inexpensive, portable, disposable, and easy-to-use. PMID:25484901

Pesticide transport with runoff from creeping bentgrass turf: Relationship of pesticide properties to mass transport.

PubMed

Rice, Pamela J; Horgan, Brian P; Rittenhouse, Jennifer L

2010-06-01

The off-site transport of pesticides with runoff is both an agronomic and environmental concern, resulting from reduced control of target pests in the area of application and contamination of surrounding ecosystems. Experiments were designed to measure the quantity of pesticides in runoff from creeping bentgrass (Agrostis palustris) turf managed as golf course fairway to gain a better understanding of factors that influence chemical availability and mass transport. Less than 1 to 23% of applied chloropyrifos, flutolanil, mecoprop-p (MCPP), dimethylamine salt of 2,4-dichlorophenoxyacetic acid (2,4-D), or dicamba was measured in edge-of-plot runoff when commercially available pesticide formulations were applied at label rates 23 +/- 9 h prior to simulated precipitation (62 +/- 13 mm). Time differential between hollow tine core cultivation and runoff did not significantly influence runoff volumes or the percentage of applied chemicals transported in the runoff. With the exception of chlorpyrifos, all chemicals of interest were detected in the initial runoff samples and throughout the runoff events. Chemographs of the five pesticides followed trends in agreement with mobility classifications associated with their soil organic carbon partition coefficient (K(OC).) Data collected from the present study provides information on the transport of chemicals with runoff from turf, which can be used in model simulations to predict nonpoint source pollution potentials and estimate ecological risks. Copyright 2010 SETAC.

Effects of multiple but low pesticide loads on aquatic fungal communities colonizing leaf litter.

PubMed

Talk, Anne; Kublik, Susanne; Uksa, Marie; Engel, Marion; Berghahn, Rüdiger; Welzl, Gerhard; Schloter, Michael; Mohr, Silvia

2016-08-01

In the first tier risk assessment (RA) of pesticides, risk for aquatic communities is estimated by using results from standard laboratory tests with algae, daphnids and fish for single pesticides such as herbicides, fungicides, and insecticides. However, fungi as key organisms for nutrient cycling in ecosystems as well as multiple pesticide applications are not considered in the RA. In this study, the effects of multiple low pesticide pulses using regulatory acceptable concentrations (RACs) on the dynamics of non-target aquatic fungi were investigated in a study using pond mesocosm. For that, fungi colonizing black alder (Alnus glutinosa) leaves were exposed to multiple, low pulses of 11 different pesticides over a period of 60days using a real farmer's pesticide application protocol for apple cropping. Four pond mesocosms served as treatments and 4 as controls. The composition of fungal communities colonizing the litter material was analyzed using a molecular fingerprinting approach based on the terminal Restriction Fragment Length Polymorphism (t-RFLP) of the fungal Internal Transcribed Spacer (ITS) region of the ribonucleic acid (RNA) gene(s). Our data indicated a clear fluctuation of fungal communities based on the degree of leaf litter degradation. However significant effects of the applied spraying sequence were not observed. Consequently also degradation rates of the litter material were not affected by the treatments. Our results indicate that the nutrient rich environment of the leaf litter material gave fungal communities the possibility to express genes that induce tolerance against the applied pesticides. Thus our data may not be transferred to other fresh water habitats with lower nutrient availability. Copyright © 2016. Published by Elsevier B.V.

Determination of polychlorinated biphenyl congeners and chlorinated pesticides in a fish tissue standard reference material.

PubMed

Poster, Dianne L; Kucklick, John R; Schantz, Michele M; Porter, Barbara J; Leigh, Stefan D; Wise, Stephen A

2003-01-01

The concentrations of a wide range of polychlorinated biphenyl congeners (PCBs) and chlorinated pesticides in a fish tissue Standard Reference Material (SRM) have been determined using multiple methods of analysis. This material, SRM 1946, Lake Superior Fish Tissue, was recently issued by the National Institute of Standards and Technology (NIST) and complements a suite of marine environmental natural-matrix SRMs that are currently available from NIST for the determination of organic contaminants such as aliphatic hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), PCBs, and chlorinated pesticides. SRM 1946 is a fresh tissue homogenate (frozen) prepared from filleted adult lake trout (Salvelinus namaycush namaycush) collected from the Apostle Islands region of Lake Superior. SRM 1946 has certified and reference concentrations for PCB congeners, including the three non- ortho PCB congeners, and chlorinated pesticides. Certified concentrations are available for 30 PCB congeners and 15 chlorinated pesticides. Reference concentrations are available for 12 PCB congeners and 2 chlorinated pesticides. In addition, SRM 1946 is characterized for additional chemical constituents and properties: fatty acids, extractable fat, methylmercury, total mercury, selected trace elements, proximates, and caloric content. The characterization of chlorinated compounds is described in this paper with an emphasis on the approach used for the certification of the concentrations of PCB congeners and chlorinated pesticides. The PCB congener and chlorinated pesticide data are also compared to concentrations in other marine natural-matrix reference materials available from NIST (fish oil, mussel tissue, whale blubber, and a second fresh frozen fish tissue homogenate prepared from filleted adult lake trout collected from Lake Michigan) and from other organizations such as the National Research Council Canada (ground whole carp), the International Atomic Energy Agency (fish homogenate), and the European Commission Joint Research Centre [fish oils (cod and mackerel) and mussel tissue].

76 FR 7703 - 1,4-Benzenedicarboxylic Acid, Dimethyl Ester, Polymer With 1,4-Butanediol, Adipic Acid, and...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-02-11

... of pesticide use in residential settings. If EPA is able to determine that a finite tolerance is not... part of its composition the atomic elements carbon, hydrogen, and oxygen. 3. The polymer does not contain as an integral part of its composition, except as impurities, any element other than those listed...

Effects of currently used pesticides and their mixtures on the function of thyroid hormone and aryl hydrocarbon receptor in cell culture

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghisari, Mandana; Long, Manhai; Tabbo, Agnese

Evidence suggest that exposure to pesticides can interfere with the endocrine system by multiple mechanisms. The endocrine disrupting potential of currently used pesticides in Denmark was analyzed as single compounds and in an equimolar mixture of 5 selected pesticides. The pesticides were previously analyzed for effects on the function of estrogen and androgen receptors, the aromatase enzyme and steroidogenesis in vitro. In this study, the effect on thyroid hormone (TH) function and aryl hydrocarbon receptor (AhR) transactivity was assessed using GH3 cell proliferation assay (T-screen) and AhR responsive luciferase reporter gene bioassay, respectively. Thirteen pesticides were analyzed as follows: 2-methyl-4-chlorophenoxyaceticmore » acid, terbuthylazine, iodosulfuron-methyl-sodium, mesosulfuron-methyl, metsulfuron-methyl, chlormequat chloride, bitertanol, propiconazole, prothioconazole, mancozeb and its metabolite ethylene thiourea, cypermethrin, tau-fluvalinate, and malathion (currently banned in DK). In the T-screen, prothioconazole, malathion, tau-fluvalinate, cypermethrin, terbuthylazine and mancozeb significantly stimulated and bitertanol and propiconazole slightly reduced the GH3 cell proliferation. In the presence of triiodothyronine (T3), prothioconazole, tau-fluvalinate, propiconazole, cypermethrin and bitertanol significantly antagonized the T3-induced GH3 cell proliferation. Eleven of the tested pesticides agonized the AhR function, and bitertanol and prothioconazole inhibited the basal AhR activity. Bitertanol, propiconazole, prothioconazole and cypermethrin antagonized the TCDD-induced AhR transactivation at the highest tested concentration. The 5-component mixture had inducing effect but the combined effect could not be predicted due to the presence of bitertanol eliciting inhibitory effect. Upon removal of bitertanol from the mixture, the remaining four pesticides acted additively. In conclusion, our data suggest that pesticides currently used in Denmark can interfere with TH signaling and AhR function in vitro and might have the potential to cause endocrine disruption. - Highlights: • Endocrine disrupting (ED) potential of currently used pesticides were evaluated in cell culture. • Pesticides were analyzed for disruption of TH and aryl hydrocarbon receptor function. • 6 pesticides increased the GH3 cell proliferation, whereasfour antagonized the T3-induced cell growth. • 11 pesticides had agonistic effect on AhR and 4 antagonized the TCDD-induced AhR transactivation. • The five component mixture had inducing effect in both assays.« less

Using Three-Dimensional Fluorescence Spectrum Technology to Analyze the Effects of Natural Dissolved Organic Matter on the Pesticide Residues in the Soil.

PubMed

Lei, Hong-jun; Han, Yu-ping; Liu, Xin; Xu, Jian-xin

2015-07-01

The behavior of pesticide in soil is influenced by dissolved organic matter (DOM) through competition adsorption, adsorption, solubilization, accelerated degradation, and so on. Thus DOM and its components play an important role in the environmental risk in the soil ecosystem and groundwater environment. Currently, most studies focused on the short-term effect of high concentration of DOM on the pesticide residues. However, soil DOM is mainly at low level. Therefore, there is of some practical significance to probe into the environmental behavior of soil pesticides under natural level of DOM. Thus a site investigation was conducted in the farmland with long-term application history of pesticide. By using the three dimensional excitation-emission fluorescence matrix (3D-EEM) technology, together with the fluorescence regional integration (FRI) quantitative method, the long-term effects of pesticide residues under low concentration of natural DOM were analyzed. Results showed that: (1) The long-term effects of the natural DOM components on the environment behavior of most soil organochlorine pesticides were not significant except for a few pesticides such as y-HCH, p, p'-DDE, etc. (2) The influencing effects of DOM components on different type of pesticides were varied. Among which, the content of tyrosine component showed a significantly negative correlation (p < 0.05) with the concentration of y-HCH and p, p'-DDE. There were significant positive correlations (p < 0.05) between the byproducts of microbial degradation in DOM components and the concentration of heptachlor. There were also a significant positive correlation (p < 0.05) between the content of active humus component of humic acid in the DOM and the concentration of heptachlor epoxide. These results suggested that the distribution of different types of pesticides residue in the soil was influenced by different components at different levels of significance. (3) The humification degree of soil organic matter showed minor effect of DOM on the pesticide residues in the soil. In this study, 3D-EEM and FRI technology were firstly coupled in use for studying the influence of different components of DOM in soil on the environmental behavior of pesticides, which provides a new idea for the research on the mechanism of pesticides transportation and transformation in soil and groundwater environment.

Water solubility enhancement of some organic pollutants and pesticides by dissolved humic and fulvic acids

USGS Publications Warehouse

Chiou, C.T.; Malcolm, R.L.; Brinton, T.I.; Kile, D.E.

1986-01-01

Water solubility enhancements by dissolved humic and fulvic acids from soil and aquatic origins and by synthetic organic polymers have been determined for selected organic pollutants and pesticides (p,p???-DDT, 2,4,5,2???,5???-PCB, 2,4,4???-PCB, 1,2,3-trichlorobenzene, and lindane). Significant solubility enhancements of relatively water-insoluble solutes by dissolved organic matter (DOM) of soil and aquatic origins may be described in terms of a partition-like interaction of the the solutes with the microscopic organic environment of the high-molecular-weight DOM species; the apparent solute solubilities increase linearly with DOM concentration and show no competitive effect between solutes. With a given DOM sample, the solute partition coefficient (Kdom) increases with a decrease of solute solubility (Sw) or with an increase of the solute's octanol-water partition coefficient (Kow). The Kdom values of solutes with soil-derived humic acid are approximately 4 times greater than with soil fulvic acid and 5-7 times greater than with aquatic humic and fulvic acids. The effectiveness of DOM in enhancing solute solubility appears to be largely controlled by the DOM molecular size and polarity. The relative inability of high-molecular-weight poly(acrylic acids) to enhance solute solubility is attributed to their high polarities and extended chain structures that do not permit the formation of a sizable intramolecular nonpolar environment.

Time trend investigation of PCBs, PBDEs, and organochlorine pesticides in selected n-3 polyunsaturated fatty acid rich dietary fish oil and vegetable oil supplements; nutritional relevance for human essential n-3 fatty acid requirements.

PubMed

Jacobs, Miriam N; Covaci, Adrian; Gheorghe, Adriana; Schepens, Paul

2004-03-24

In addition to being used in the food and animal feed industry, fish oils have also been used traditionally as dietary supplements. Due to the presence of long-chain n-3 fatty acids, fish oils have therapeutic benefits in the prevention and treatment of cardiovascular, immunological, and arthritic diseases, as well as childhood deficiency diseases such as rickets, because of a high content of vitamin D. However, fish oils are also susceptible to contamination with lipophilic organic chemicals that are now ubiquitous contaminants of marine ecosystems. Many vegetable oils are sources of the shorter chain precursor forms of n-3 fatty acids, and in recent years the specialist dietary supplement market has expanded to include these oils in a variety of different formulations. This paper reports analytical results of selected contaminants, including polychlorinated biphenyls, organochlorine pesticides, and polybrominated diphenyl ethers, for a range of commercially available n-3 fatty acid rich fish and vegetable oil dietary supplements. Using principal component analysis, the values are compared with historic samples to elucidate time trends in contamination profiles. Levels of contaminants are discussed in relation to the nutritional benefits to the consumer of long- and short-chain forms of n-3 fatty acids.

Silencing of ACO decreases reproduction and energy metabolism in triazophos-treated female brown plant hoppers, Nilaparvata lugens Stål (Hemiptera: Delphacidae).

PubMed

Liu, Zong-Yu; Jiang, Yi-Ping; Li, Lei; You, Lin-Lin; Wu, You; Xu, Bin; Ge, Lin-Quan; Wu, Jin-Cai

2016-03-01

The brown plant hopper (BPH), Nilaparvata lugens Stål (Hemiptera: Delphacidae), is a major pest affecting rice in Asia, and outbreaks of this pest are closely linked to pesticide-induced stimulation of reproduction. Therefore, the BPH is a classic example of a resurgent pest. However, the effects of different genes on the regulation of pesticide-induced reproductive stimulation in the BPH are unclear. In this study, the regulatory effects of acyl-coenzyme A oxidase (ACO) on the reproduction and biochemistry of the BPH were investigated with gene silencing. The number of eggs laid per female by triazophos (TZP)+dsACO BPH females was significantly lower than those of TZP-treated (without ACO silencing) or TZP+GFP females (negative control), with the number of eggs decreasing by 30.8% (from 529.5 to 366.3) and 32.0% (from 540.5 to 366.3), respectively. The preoviposition period, oviposition period, and longevity of the TZP-treated females were also influenced by dsACO treatment. Additionally, the amounts of crude fat, protein, and some fatty acids (oleic acid, palmitic acid, linoleic acid, stearic acid, and myristoleic acid) in TZP+dsACO females were significantly lower than in TZP-treated females. Thus, ACO is one of the key genes regulating the TZP-induced stimulation of reproduction in BPH females. Copyright © 2015 Elsevier Inc. All rights reserved.

Comparison of Fiber Optic and Conduit Attenuated Total Reflection (ATR) Fourier Transform Infrared (FT-IR) Setup for In-Line Fermentation Monitoring.

PubMed

Koch, Cosima; Posch, Andreas E; Herwig, Christoph; Lendl, Bernhard

2016-12-01

The performance of a fiber optic and an optical conduit in-line attenuated total reflection mid-infrared (IR) probe during in situ monitoring of Penicillium chrysogenum fermentation were compared. The fiber optic probe was connected to a sealed, portable, Fourier transform infrared (FT-IR) process spectrometer via a plug-and-play interface. The optical conduit, on the other hand, was connected to a FT-IR process spectrometer via a knuckled probe with mirrors that had to be adjusted prior to each fermentation, which were purged with dry air. Penicillin V (PenV) and its precursor phenoxyacetic acid (POX) concentrations were determined by online high-performance liquid chromatography and the obtained concentrations were used as reference to build partial least squares regression models. Cross-validated root-mean-square errors of prediction were found to be 0.2 g L -1 (POX) and 0.19 g L -1 (PenV) for the fiber optic setup and 0.17 g L -1 (both POX and PenV) for the conduit setup. Higher noise-levels and spectrum-to-spectrum variations of the fiber optic setup lead to higher noise of estimated (i.e., unknown) POX and PenV concentrations than was found for the conduit setup. It seems that trade-off has to be made between ease of handling (fiber optic setup) and measurement accuracy (optical conduit setup) when choosing one of these systems for bioprocess monitoring. © The Author(s) 2016.

40 CFR 180.1023 - Propanoic acid; exemptions from the requirement of a tolerance.

Code of Federal Regulations, 2014 CFR

2014-07-01

... byproducts; milk, and egg when applied as a bactericide/fungicide to livestock drinking water, poultry litter... either an active or inert ingredient in accordance with good agricultural practice in pesticide...

40 CFR 180.1023 - Propanoic acid; exemptions from the requirement of a tolerance.

Code of Federal Regulations, 2012 CFR

2012-07-01

... byproducts; milk, and egg when applied as a bactericide/fungicide to livestock drinking water, poultry litter... either an active or inert ingredient in accordance with good agricultural practice in pesticide...

40 CFR 180.1023 - Propanoic acid; exemptions from the requirement of a tolerance.

Code of Federal Regulations, 2013 CFR

2013-07-01

... byproducts; milk, and egg when applied as a bactericide/fungicide to livestock drinking water, poultry litter... either an active or inert ingredient in accordance with good agricultural practice in pesticide...

Meta-analysis of pesticide sorption in subsoils

NASA Astrophysics Data System (ADS)

Jarvis, Nicholas

2017-04-01

It has been known for several decades that sorption koc values tend to be larger in soils that are low in organic carbon (i.e. subsoils). Nevertheless, in a regulatory context, the models used to assess leaching of pesticides to groundwater still rely on a constant koc value, which is usually measured on topsoil samples. This is mainly because the general applicability of any improved model approach that is also simple enough to use for regulatory purposes has not been demonstrated. The objective of this study was therefore first to summarize and generalize available literature data in order to assess the magnitude of any systematic increase of koc values in subsoil and to test an alternative model of subsoil sorption that could be useful in pesticide risk assessment and management. To this end, a database containing the results of batch sorption experiments for pesticides was compiled from published studies in the literature, which placed at least as much emphasis on measurements in subsoil horizons as in topsoil. The database includes 967 data entries from 46 studies and for 34 different active substances (15 non-ionic compounds, 13 weak acids, 6 weak bases). In order to minimize pH effects on sorption, data for weak acids and bases were only included if the soil pH was more than two units larger than the compound pKa. A simple empirical model, whereby the sorption constant is given as a power law function of the soil organic carbon content, gave good fits to most data sets. Overall, the apparent koc value, koc(app), for non-ionic compounds and weak bases roughly doubled as the soil organic carbon content decreased by a factor of ten. The typical increase in koc(app) was even larger for weak acids: on average koc(app) increased by a factor of six as soil organic carbon content decreased by a factor of ten. These results suggest the koc concept currently used in leaching models should be replaced by an alternative approach that gives a more realistic representation of pesticide sorption in subsoil. The model tested in this study appears to be widely applicable and simple enough to parameterize for risk assessment purposes. However, more data on subsoil sorption should first be included in the analysis to enable reliable estimation of worst-case percentile values of the power law exponent in the model.

Simultaneous determination of 117 pesticides and 30 mycotoxins in raw coffee, without clean-up, by LC-ESI-MS/MS analysis.

PubMed

Reichert, Bárbara; de Kok, André; Pizzutti, Ionara Regina; Scholten, Jos; Cardoso, Carmem Dickow; Spanjer, Martien

2018-04-03

This paper describes the optimization and validation of an acetonitrile based method for simultaneous extraction of multiple pesticides and mycotoxins from raw coffee beans followed by LC-ESI-MS/MS determination. Before extraction, the raw coffee samples were milled and then slurried with water. The slurried samples were spiked with two separate standard solutions, one containing 131 pesticides and a second with 35 mycotoxins, which were divided into 3 groups of different relative concentration levels. Optimization of the QuEChERS approach included performance tests with acetonitrile acidified with acetic acid or formic acid, with or without buffer and with or without clean-up of the extracts before LC-ESI-MS/MS analysis. For the clean-up step, seven d-SPE sorbents and their various mixtures were evaluated. After method optimization a complete validation study was carried out to ensure adequate performance of the extraction and chromatographic methods. The samples were spiked at 3 concentrations levels with both mycotoxins and pesticides (with 6 replicates at each level, n = 6) and then submitted to the extraction procedure. Before LC-ESI-MS/MS analysis, the acetonitrile extracts were diluted 2-fold with methanol, in order to improve the chromatographic performance of the early-eluting polar analytes. Calibration standard solutions were prepared in organic solvent and in blank coffee extract at 7 concentration levels and analyzed 6 times each. The method was assessed for accuracy (recovery %), precision (RSD%), selectivity, linearity (r 2 ), limit of quantification (LOQ) and matrix effects (%). Copyright © 2017 Elsevier B.V. All rights reserved.

Comparison of two extraction methods for the determination of 135 pesticides in Corydalis Rhizoma, Chuanxiong Rhizoma and Angelicae Sinensis Radix by liquid chromatography-triple quadrupole-mass spectrometry. Application to the roots and rhizomes of Chinese herbal medicines.

PubMed

Liu, Jie; Tong, Ling; Li, Dongxiang; Meng, Wenting; Sun, Wanyang; Zhao, Yunli; Yu, Zhiguo

2016-04-01

In this study, two simple pretreatment methods were comprehensively evaluated for the determination of 135 pesticide residues in roots and rhizomes of Chinese herbal medicines (CHMs). The studied methodologies are (a) solid-phase extraction (SPE) and (b) Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS). For SPE, extraction solvents, SPE cartridges and types and volume of eluent were accessed and optimized. For QuEChERS, different versions, acetic acid concentration and dispersive solid-phase extraction (dSPE) sorbent materials were tested. SPE and QuEChERS were estimated in recovery range, the number of pesticides that were recovered ranging from 90% to 110% and expenses in Corydalis Rhizoma, Chuanxiong Rhizoma and Angelicae Sinensis Radix. QuEChERS method showed better performance than SPE. The method showed good linearity over the range assayed 0.9986-0.9999 (1-80ng/mL for 124 pesticides, 1-50ng/mL for 10 pesticides, 1-20ng/mL for satisfar). The matrix effect was compensated by matrix-based calibration curves with internal standard. The average recoveries of all pesticides were ranging from 70% to 120% at three levels of 10, 50 and 100ng/g with relative standard deviations less than 20%. The limits of quantification of the 135 pesticides in three matrices were 1-5ng/g, which were below the maximum residue levels (MRLs) established by the European Union. The verified QuEChERS method was successfully applied to the analysis of 65 actual samples from eight different types of roots and rhizomes of CHMs. Angelicae Sinensis Radix was the most susceptible to pesticides among these samples, and the most frequently detected pesticide was carbendazim with levels below MRLs. Metalaxyl, phorate, atrazine, diniconazole, coumaphos and paclobutrazol were also detected in some samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Fluorescent spectral studies of the toxic effect of chlororganic pesticides on the biochemical parameters of synaptosomes

NASA Astrophysics Data System (ADS)

Giraev, K. M.; Bekshokov, K. S.; Ashurbekov, N. A.; Abdullaeva, N. M.; Israpov, E. Kh.; Gashimov, I. Sh.

2017-04-01

The results of the study of the fluorescence spectra of suspensions of synaptosomes, which have been exposed to a chlororganic pesticide, thiamethoxam, at a concentration of 50 MPC during different time periods, at the excitation/emission wavelengths of 290 ± 5/310-600, 340 ± 5/360-700, and 420 ± 5/450-800 nm are given for the first time. It has been demonstrated that the development of intoxication results in weakening of the fluorescence intensity of tryptophan, NAD(P)·H, derivatives of vitamin B6, and vitamin A and in an increase in the fluorescence of pyridoxic acid, lipofuscin, and flavin and porphyrin complexes. The results of the spectral studies indicate that the toxic effect of the chlororganic pesticide for the functioning of living systems is based on free radical toxicity.

Proceedings of Neurotox 󈨜, Molecular Basis of Drug and Pesticide Action (3rd) Held in Bath, England on April 10-15, 1988

DTIC Science & Technology

1988-06-01

Jasmine (Jasminium gradiflorum L) essence . [(ely. Chim. Acta 47, 1152. 55 Vick. B.A. and Zimmerman. D.C. (1984) Biosynthesis of Jasmonic acid by...expensive perfumery material found in the extract of jasmine flowers and I was able to show that the natural material was cis- with an odour much...theory of rethrolone formation. Extract of jasmine flowers contains jasmonic acid, jasmone lactone and jasmone (Fig. 33) [541. trans-(Z)-Jasmonic acid can

Low molecular weight polylactic acid as a matrix for the delayed release of pesticides.

PubMed

Zhao, Jing; Wilkins, Richard M

2005-05-18

Low molecular weight polylactic acid (LMW PLA) was used as a matrix to formulate biodegradable matrix granules and films with bromacil using a melt process. The compatibility of the PLA with bromacil was evaluated. The release characteristics of the formulations were investigated in vitro. The degradation and erosion of the formulations were monitored by pH and gravimetric analysis during the course of release. Various granules and films had similar biphasic release patterns, a delayed release followed by an explosive release. The release rates were independent of bromacil content in the matrix, but varied with the geometry of matrices. The mechanisms of diffusion and erosion were involved in the release. The delayed release of the formulations was dominantly governed by the degradation and erosion of PLA. LMW PLA underwent bulk erosion. LMW PLA-based matrix formulations could thus be useful for the application of pesticides to sensitive targets such as seed treatment.

CEC-atmospheric pressure ionization MS of pesticides using a surfactant-bound monolithic column.

PubMed

Gu, Congying; Shamsi, Shahab A

2010-04-01

A surfactant bound poly (11-acrylaminoundecanoic acid-ethylene dimethacrylate) monolithic column was simply prepared by in situ co-polymerization of 11-acrylaminoundecanoic acid and ethylene dimethacrylate with 1-propanol, 1,4-butanediol and water as porogens in 100 microm id fused-silica capillary in one step. This column was used in CEC-atmospheric pressure photoionization (APPI)-MS system for separation and detection of N-methylcarbamates pesticides. Numerous parameters are optimized for CEC-APPI-MS. After evaluation of the mobile phase composition, sheath liquid composition and the monolithic capillary outlet position, a fractional factorial design was selected as a screening procedure to identify factors of ionization source parameters, such as sheath liquid flow rate, drying gas flow rate, drying gas temperature, nebulizing gas pressure, vaporizer temperature and capillary voltage, which significantly influence APPI-MS sensitivity. A face-centered central composite design was further utilized to optimize the most significant parameters and predict the best sensitivity. Under optimized conditions, S/Ns around 78 were achieved for an injection of 100 ng/mL of each pesticide. Finally, this CEC-APPI-MS method was successfully applied to the analysis of nine N-methylcarbamates in spiked apple juice sample after solid phase extraction with recoveries in the range of 65-109%.

Multi-pesticides residue analysis of grains using modified magnetic nanoparticle adsorbent for facile and efficient cleanup.

PubMed

Liu, Zhenzhen; Qi, Peipei; Wang, Xiangyun; Wang, Zhiwei; Xu, Xiahong; Chen, Wenxue; Wu, Liyu; Zhang, Hu; Wang, Qiang; Wang, Xinquan

2017-09-01

A facile, rapid sample pretreatment method was developed based on magnetic nanoparticles for multi-pesticides residue analysis of grains. Magnetite (Fe 3 O 4 ) nanoparticles modified with 3-(N,N-diethylamino)propyltrimethoxysilane (Fe 3 O 4 -PSA) and commercial C18 were selected as the cleanup adsorbents to remove the target interferences of the matrix, such as fatty acids and non-polar compounds. Rice was used as the representative grain sample for method optimization. The amount of Fe 3 O 4 -PSA and C18 were systematically investigated for selecting the suitable purification conditions, and the simultaneous determination of 50 pesticides and 8 related metabolites in rice was established by liquid chromatography-tandem mass spectrometry. Under the optimal conditions, the method validation was performed including linearity, sensitivity, matrix effect, recovery and precision, which all satisfy the requirement for pesticides residue analysis. Compared to the conventional QuEChERS method with non-magnetic material as cleanup adsorbent, the present method can save 30% of the pretreatment time, giving the high throughput analysis possible. Copyright © 2017 Elsevier Ltd. All rights reserved.

Combining experimental techniques with non-linear numerical models to assess the sorption of pesticides on soils

NASA Astrophysics Data System (ADS)

Magga, Zoi; Tzovolou, Dimitra N.; Theodoropoulou, Maria A.; Tsakiroglou, Christos D.

2012-03-01

The risk assessment of groundwater pollution by pesticides may be based on pesticide sorption and biodegradation kinetic parameters estimated with inverse modeling of datasets from either batch or continuous flow soil column experiments. In the present work, a chemical non-equilibrium and non-linear 2-site sorption model is incorporated into solute transport models to invert the datasets of batch and soil column experiments, and estimate the kinetic sorption parameters for two pesticides: N-phosphonomethyl glycine (glyphosate) and 2,4-dichlorophenoxy-acetic acid (2,4-D). When coupling the 2-site sorption model with the 2-region transport model, except of the kinetic sorption parameters, the soil column datasets enable us to estimate the mass-transfer coefficients associated with solute diffusion between mobile and immobile regions. In order to improve the reliability of models and kinetic parameter values, a stepwise strategy that combines batch and continuous flow tests with adequate true-to-the mechanism analytical of numerical models, and decouples the kinetics of purely reactive steps of sorption from physical mass-transfer processes is required.

Sequential two-column electro-Fenton-photolytic reactor for the treatment of winery wastewater.

PubMed

Díez, A M; Sanromán, M A; Pazos, M

2017-01-01

The high amount of winery wastewaters produced each year makes their treatment a priority issue due to their problematic characteristics such as acid pH, high concentration of organic load and colourful compounds. Furthermore, some of these effluents can have dissolved pesticides, due to the previous grape treatments, which are recalcitrant to conventional treatments. Recently, photo-electro-Fenton process has been reported as an effective procedure to mineralize different organic contaminants and a promising technology for the treatment of these complex matrixes. However, the reactors available for applying this process are scarce and they show several limitations. In this study, a sequential two-column reactor for the photo-electro-Fenton treatment was designed and evaluated for the treatment of different pesticides, pirimicarb and pyrimethanil, used in wine production. Both studied pesticides were efficiently removed, and the transformation products were determined. Finally, the treatment of a complex aqueous matrix composed by winery wastewater and the previously studied pesticides was carried out in the designed sequential reactor. The high removals of TOC and COD reached and the low energy consumption demonstrated the efficiency of this new configuration.

Associations between self-reported pest treatments and pesticide concentrations in carpet dust.

PubMed

Deziel, Nicole C; Colt, Joanne S; Kent, Erin E; Gunier, Robert B; Reynolds, Peggy; Booth, Benjamin; Metayer, Catherine; Ward, Mary H

2015-03-25

Recent meta-analyses demonstrate an association between self-reported residential pesticide use and childhood leukemia risk. Self-reports may suffer from recall bias and provide information only on broad pesticide categories. We compared parental self-reported home and garden pest treatments to pesticides measured in carpet dust. Parents of 277 children with leukemia and 306 controls in Northern and Central California (2001-2007) were asked about insect and weed treatments during the previous year. Carpet dust samples were analyzed for 47 pesticides. We present results for the 7 insecticides (carbaryl, propoxur, chlorpyrifos, diazinon, cyfluthrin, cypermethrin, permethrin), 5 herbicides (2,4-dichlorophenoxyacetic acid [2,4-D], chlorthal, dicamba, mecoprop, simazine), and 1 synergist (piperonyl butoxide) that were present in home and garden products during the study period and were detected in ≥25% of carpet dust samples. We constructed linear regression models for the relative change in pesticide concentrations associated with self-reported treatment of pest types in cases and controls separately and combined, adjusting for demographics, housing characteristics, and nearby agricultural pesticide applications. Several self-reported treatments were associated with pesticide concentrations in dust. For example, households with flea/tick treatments had 2.3 (95% Confidence Interval [CI]: 1.4, 3.7) times higher permethrin concentrations than households not reporting this treatment. Households reporting treatment for ants/cockroaches had 2.5 (95% CI: 1.5, 4.2) times higher cypermethrin levels than households not reporting this treatment. Weed treatment by a household member was associated with 1.9 (1.4, 2.6), 2.2 (1.6, 3.1), and 2.8 (2.1, 3.7) times higher dust concentrations of dicamba, mecoprop, and 2,4-D, respectively. Weed treatments by professional applicators were null/inversely associated with herbicide concentrations in dust. Associations were generally similar between cases and controls and were consistent with pesticide active ingredients in these products during the study time period. Consistency between self-reported pest treatments, concentrations in dust, and pesticides in products lends credibility to the exposure assessment methods and suggests that differential recall by case-control status is minimal.

Early Pregnancy Agricultural Pesticide Exposures and Risk of Gastroschisis among Offspring in the San Joaquin Valley of California

PubMed Central

Shaw, Gary M.; Yang, Wei; Roberts, Eric; Kegley, Susan E.; Padula, Amy; English, Paul B.; Carmichael, Suzan L.

2017-01-01

Background Prevalence of gastroschisis has inexplicably been increasing over the past few decades. Our intent was to explore whether early gestational exposures to pesticides were associated with risk of gastroschisis. Methods We used population-based data, accompanied by detailed information from maternal interviews as well as information on residential proximity to a large number of commercial pesticide applications during early pregnancy. The study population derived from the San Joaquin Valley of California (1997–2006). Cases were 156 infants/fetuses with gastroschisis and controls were 785 infants without birth defects. Results Among 22 chemical pesticide groups analyzed, none had an elevated odds ratio with an associated confidence interval that excluded 1.0, although exposure to the triazine group showed borderline significance. Among 36 specific pesticide chemicals analyzed, only exposure to petroleum distillates was associated with an elevated risk, odds ratio = 2.5 (1.1–5.6). In general, a substantially different inference was not derived when analyses were stratified by maternal age or when risk estimation included adjustment for race/ethnicity, body mass index, folic acid supplement use, and smoking. Conclusion Our study rigorously adds to the scant literature on this topic. Our a priori expectation was that we would observe certain pesticide compounds to be particularly associated with young age owing to the disproportionate risk observed for young women to have offspring with gastroschisis. We did not observe an exposure profile unique to young women. PMID:24910073

Multiresidue determination of 114 multiclass pesticides in flue-cured tobacco by solid-phase extraction coupled with gas chromatography and tandem mass spectrometry.

PubMed

Cao, Jianmin; Sun, Na; Yu, Weisong; Pang, Xueli; Lin, Yingnan; Kong, Fanyu; Qiu, Jun

2016-12-01

A sensitive and robust multiresidue method for the simultaneous analysis of 114 pesticides in tobacco was developed based on solid-phase extraction coupled with gas chromatography and tandem mass spectrometry. In this strategy, tobacco samples were extracted with acetonitrile and cleaned up with a multilayer solid-phase extraction cartridge Cleanert TPT using acetonitrile/toluene (3:1) as the elution solvent. Two internal standards of different polarity were used to meet simultaneous pesticides quantification demands in the tobacco matrix. Satisfactory linearity in the range of 10-500 ng/mL was obtained for all 114 pesticides with linear regression coefficients higher than 0.994. The limit of detection and limit of quantification values were 0.02-5.27 and 0.06-17.6 ng/g, respectively. For most of the pesticides, acceptable recoveries in the range of 70-120% and repeatabilities (relative standard deviation) of <11% were achieved at spiking levels of 20, 100, and 400 ng/g. Compared with the reported multiresidue analytical method, the proposed method provided a cleaner test solution with smaller amounts of pigments, fatty acids as well as other undesirable interferences. The development and validation of the high sensitivity, high selectivity, easy automation, and high-throughput analytical method meant that it could be successfully used for the determination of pesticides in tobacco samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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. Copyright © 2016 Elsevier Ltd. All rights reserved.

Honey constituents up-regulate detoxification and immunity genes in the western honey bee Apis mellifera.

PubMed

Mao, Wenfu; Schuler, Mary A; Berenbaum, May R

2013-05-28

As a managed pollinator, the honey bee Apis mellifera is critical to the American agricultural enterprise. Recent colony losses have thus raised concerns; possible explanations for bee decline include nutritional deficiencies and exposures to pesticides and pathogens. We determined that constituents found in honey, including p-coumaric acid, pinocembrin, and pinobanksin 5-methyl ether, specifically induce detoxification genes. These inducers are primarily found not in nectar but in pollen in the case of p-coumaric acid (a monomer of sporopollenin, the principal constituent of pollen cell walls) and propolis, a resinous material gathered and processed by bees to line wax cells. RNA-seq analysis (massively parallel RNA sequencing) revealed that p-coumaric acid specifically up-regulates all classes of detoxification genes as well as select antimicrobial peptide genes. This up-regulation has functional significance in that that adding p-coumaric acid to a diet of sucrose increases midgut metabolism of coumaphos, a widely used in-hive acaricide, by ∼60%. As a major component of pollen grains, p-coumaric acid is ubiquitous in the natural diet of honey bees and may function as a nutraceutical regulating immune and detoxification processes. The widespread apicultural use of honey substitutes, including high-fructose corn syrup, may thus compromise the ability of honey bees to cope with pesticides and pathogens and contribute to colony losses.

Honey constituents up-regulate detoxification and immunity genes in the western honey bee Apis mellifera

PubMed Central

Mao, Wenfu; Schuler, Mary A.; Berenbaum, May R.

2013-01-01

As a managed pollinator, the honey bee Apis mellifera is critical to the American agricultural enterprise. Recent colony losses have thus raised concerns; possible explanations for bee decline include nutritional deficiencies and exposures to pesticides and pathogens. We determined that constituents found in honey, including p-coumaric acid, pinocembrin, and pinobanksin 5-methyl ether, specifically induce detoxification genes. These inducers are primarily found not in nectar but in pollen in the case of p-coumaric acid (a monomer of sporopollenin, the principal constituent of pollen cell walls) and propolis, a resinous material gathered and processed by bees to line wax cells. RNA-seq analysis (massively parallel RNA sequencing) revealed that p-coumaric acid specifically up-regulates all classes of detoxification genes as well as select antimicrobial peptide genes. This up-regulation has functional significance in that that adding p-coumaric acid to a diet of sucrose increases midgut metabolism of coumaphos, a widely used in-hive acaricide, by ∼60%. As a major component of pollen grains, p-coumaric acid is ubiquitous in the natural diet of honey bees and may function as a nutraceutical regulating immune and detoxification processes. The widespread apicultural use of honey substitutes, including high-fructose corn syrup, may thus compromise the ability of honey bees to cope with pesticides and pathogens and contribute to colony losses. PMID:23630255

A multi-residue method for characterization and determination of atmospheric pesticides measured at two French urban and rural sampling sites.

PubMed

Baraud, Laurent; Tessier, Didier; Aaron, Jean-Jacques; Quisefit, Jean-Paul; Pinart, Johann

2003-12-01

The extensive use of pesticides to protect agricultural crops can result in the transfer of these compounds into the atmosphere and their diffusion towards urban areas. Precise evaluation of the geographic impact of this type of pollution is important environmentally. In this paper, analytical methods for the sampling, characterization, and determination of agricultural pesticides in air were developed; the methods were then applied in the Paris and Champagne regions. Sixteen pesticides belonging to nine chemical families were monitored. Sampling was carried out in urban (Paris) and rural (Aube district) sites, utilizing either a high-volume pump (12.5 m3 h(-1)) (urban site) or a low-volume pump (2.3 m3 h(-1)) for the rural site. Quartz filters and polyurethane foams (PUF) were used for sampling in all cases. After extracting the samples and concentrating the recovered solutions, high-performance liquid chromatography (HPLC) analysis with UV detection was performed. Identification of the pesticides was confirmed by applying to the HPLC measurements a novel UV-detection procedure based on the normalized absorbance variation with wavelength (Noravawa procedure). The presence of metsulfuron methyl, isoproturon, linuron, deltamethrin (and/or malathion), and chlorophenoxy acids (2,4-D and MCPP) was found at the urban sampling site at levels ranging from about 1 to 1130 ng m(-3) of air, depending on the compound and sampling period. On the rural sampling site residues of isoproturon, deltamethrin (and/or malathion), MCPP, and 2,4-D were generally detected at higher levels (19-5130 ng m(-3)) than on the urban site, as expected. The effects of the weather conditions and agricultural activity on the atmospheric concentrations of pesticides are discussed, as are long-range atmospheric transfer processes for these pesticides.

Spatial and temporal trends and flow dynamics of glyphosate and other pesticides within an agricultural watershed in Argentina.

PubMed

Pérez, Débora J; Okada, Elena; De Gerónimo, Eduardo; Menone, Mirta L; Aparicio, Virginia C; Costa, José L

2017-12-01

In the present study, we evaluated the spatial and temporal trends of current-use pesticides in surface water and sediments as well as their relationship with hydrological stream dynamics within the agricultural watershed of El Crespo stream (Buenos Aires Province, Argentina). We sampled 2 contrasting sites: site 1 (upstream), surrounded by agricultural lands, and site 2 (downstream), surrounded by natural grasslands. Most of the applied pesticides (glyphosate, 2,4-D, atrazine, tebuconazole, and imidacloprid) were detected at high frequencies in surface water samples at both sites. However, only glyphosate and aminomethylphosphonic acid (AMPA) were present at high concentrations and had a significant spatial-temporal trend. The highest concentrations were found during spring 2014 at site 1, in association with the intense rains that occurred in that season. The fact that glyphosate and AMPA concentrations were higher than the rest of the studied compounds is closely related to the land use within the watershed, as glyphosate was the most applied herbicide during the fallow period of glyphosate-resistant crops (soybean, maize). The pesticide mixture had a significant spatial-temporal trend, reaching the highest levels during storm flow events in spring 2014. The intensive rains in spring 2014 could be the main factor influencing stream hydrology and pesticide behavior at El Crespo watershed. The estimated annual pesticide losses were 3.11 g/ha at site 1 and 0.72 g/ha at site 2. This result indicates that an attenuation process could be decreasing pesticide loads during downstream transport from site 1 to site 2. Environ Toxicol Chem 2017;36:3206-3216. © 2017 SETAC. © 2017 SETAC.

Use of ammonium formate in QuEChERS for high-throughput analysis of pesticides in food by fast, low-pressure gas chromatography and liquid chromatography tandem mass spectrometry.

PubMed

González-Curbelo, Miguel Ángel; Lehotay, Steven J; Hernández-Borges, Javier; Rodríguez-Delgado, Miguel Ángel

2014-09-05

The "quick, easy, cheap, effective, rugged, and safe" (QuEChERS) approach to sample preparation is widely applied in pesticide residue analysis, but the use of magnesium sulfate and other nonvolatile compounds for salting out in the method is not ideal for mass spectrometry. In this study, we developed and evaluated three new different versions of the QuEChERS method using more volatile salts (ammonium chloride and ammonium formate and acetate buffers) to induce phase separation and extraction of 43 representative pesticide analytes of different classes. Fast low-pressure gas chromatography tandem mass spectrometry (LPGC-MS/MS) and liquid chromatography (LC)-MS/MS were used for analysis. The QuEChERS AOAC Official Method 2007.01 was also tested for comparison purposes. Of the studied methods, formate buffering using 7.5g of ammonium formate and 15mL of 5% (v/v) formic acid in acetonitrile for the extraction of 15g of sample (5g for wheat grain) provided the best performance and practical considerations. Method validation was carried out with and without the use of dispersive solid-phase extraction for cleanup, and no significant differences were observed for the majority of pesticides. The method was demonstrated in quantitative analysis for GC- and LC-amenable pesticides in 4 representative food matrices (apple, lemon, lettuce, and wheat grain). With the typical exceptions of certain pH-dependent and labile pesticides, 90-110% recoveries and <10% RSD were obtained. Detection limits were mostly <5ng/g, which met the general need to determine pesticide concentrations as low as 10ng/g for monitoring purposes in food applications. Published by Elsevier B.V.

[Analysis on influencing factors of prognosis of patients with acute organophosphorus pesticide poisoning].

PubMed

Guo, C F; Wang, Y; Liu, J H; Shen, P; Wang, H; Wei, Y J; Shi, X F; Zhou, X J; Wang, W W

2016-05-20

To analyze the relationship between risk factors and prognosis of acute organophosphorus pesticide poisoning (AOPP). The clinical data including APACHEⅡ, D-dimer, C-reactive protein, procalcitonin, lactic acid of the 67 cases of acute organophosphorus pesticide poisoning which respectively divided into survival group and death group by the outcome were collected. The independent influcing factors were got by logistic regression analysis. The analysis showed that APACHEⅡ, D-dimer、C-reactive protein and Procalcitonin were influencing factors to evaluate prognosis of AOPP (P<0.05) .Meanwhile, APACHEⅡ and CRP were the independent influencing factors to evaluate prognosis of AOPP (P<0.05). APACHEⅡ26was the optimum thresholds to acess the prognosis of AOPP and its Youden index was largest. APACHEⅡ and CRP played an important role in the assessment of prognosis on AOPP. When APACHEⅡwas more than 26, it suggested the patient of AOPP will have a bad prognosis.

Acephate affects migratory orientation of the white-throated sparrow (Zonotrichia albicollis)

USGS Publications Warehouse

Vyas, N.B.; Kuenzel, W.J.; Hill, E.F.; Sauer, J.R.

1995-01-01

Migratory white-throated sparrows (Zonotrichia albicollis) were exposed to acephate (acetylphosphoramidothioic acid O,S-dimethyl ester), an organophosphorus pesticide, to determine its effects on migratory orientation and behavior. Birds were also exposed to polarizer sheets to determine the mechanism by which acephate may affect migratory orientation. Adult birds exposed to 256 ppm acephate a.i. were not able to establish a preferred migratory orientation and exhibited random activity. All juvenile treatment groups displayed a seasonally correct southward migratory orientation. We hypothesize that acephate may have produced aberrant migratory behavior by affecting the memory of the migratory route and wintering ground. This experiment reveals that an environmentally relevant concentration of a common organophosphorus pesticide can alter migratory orientation, but its effect is markedly different between adult and juvenile sparrows. Results suggest that the survival of free-flying adult passerine migrants may be compromised following organophosphorus pesticide exposure.

Ecotoxicological effects of carbofuran and oxidised multiwalled carbon nanotubes on the freshwater fish Nile tilapia: nanotubes enhance pesticide ecotoxicity.

PubMed

Campos-Garcia, Janaína; Martinez, Diego Stéfani T; Alves, Oswaldo L; Leonardo, Antônio Fernando Gervásio; Barbieri, Edison

2015-01-01

The interactions of carbon nanotubes with pesticides, such as carbofuran, classical contaminants (e.g., pesticides, polyaromatic hydrocarbons, heavy metals, and dyes) and emerging contaminants, including endocrine disruptors, are critical components of the environmental risks of this important class of carbon-based nanomaterials. In this work, we studied the modulation of acute carbofuran toxicity to the freshwater fish Nile tilapia (Oreochromis niloticus) by nitric acid treated multiwalled carbon nanotubes, termed HNO3-MWCNT. Nitric acid oxidation is a common chemical method employed for the purification, functionalisation and aqueous dispersion of carbon nanotubes. HNO3-MWCNT were not toxic to Nile tilapia at concentrations ranging from 0.1 to 3.0 mg/L for exposure times of up to 96 h. After 24, 48, 72 and 96 h, the LC50 values of carbofuran were 4.0, 3.2, 3.0 and 2.4 mg/mL, respectively. To evaluate the influence of carbofuran-nanotube interactions on ecotoxicity, we exposed the Nile tilapia to different concentrations of carbofuran mixed together with a non-toxic concentration of HNO3-MWCNT (1.0 mg/L). After 24, 48, 72, and 96 h of exposure, the LC50 values of carbofuran plus nanotubes were 3.7, 1.6, 0.7 and 0.5 mg/L, respectively. These results demonstrate that HNO3-MWCNT potentiate the acute toxicity of carbofuran, leading to a more than five-fold increase in the LC50 values. Furthermore, the exposure of Nile tilapia to carbofuran plus nanotubes led to decreases in both oxygen consumption and swimming capacity compared to the control. These findings indicate that carbon nanotubes could act as pesticide carriers affecting fish survival, metabolism and behaviour. Copyright © 2014 Elsevier Inc. All rights reserved.

Acetonitrile extraction and dual-layer solid phase extraction clean-up for pesticide residue analysis in propolis.

PubMed

Oellig, Claudia

2016-05-06

Propolis is a very complex mixture of substances that is produced by honey bees and is known to be a rather challenging matrix for residue analysis. Besides resins, flavonoids and phenols, high amount of wax is co-extracted resulting in immense matrix effects. Therefore a suitable clean-up is crucial and indispensable. In this study, a reliable solid phase extraction (SPE) clean-up was developed for pesticide residue analysis in propolis. The clean-up success was quickly and easily monitored by high-performance thin-layer chromatography with different detection possibilities. The final method consists of the extraction of propolis with acetonitrile according to the QuEChERS method followed by an effective extract purification on dual-layer SPE cartridges with spherical hydrophobic polystyrene-divinylbenzene resin/primary secondary amine as sorbent and a mixture of toluene/acetone (95:5, v/v) for elution. Besides fat-soluble components like waxes, flavonoids, and terpenoids, more polar compounds like organic acids, fatty acids, sugars and anthocyanins were also removed to large extent. Method performance was assessed by recovery experiments at spiking levels of 0.5 and 1mg/kg (n=5) for fourteen pesticides that are relevant for propolis. Mean recoveries determined by HPLC-MS against solvent standards were between 40 and 101%, while calculation against matrix-matched standards provided recoveries of 79-104%. Precision of recovery, assessed by relative standard deviations, were below 9%. Thus, the developed dual-layer SPE clean-up enables the reliable pesticide residue analysis in propolis and provides a suitable alternative to time-consuming clean-up procedures proposed in literature. Copyright © 2016 Elsevier B.V. All rights reserved.

Multi-residue method for the determination of pesticides and pesticide metabolites in honeybees by liquid and gas chromatography coupled with tandem mass spectrometry--Honeybee poisoning incidents.

PubMed

Kiljanek, Tomasz; Niewiadowska, Alicja; Semeniuk, Stanisław; Gaweł, Marta; Borzęcka, Milena; Posyniak, Andrzej

2016-02-26

A method for the determination of 200 pesticides and pesticide metabolites in honeybee samples has been developed and validated. Almost 98% of compounds included in this method are approved to use within European Union, as active substances of plant protection products or veterinary medicinal products used by beekeepers to control mites Varroa destructor in hives. Many significant metabolites, like metabolites of imidacloprid, thiacloprid, fipronil, methiocarb and amitraz, are also possible to detect. The sample preparation was based on the buffered QuEChERS method. Samples of bees were extracted with acetonitrile containing 1% acetic acid and then subjected to clean-up by dispersive solid phase extraction (dSPE) using a new Z-Sep+ sorbent and PSA. The majority of pesticides, including neonicotionoids and their metabolites, were analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS) but some of pesticides, especially pyrethroid insecticides, were analyzed by gas chromatography tandem mass spectrometry (GC-MS/MS). The procedure was validated according to the Guidance document SANCO/12571/2013 at four concentration levels: 1, 5, 10 and 100 ng/g bees and verified in the international proficiency test. The analysis of bee samples spiked at the limit of quantification (LOQ) showed about 98% mean recovery value (trueness) and 97% of analytes showed recovery in the required range of 70-120% and RSDr (precision) below 20%. Linearity and matrix effects were also established. The LOQs of pesticides were in the range of 1-100 ng/g. The developed method allows determination of insecticides at concentrations of 10 ng/g or less, except abamectin and tebufenozide. LOQ values are lower than the median lethal doses LD50 for bees. The method was used to investigate more than 70 honeybee poisoning incidents. Data about detected pesticides and their metabolites are included. Copyright © 2016 Elsevier B.V. All rights reserved.

[Determination of eight pesticide residues in tea by liquid chromatography-tandem mass spectrometry and its uncertainty evaluation].

PubMed

Hu, Beizhen; Cai, Haijiang; Song, Weihua

2012-09-01

A method was developed for the determination of eight pesticide residues (fipronil, imidacloprid, acetamiprid, buprofezin, triadimefon, triadimenol, profenofos, pyridaben) in tea by liquid chromatography-tandem mass spectrometry. The sample was extracted by accelerated solvent extraction with acetone-dichloromethane (1:1, v/v) as solvent, and the extract was then cleaned-up with a Carb/NH2 solid phase extraction (SPE) column. The separation was performed on a Hypersil Gold C, column (150 mm x 2. 1 mm, 5 microm) and with the gradient elution of acetonitrile and 0. 1% formic acid. The eight pesticides were determined in the modes of electrospray ionization (ESI) and multiple reaction monitoring (MRM). The analytes were quantified by matrix-matched internal standard method for imidacloprid and acetamiprid, by matrix-matched external standard method for the other pesticides. The calibration curves showed good linearity in 1 - 100 microg/L for fipronil, and in 5 -200 microg/L for the other pesticides. The limits of quantification (LOQs, S/N> 10) were 2 p.g/kg for fipronil and 10 microg/kg for the other pesticides. The average recoveries ranged from 75. 5% to 115.0% with the relative standard deviations of 2.7% - 7.7% at the spiked levels of 2, 5, 50 microg/kg for fipronil and 10, 50, 100 microg/kg for the other pesticides. The uncertainty evaluation for the results was carried out according to JJF 1059-1999 "Evaluation and Expression of Uncertainty in Measurement". Items constituting measurement uncertainty involved standard solution, weighing of sample, sample pre-treatment, and the measurement repeatability of the equipment were evaluated. The results showed that the measurement uncertainty is mainly due to sample pre-treatment, standard curves and measurement repeatability of the equipment. The method developed is suitable for the conformation and quantification of the pesticides in tea.

Efficiency control of dietary pesticide intake reduction by human biomonitoring.

PubMed

Göen, Thomas; Schmidt, Lukas; Lichtensteiger, Walter; Schlumpf, Margret

2017-03-01

In spite of food safety controls for pesticide residues, a conventional diet still leads to a noticeable exposure of the general population to several pesticides. In a pilot study the response of exposure reduction by organic diet intervention on the urinary levels of pesticide metabolites was investigated. In the study two adult individuals were kept on a conventional diet for 11days and morning urine voids were collected at the last four days of the period. Afterwards, the participants switched to exclusively organic food intake for 18days and likewise morning urine samples were collected at the last four days of this period. In the urine samples six pyrethroid metabolites, six dialkylphosphates, four phenolic parameter for organophosphate pesticides and carbamates, 6-chloronicotinic acid (ClNA) as parameter for neonicotinoid insecticides, seven phenoxy herbicides, glyphosate and its metabolite AMPA were quantified using gas chromatographic mass spectrometric methods. Generally, the comparative analyses revealed greater shares as well as higher levels of the parameters in the samples taken during the common diet period compared to the organic diet period. Considerable decrease of the levels was found for almost all pyrethroid metabolites, dialkyphosphates and phenoxy herbicids, as well as for the phenolic metabolites 4-nitrophenol and 3,5,6-trichloropyridinol. In contrast, higher values were found for the organic diet period for ClNA and the metabolite of coumaphos in one of the volunteers. The present study confirms the results of former studies which indicated that an organic diet intervention results in considerable lower exposure to organophosphate pesticides and pyrethroids. It also verifies the former experience that monitoring of urinary parameters for non-persistent pesticides permits a reliable efficiency control of short-time effects by dietary interventions. Additionally to former studies, the results of the present study highlight the need of an extension of the parameter spectrum to all prominent pesticide groups. Copyright © 2016 Elsevier GmbH. All rights reserved.

Effects of dietary exposure to herbicide and of the nutritive quality of contaminated food on the reproductive output of Daphnia magna.

PubMed

Bessa da Silva, M; Abrantes, N; Rocha-Santos, T A P; Duarte, A C; Freitas, A C; Gomes, A M; Carvalho, A P; Marques, J C; Gonçalves, F; Pereira, R

2016-10-01

Risk assessment of pesticides has been based on direct toxic effects on aquatic organisms. Indirect effects data are taken into account but with limitations, as it is frequently difficult to predict their real impacts in the ecosystems. In this context the main aim of this work was to assess how the exposure to the herbicide pendimethalin (Prowl(®)), under environmentally relevant concentrations, may compromise the nutritional composition of food for a relevant group of primary consumers of freshwater food webs-the daphnids, thus affecting their reproduction performance and subsequently the long-term sustainability of active populations of this grazer. Therefore, Daphnia magna individuals were chronically exposed in a clean medium to a control diet (NCF - i.e., non-contaminated green algae Raphidocelis subcapitata) and to a contaminated diet (CF - i.e., the same monoalgal culture grown in a medium enriched with pendimethalin in a concentration equivalent to the EC20 for growth inhibition of algae), during which reproductive endpoints were assessed. The algae were analysed for protein, carbohydrate and fatty acid content. The chemical composition of R. subcapitata in the CF revealed a slight decrease on total fatty acid levels, with a particular decrease of essential ω9 monounsaturated fatty acids. In contrast, the protein content was high in the CF. D. magna exposed to CF experienced a 16% reduction in reproduction, measured as the total number of offspring produced per female. Additionally, an internal pendimethalin body burden of 4.226μgg(-1) was accumulated by daphnids fed with CF. Hence, although it is difficult to discriminate the contribution of the pesticide (as a toxic agent transferred through the food web) from that of the food with a poor quality-compromised by the same pesticide, there are no doubts that, under environmentally relevant concentrations of pesticides, both pathways may compromise the populations of freshwater grazers in the long term, with consequences in the control of the primary productivity of these systems. Copyright © 2016 Elsevier B.V. All rights reserved.

EFFECTS OF DEVELOPMENTAL EXPOSURE TO HEPTACHLOR ON THE CHOLINERGIC SYSTEM IN RATS.

EPA Science Inventory

Heptachlor is an environmentally persistent cyclodiene pesticide which is a known antagonist of the -aminobutyric acid (GABA)A receptor. Since GABA is a trophic factor for the development of other neurotransmitter systems (Lauder et al., Perspectives in Developmental Neurobiolog...

Hypospadias and residential proximity to pesticide applications.

PubMed

Carmichael, Suzan L; Yang, Wei; Roberts, Eric M; Kegley, Susan E; Wolff, Craig; Guo, Liang; Lammer, Edward J; English, Paul; Shaw, Gary M

2013-11-01

Experimental evidence suggests pesticides may be associated with hypospadias. Examine the association of hypospadias with residential proximity to commercial agricultural pesticide applications. The study population included male infants born from 1991 to 2004 to mothers residing in 8 California counties. Cases (n = 690) were ascertained by the California Birth Defects Monitoring Program; controls were selected randomly from the birth population (n = 2195). We determined early pregnancy exposure to pesticide applications within a 500-m radius of mother's residential address, using detailed data on applications and land use. Associations with exposures to physicochemical groups of pesticides and specific chemicals were assessed using logistic regression adjusted for maternal race or ethnicity and age and infant birth year. Forty-one percent of cases and controls were classified as exposed to 57 chemical groups and 292 chemicals. Despite >500 statistical comparisons, there were few elevated odds ratios with confidence intervals that excluded 1 for chemical groups or specific chemicals. Those that did were for monochlorophenoxy acid or ester herbicides; the insecticides aldicarb, dimethoate, phorate, and petroleum oils; and adjuvant polyoxyethylene sorbitol among all cases; 2,6-dinitroaniline herbicides, the herbicide oxyfluorfen, and the fungicide copper sulfate among mild cases; and chloroacetanilide herbicides, polyalkyloxy compounds used as adjuvants, the insecticides aldicarb and acephate, and the adjuvant nonyl-phenoxy-poly(ethylene oxy)ethanol among moderate and severe cases. Odds ratios ranged from 1.9 to 2.9. Most pesticides were not associated with elevated hypospadias risk. For the few that were associated, results should be interpreted with caution until replicated in other study populations.

Hypospadias and Residential Proximity to Pesticide Applications

PubMed Central

Yang, Wei; Roberts, Eric M.; Kegley, Susan E.; Wolff, Craig; Guo, Liang; Lammer, Edward J.; English, Paul; Shaw, Gary M.

2013-01-01

BACKGROUND: Experimental evidence suggests pesticides may be associated with hypospadias. OBJECTIVE: Examine the association of hypospadias with residential proximity to commercial agricultural pesticide applications. METHODS: The study population included male infants born from 1991 to 2004 to mothers residing in 8 California counties. Cases (n = 690) were ascertained by the California Birth Defects Monitoring Program; controls were selected randomly from the birth population (n = 2195). We determined early pregnancy exposure to pesticide applications within a 500-m radius of mother’s residential address, using detailed data on applications and land use. Associations with exposures to physicochemical groups of pesticides and specific chemicals were assessed using logistic regression adjusted for maternal race or ethnicity and age and infant birth year. RESULTS: Forty-one percent of cases and controls were classified as exposed to 57 chemical groups and 292 chemicals. Despite >500 statistical comparisons, there were few elevated odds ratios with confidence intervals that excluded 1 for chemical groups or specific chemicals. Those that did were for monochlorophenoxy acid or ester herbicides; the insecticides aldicarb, dimethoate, phorate, and petroleum oils; and adjuvant polyoxyethylene sorbitol among all cases; 2,6-dinitroaniline herbicides, the herbicide oxyfluorfen, and the fungicide copper sulfate among mild cases; and chloroacetanilide herbicides, polyalkyloxy compounds used as adjuvants, the insecticides aldicarb and acephate, and the adjuvant nonyl-phenoxy-poly(ethylene oxy)ethanol among moderate and severe cases. Odds ratios ranged from 1.9 to 2.9. CONCLUSIONS: Most pesticides were not associated with elevated hypospadias risk. For the few that were associated, results should be interpreted with caution until replicated in other study populations. PMID:24167181

Impact of non-functionalized and amino-functionalized multiwall carbon nanotubes on pesticide uptake by lettuce (Lactuca sativa L.).

PubMed

Hamdi, Helmi; De La Torre-Roche, Roberto; Hawthorne, Joseph; White, Jason C

2015-03-01

The effect of non-functionalized and amino-functionalized multiwall carbon nanotube (CNT) exposure, as well as the impact of CNT presence on coexistent pesticide accumulation, was investigated in lettuce (Lactuca sativa L.). Lettuce seeds were sown directly into CNT-amended vermiculite (1000 mg L(-1)) to monitor phytotoxicity during germination and growth. During growth, lettuce seedlings were subsequently exposed to chlordane (cis-chlordane [CS], trans-chlordane [TC] and trans-nonachlor [TN]) and p,p'-DDE (all at 100 ng/L) in the irrigation solution for a 19-d growth period. CNT exposure did not significantly influence seed germination (82-96%) or plant growth. Similarly, pesticide exposure had no impact on plant growth, total pigment production or tissue lipid peroxidation. After 19 d, the root content of total chlordane and p,p'-DDE was 390 and 73.8 µg g(-1), respectively; in plants not exposed to CNTs, the shoot levels were 1.58 and 0.40 µg g(-1), respectively. The presence and type of CNT significantly influenced pesticide availability to lettuce seedlings. Non-functionalized CNT decreased the root and shoot pesticide content by 88% and 78%, respectively, but amino-functionalized CNT effects were significantly more modest, with decreases of 57% in the roots and 23% in the shoots, respectively. The presence of humic acid completely reversed the reduced accumulation of pesticides induced by amino-functionalized CNT, likely due to strong competition over adsorption sites on the nanomaterial (NM). These findings have implications for food safety and for the use of engineered NMs in agriculture, especially with leafy vegetables.

Sorption of selected pesticides on soils, sediment and straw from a constructed agricultural drainage ditch or pond.

PubMed

Vallée, Romain; Dousset, Sylvie; Billet, David; Benoit, Marc

2014-04-01

Buffer zones such as ponds and ditches are used to reduce field-scale losses of pesticides from subsurface drainage waters to surface waters. The objective of this study was to assess the efficiency of these buffer zones, in particular constructed wetlands, focusing specifically on sorption processes. We modelled the sorption processes of three herbicides [2-methyl-4-chlorophenoxyacetic acid (2,4-MCPA), isoproturon and napropamide] and three fungicides (boscalid, prochloraz and tebuconazole) on four substrates (two soils, sediment and straw) commonly found in a pond and ditch in Lorraine (France). A wide range of Freundlich coefficient (K fads) values was obtained, from 0.74 to 442.63 mg(1 - n) L (n) kg(-1), and the corresponding K foc values ranged from 56 to 3,725 mg(1 - n) L (n) kg(-1). Based on potential retention, the substrates may be classified as straw > sediments > soils. These results show the importance of organic carbon content and nature in the process of sorption. Similarly, the studied pesticides could be classified according to their adsorption capacity as follows: prochloraz > tebuconazole-boscalid > napropamide > MCPA-isoproturon. This classification is strongly influenced by the physico-chemical properties of pesticides, especially solubility and K oc. Straw exhibited the largest quantity of non-desorbable pesticide residues, from 12.1 to 224.2 mg/L for all pesticides. The presence of plants could increase soil-sediment sorption capacity. Thus, establishment and maintenance of plants and straw filters should be promoted to optimise sorption processes and the efficiency of ponds and ditches in reducing surface water pollution.

The in vitro effects of some pesticides on carbonic anhydrase activity of Oncorhynchus mykiss and Cyprinus carpio carpio fish.

PubMed

Doğan, Serap

2006-05-20

Systemic carbonic anhydrase (CA) inhibitors are among the most powerful agents to lower intraocular pressure. Unfortunately, their use is frequently accompanied by undesired side effects. Some are due to the relatively large amounts of drug that have to be systematically administered to inhibit the CA in the ciliary processes. The aim of the present work was to study in vitro effects of some pesticides on CA enzyme obtained from blood of fish, which play a key role in salt- and osmoregulation and acid-base balance in the fish, Oncorhynchus mykiss and Cyprinus carpio carpio living in freshwaters, and compared with CA inhibitors. CA activities were significantly inhibited by pesticides and inhibitors. I(50) values of O. mykiss CA enzyme inhibited by lambda-cyhalothrin, deltametrin, diozinon, dorzolamide and brinzolamide were 6.05 x 10(-4), 1.48 x 10(-5), 6.84 x 10(-3), 3.82 x 10(-5) and 1.80 x 10(-6) mol/l, and that for C. c. carpio 6.86 x 10(-4), 4.70 x 10(-4), 3.92 x 10(-3), 8.34 x 10(-6) and 1.42 x 10(-6) mol/l, respectively. The pesticides used in this study inhibited the CA activity from different fish species to various degrees. It was found that the most effective inhibitor of CA enzyme within pesticides used was detrametrin. These findings observed in vitro could be useful in the understanding of the toxic effects that pesticides elicit on aquatic organisms in vivo.

Essential oil from Eupatorium buniifolium leaves as potential varroacide.

PubMed

Umpiérrez, María Laura; Santos, Estela; Mendoza, Yamandú; Altesor, Paula; Rossini, Carmen

2013-10-01

Beekeeping has experienced a great expansion worldwide. Nowadays, several conventional pesticides, some organic acids, and essential oil components are the main means of chemical control used against Varroa destructor, an ectoparasite that may contribute to the colony collapse disorders. Varroa resistance against conventional pesticides has already been reported; therefore it is imperative to look for alternative control agents to be included in integrated pest management programs. A good alternative seems to be the use of plant essential oils (EOs) which, as natural products, are less toxic and leave fewer residues. Within this context, a bioprospecting program of the local flora searching for botanical pesticides to be used as varroacides was launched. A primary screening (driven by laboratory assays testing for anti-Varroa activity, and safety to bees) led us to select the EOs from Eupatorium buniifolium (Asteraceae) for follow up studies. We have chemical characterized EOs from twigs and leaves collected at different times. The three E. buniifolium EOs tested were active against Varroa in laboratory assays; however, there are differences that might be attributable to chemical differences also found. The foliage EO was selected for a preliminary field trial (on an experimental apiary with 40 hives) that demonstrated acaricidal activity when applied to the hives. Although activity was less than that for oxalic acid (the positive control), this EO was less toxic to bees than the control, encouraging further studies.

Field solar degradation of pesticides and emerging water contaminants mediated by polymer films containing titanium and iron oxide with synergistic heterogeneous photocatalytic activity at neutral pH.

PubMed

Mazille, F; Schoettl, T; Klamerth, N; Malato, S; Pulgarin, C

2010-05-01

Photocatalytic degradation of phenol, nalidixic acid, mixture of pesticides, and another of emerging contaminants in water was mediated by TiO(2) and iron oxide immobilized on functionalized polyvinyl fluoride films (PVF(f)-TiO(2)-Fe oxide) in a compound parabolic collector (CPC) solar photoreactor. During degradation, little iron leaching (<0.2mgL(-1)) was observed. Phenol was efficiently degraded and mineralized at operational pH<5 and nalidixic acid degradation was complete even at pH 7, but mineralization stopped at 35%. Pesticide mixture was slowly degraded (50%) after 150min of irradiation. Degradation of the emergent contaminant mixture was successful for eight compounds and less efficient for six other compounds. The significant reactivity differences between tested compounds were assigned to the differences in structure namely that the presence of complexing or chelating groups enhanced the rates. PVF(f)-TiO(2)-Fe oxide photoactivity gradually increased during 20 days of experiments. X-ray photoelectron spectroscopy (XPS) measurements revealed significant changes on the catalyst surface. These analyses confirm that during photocatalysis mediated by PVF(f)-TiO(2)-Fe oxide, some iron leaching led to enlargement of the TiO(2) surface exposed to light, increasing its synergy with iron oxides and leading to enhanced pollutant degradation.

Chemometric-assisted QuEChERS extraction method for post-harvest pesticide determination in fruits and vegetables

NASA Astrophysics Data System (ADS)

Li, Minmin; Dai, Chao; Wang, Fengzhong; Kong, Zhiqiang; He, Yan; Huang, Ya Tao; Fan, Bei

2017-02-01

An effective analysis method was developed based on a chemometric tool for the simultaneous quantification of five different post-harvest pesticides (2,4-dichlorophenoxyacetic acid (2,4-D), carbendazim, thiabendazole, iprodione, and prochloraz) in fruits and vegetables. In the modified QuEChERS (quick, easy, cheap, effective, rugged and safe) method, the factors and responses for optimization of the extraction and cleanup analyses were compared using the Plackett-Burman (P-B) screening design. Furthermore, the significant factors (toluene percentage, hydrochloric acid (HCl) percentage, and graphitized carbon black (GCB) amount) were optimized using a central composite design (CCD) combined with Derringer’s desirability function (DF). The limits of quantification (LOQs) were estimated to be 1.0 μg/kg for 2,4-D, carbendazim, thiabendazole, and prochloraz, and 1.5 μg/kg for iprodione in food matrices. The mean recoveries were in the range of 70.4-113.9% with relative standard deviations (RSDs) of less than 16.9% at three spiking levels. The measurement uncertainty of the analytical method was determined using the bottom-up approach, which yielded an average value of 7.6%. Carbendazim was most frequently found in real samples analyzed using the developed method. Consequently, the analytical method can serve as an advantageous and rapid tool for determination of five preservative pesticides in fruits and vegetables.

Growth promotion of peanut (Arachis hypogaea L.) and maize (Zea mays L.) plants by single and mixed cultures of efficient phosphate solubilizing bacteria that are tolerant to abiotic stress and pesticides.

PubMed

Anzuay, María Soledad; Ciancio, María Gabriela Ruiz; Ludueña, Liliana Mercedes; Angelini, Jorge Guillermo; Barros, Germán; Pastor, Nicolás; Taurian, Tania

2017-06-01

The aims of this study were, to analyze in vitro phosphate solubilization activity of six native peanut bacteria and to determine the effect of single and mixed inoculation of these bacteria on peanut and maize plants. Ability to produce organic acids and cofactor PQQ, to solubilize FePO 4 and AlPO 4 and phosphatase activity were analyzed. Also, the ability to solubilize phosphate under abiotic stress and in the presence of pesticides of the selected bacteria was determined. The effect of single and mixed bacterial inocula was analyzed on seed germination, maize plant growth and in a crop rotation plant assay with peanut and maize. The six strains produced gluconic acid and five released cofactor PQQ into the medium. All bacteria showed ability to solubilize phosphate from FePO 4 and AlPO 4 and phosphatase activity. The ability of the bacteria to solubilize tricalcium phosphate under abiotic stress and in presence of pesticides indicated encouraging results. Bacterial inoculation on peanut and maize increased seed germination, plant́s growth and P content. Phosphate solubilizing bacteria used in this study showed efficient phosphate mineralizing and solubilization ability and would be potential P-biofertilizers for peanut and maize. Copyright © 2017 Elsevier GmbH. All rights reserved.

Chemometric-assisted QuEChERS extraction method for post-harvest pesticide determination in fruits and vegetables

PubMed Central

Li, Minmin; Dai, Chao; Wang, Fengzhong; Kong, Zhiqiang; He, Yan; Huang, Ya Tao; Fan, Bei

2017-01-01

An effective analysis method was developed based on a chemometric tool for the simultaneous quantification of five different post-harvest pesticides (2,4-dichlorophenoxyacetic acid (2,4-D), carbendazim, thiabendazole, iprodione, and prochloraz) in fruits and vegetables. In the modified QuEChERS (quick, easy, cheap, effective, rugged and safe) method, the factors and responses for optimization of the extraction and cleanup analyses were compared using the Plackett–Burman (P–B) screening design. Furthermore, the significant factors (toluene percentage, hydrochloric acid (HCl) percentage, and graphitized carbon black (GCB) amount) were optimized using a central composite design (CCD) combined with Derringer’s desirability function (DF). The limits of quantification (LOQs) were estimated to be 1.0 μg/kg for 2,4-D, carbendazim, thiabendazole, and prochloraz, and 1.5 μg/kg for iprodione in food matrices. The mean recoveries were in the range of 70.4–113.9% with relative standard deviations (RSDs) of less than 16.9% at three spiking levels. The measurement uncertainty of the analytical method was determined using the bottom-up approach, which yielded an average value of 7.6%. Carbendazim was most frequently found in real samples analyzed using the developed method. Consequently, the analytical method can serve as an advantageous and rapid tool for determination of five preservative pesticides in fruits and vegetables. PMID:28225030

Chemometric-assisted QuEChERS extraction method for post-harvest pesticide determination in fruits and vegetables.

PubMed

Li, Minmin; Dai, Chao; Wang, Fengzhong; Kong, Zhiqiang; He, Yan; Huang, Ya Tao; Fan, Bei

2017-02-22

An effective analysis method was developed based on a chemometric tool for the simultaneous quantification of five different post-harvest pesticides (2,4-dichlorophenoxyacetic acid (2,4-D), carbendazim, thiabendazole, iprodione, and prochloraz) in fruits and vegetables. In the modified QuEChERS (quick, easy, cheap, effective, rugged and safe) method, the factors and responses for optimization of the extraction and cleanup analyses were compared using the Plackett-Burman (P-B) screening design. Furthermore, the significant factors (toluene percentage, hydrochloric acid (HCl) percentage, and graphitized carbon black (GCB) amount) were optimized using a central composite design (CCD) combined with Derringer's desirability function (DF). The limits of quantification (LOQs) were estimated to be 1.0 μg/kg for 2,4-D, carbendazim, thiabendazole, and prochloraz, and 1.5 μg/kg for iprodione in food matrices. The mean recoveries were in the range of 70.4-113.9% with relative standard deviations (RSDs) of less than 16.9% at three spiking levels. The measurement uncertainty of the analytical method was determined using the bottom-up approach, which yielded an average value of 7.6%. Carbendazim was most frequently found in real samples analyzed using the developed method. Consequently, the analytical method can serve as an advantageous and rapid tool for determination of five preservative pesticides in fruits and vegetables.

Enantioselective Phytotoxicity and the Relative Mechanism of Current Chiral Herbicides.

PubMed

Wang, Cui; Lu, Dezhao; Yang, Jinhuan; Xu, Yingling; Gong, Chenxue; Li, Zhuoyu

2017-01-01

Regardless of the achievable of chiral switch, most of the chiral nature agrochemical is still sold as racemate or enantiomer-enriched pesticides. Herbicides, accounted for a large proportion in pesticide market, are of great concern due to the frequent occurrence in environment and the structure selective phyto-biochemical impact on plants. We give a systematic search on the literature database and included approximately 50 papers which were related to the review. We do careful categories for the chiral herbicides according to their structure and listed out the acute phytotoxicity endpoints. The potential mechanism for the enantioselective toxicity was concluded into 5 main points. The enantiomer-specific toxicity on plant growth and flowers are limited on phenoxyalkanoic acid herbicide, aryloxyphenoxypropanoic acid, imidazolinone herbicide, and acetamide pesticide. Data available on the potential mechanism explanation of enantioselective phytotoxicity has been concerned on the genetic transcription, oxidative stress, and photosynthesis disruption, etc. A comparison between the two enantiomers' enantioselective effects identified an organ-specific and species-specific phenomenon for several herbicides. Moreover, a more herbicidal activity enantiomer is also displayed the more toxicity than its antipode. The review elucidated a paucity of information on the enantioselective effect research on various types of plants at the different life stages. It appealed us to conduct a more holistic approach to balance the benefit between herbicidal activity and phytotoxicity when try to develop an enantio-pure herbicide.

Layered double hydroxides as adsorbents and carriers of the herbicide (4-chloro-2-methylphenoxy)acetic acid (MCPA): systems Mg-Al, Mg-Fe and Mg-Al-Fe.

PubMed

Bruna, F; Celis, R; Pavlovic, I; Barriga, C; Cornejo, J; Ulibarri, M A

2009-09-15

Hydrotalcite-like compounds [Mg(3)Al(OH)(8)]Cl x 4H(2)O; [Mg(3)Fe(OH)(8)]Cl x 4H(2)O; [Mg(3)Al(0.5)Fe(0.5)(OH)(8)]Cl x 4H(2)O (LDHs) and calcined product of [Mg(3)Al(OH)(8)]Cl x 4H(2)O, Mg(3)AlO(4.5) (HT500), were studied as potential adsorbents of the herbicide MCPA [(4-chloro-2-methylphenoxy)acetic acid] as a function of pH, contact time and pesticide concentration, and also as support for the slow release of this pesticide, with the aim to reduce the hazardous effects that it can pose to the environment. The information obtained in the adsorption study was used for the preparation of LDH-MCPA complexes. The results showed high and rapid adsorption of MCPA on the adsorbents as well as that MCPA formulations based on LDHs and HT500 as pesticide supports displayed controlled release properties and reduced herbicide leaching in soil columns compared to a standard commercial MCPA formulation. Thereby, we conclude that the LDHs employed in this study can be used not only as adsorbents to remove MCPA from aqueous solutions, but also as supports for the slow release of this highly mobile herbicide, thus controlling its immediate availability and leaching.

Pretreatment of agriculture field water for improving membrane flux during pesticide removal

NASA Astrophysics Data System (ADS)

Mehta, Romil; Saha, N. K.; Bhattacharya, A.

2017-10-01

Pretreatment of feed water to improve membrane flux during filtration of agriculture field water containing substituted phenyl urea pesticide diuron has been reported. Laboratory-made reverse osmosis membrane was used for filtration. Preliminary experiments were conducted with model solution containing natural organic matter extracted from commercial humic acids, divalent ions Ca2+, Mg2+. Membrane fouling was characterized by pure water flux decline, change in membrane hydrophilicity and infrared spectroscopy. Natural organic matter present in field water causes severe membrane fouling. The presence of divalent cations further aggravated fouling. Use of ethylenediaminetetraacetic acid (EDTA) and polyacrylic acids (PAA) in feed resulted in the decrease in membrane fouling. Pretreatment of field water is a must if it is contaminated with micro-organism having membrane fouling potential. Feed water pretreatment and use of PAA restricted membrane fouling to 16 % after 60 h of filtration. Membrane permeate flux decline was maximum at the first 12 h and thereafter remained steady at around 45-46 lm-2h-1 till the end of 60 h. Diuron rejection remained consistently greater than 93 % throughout the experiment. Diuron rejection was found to be unaffected by membrane fouling.

Binding and detoxification of chlorpyrifos by lactic acid bacteria on rice straw silage fermentation.

PubMed

Wang, Yan-Su; Wu, Tian-Hao; Yang, Yao; Zhu, Cen-Ling; Ding, Cheng-Long; Dai, Chuan-Chao

2016-01-01

This investigation examined the reduction of pesticide residues on straw inoculated with lactic acid bacteria (LAB) during ensiling. Lactobacillus casei WYS3 was isolated from rice straw that contained pesticide residues. Non-sterilized rice straw, which was inoculated with L. casei WYS3, showed increased removal of chlorpyrifos after ensiling, compared with rice straw that was not inoculated with L. casei WYS3 or sterilized rice straw. In pure culture, these strains can bind chlorpyrifos as indicated by high-performance liquid chromatography analysis. Viable L. casei WYS3 was shown to bind 33.3-42% of exogenously added chlorpyrifos. These results are similar to those of acid-treated cells but less than those of heat-treated cells, which were found to bind 32.0% and 77.2% of the added chlorpyrifos respectively. Furthermore, gas chromatography-mass spectrometry analysis determined that L. casei WYS3 detoxified chlorpyrifos via P-O-C cleavage. Real-time polymerized chain reaction analysis determined that organophosphorus hydrolase gene expression tripled after the addition of chlorpyrifos to LAB cultures, compared with the control group (without chlorpyrifos). This paper highlights the potential use of LAB starter cultures for the detoxification and removal of chlorpyrifos residues in the environment.

A multiresidue method for determination of trace levels of pesticides in air and water.

PubMed

Millet, M; Wortham, H; Sanusi, A; Mirabel, P

1996-11-01

A multiresidue analytical method is described for the analysis of 13 pesticides in fogwater, rainwater, gas, and particles. This method is based upon solid-liquid extraction using Sep-Pak tC18 light cartridges for aqueous samples, soxhlet for gas (adsorbed on XAD-2) and particles (on glass fiber filters), HPLC-based fractionation of the extracted residues using a silica column, and a linear gradient of n-hexane/tert butyl methyl ether followed by GC-ECD and HPLC-UV analyses of each fraction. Prior to analysis with GC-ECD, a methylation procedure using BF3/methanol was developed for the analysis of the fraction which contains chlorophenoxy acid herbicides. The recoveries of the extraction procedure of liquid samples and of the methylation were greater than 92 and 97% with a standard deviation lower than 8 and 5%, respectively. The detection limits varied between 0.1 and 0.01 microgram.ml-1 for the 13 pesticides studied with a standard deviation less than 9%. This method was used for the determination of pesticides in 18 fogwater samples (soluble + insoluble), 31 rainwater samples, and 17 air (gas + particles) samples collected between 1991 and 1993 in Colmar (east of France).

Endocrine Activities of Pesticides During Ozonation of Waters.

PubMed

Westlund, Paul; Isazadeh, Siavash; Therrien, Alexandre; Yargeau, Viviane

2018-01-01

Two yeast-based bioassays were used to assess the endocrine activity potential of transformation products formed during the ozonation of water containing a variety of pesticides (propiconazole, atrazine, 2,4-dichlorophenoxyacetic acid [2,4-D], tebuconazole, climbazole, myclobutanil, irgarol, terbutryn, dicamba, mecoprop and diuron). Ozone experiments were conducted first in reverse osmosis water to isolate the effects of the pesticides and then in synthetic wastewater and wastewater effluent to investigate whether the results translated to more complex matrices. The findings demonstrate the recalcitrant nature of most pesticides during ozonation, with removals below 50%, except for irgarol, terbutryn and climbazole with removals up to 70%. This study is the first one to investigate the removal of the fungicides myclobutanil and tebuconazole by ozonation and is one of the first studies to investigate the androgenic activity of ozonation transformation products of contaminants of emerging concern. These findings also demonstrated that during ozonation the initial anti-androgenic activity was removed while the estrogenic activity remained undetected and the androgenic activity increased to levels up to 60% of the anti-androgenic activity of the DHT control. These results indicate that bioactivity should be considered in the evaluation of treatment performance and risks assessment associated to wastewater discharges.

Toxicokinetics, including saturable protein binding, of 4-chloro-2-methyl phenoxyacetic acid (MCPA) in patients with acute poisoning

PubMed Central

Roberts, Darren M.; Dawson, Andrew H.; Senarathna, Lalith; Mohamed, Fahim; Cheng, Ron; Eaglesham, Geoffrey; Buckley, Nick A.

2011-01-01

Human data on protein binding and dose-dependent changes in toxicokinetics for MCPA are very limited. 128 blood samples were obtained in 49 patients with acute MCPA poisoning and total and unbound concentrations of MCPA were determined. The Scatchard plot was biphasic suggesting protein binding to two sites. The free MCPA concentration increased when the total concentration exceeded 239 mg/L (95% confidence interval 198–274 mg/L). Nonlinear regression using a two-site binding hyperbola model estimated saturation of the high affinity binding site at 115 mg/L (95%CI 0–304). Further analyses using global fitting of serial data and adjusting for the concentration of albumin predicted similar concentrations for saturable binding (184 mg/L and 167 mg/L, respectively) without narrowing the 95%CI. In 25 patients, the plasma concentration–time curves for both bound and unbound MCPA were approximately log-linear which may suggest first order elimination, although sampling was infrequent so zero order elimination cannot be excluded. Using a cut-off concentration of 200 mg/L, the half-life of MCPA at higher concentrations was 25.5 h (95%CI 15.0–83.0 h; n = 16 patients) compared to 16.8 h (95%CI 13.6–22.2 h; n = 10 patients) at lower concentrations. MCPA is subject to saturable protein binding but the influence on half-life appears marginal. PMID:21256202

Pesticides in Ichkeul Lake-Bizerta Lagoon Watershed in Tunisia: use, occurrence, and effects on bacteria and free-living marine nematodes.

PubMed

Salem, Fida Ben; Said, Olfa Ben; Aissa, Patricia; Mahmoudi, Ezzeddine; Monperrus, Mathilde; Grunberger, Olivier; Duran, Robert

2016-01-01

This study aimed to identify the most commonly used agricultural pesticides around Ichkeul Lake-Bizerta Lagoon watershed. First survey of pesticide use on agricultural watershed was performed with farmers, Regional Commissioner for Agricultural Development, and pesticide dealers. Then, sediment contamination by pesticides and response of benthic communities (bacteria and free-living marine nematode) were investigated. The analysis of 22 active organochlorine pesticides in sediments was performed according to quick, easy, cheap, effective, rugged, and safe (QuEChERS) method, biodiversity of indigenous bacterial community sediment was determined by terminal restriction fragment length polymorphism (T-RFLP), and free-living marine nematodes were counted. The results of the field survey showed that iodosulfuron, mesosulfuron, 2,4-dichlorophenoxyacetic acid (2,4 D), glyphosate, and fenoxaprops were the most used herbicides, tebuconazole and epoxiconazole the most used fungicides, and deltamethrin the most used insecticide. Sixteen organochlorine pesticide compounds among the 22 examined were detected in sediments up to 2 ppm in Ichkeul Lake, endrin, dieldrin, and hexachlorocyclohexane being the most detected molecules. The most pesticide-contaminated site in the lake presented the higher density of nematode, but when considering all sites, no clear correlation with organochlorine pesticide (OCP) content could be established. The bacterial community structure in the most contaminated site in the lake was characterized by the terminal restriction fragments (T-RFs) 97, 146, 258, 285, and 335 while the most contaminated site in the lagoon was characterized by the T-RFs 54, 263, 315, 403, and 428. Interestingly, T-RFs 38 and 143 were found in the most contaminated sites of both lake and lagoon ecosystems, indicating that they were resistant to OCPs and able to cope with environmental fluctuation of salinity. In contrast, the T-RFs 63, 100, 118, and 381 in the lake and the T-RFs 40, 60, 80, 158, 300, 321, and 357 in the lagoon were sensitive to OCPs. This study highlighted that the intensive use of pesticides in agriculture, through transfer to aquatic ecosystem, may disturb the benthic ecosystem functioning of the protected area. The free-living marine nematodes and bacterial communities represent useful proxy to follow the ecosystem health and its capacity of resilience.

Water Quality and Evaluation of Pesticides in Lakes in the Ridge Citrus Region of Central Florida

USGS Publications Warehouse

Choquette, Anne F.; Kroening, Sharon E.

2009-01-01

Water chemistry, including major inorganic constituents, nutrients, and pesticide compounds, was compared between seven lakes surrounded by citrus agriculture and an undeveloped lake on the Lake Wales Ridge (herein referred to as the Ridge) in central Florida. The region has been recognized for its vulnerability to the leaching of agricultural chemicals into the subsurface due to factors including soils, climate, and land use. About 40 percent of Florida's citrus cultivation occurs in 'ridge citrus' areas characterized by sandy well drained soils, with the remainder in 'flatwoods citrus' characterized by high water tables and poorly drained soils. The lakes on the Ridge are typically flow-through lakes that exchange water with adjacent and underlying aquifer systems. This study is the first to evaluate the occurrence of pesticides in lakes on the Ridge, and also represents one of the first monitoring efforts nationally to focus on regional-scale assessment of current-use pesticides in small- to moderate-sized lakes (5 to 393 acres). The samples were collected between December 2003 and September 2005. The lakes in citrus areas contained elevated concentrations of major inorganic constituents (including alkalinity, total dissolved solids, calcium, magnesium, sodium, potassium, chloride, and sulfate), total nitrogen, pH, and pesticides compared to the undeveloped lake. Nitrate (as N) and total nitrogen concentrations were typically elevated in the citrus lakes, with maximum values of 4.70 and 5.19 mg/L (milligrams per liter), respectively. Elevated concentrations of potassium, nitrate, and other inorganic constituents in the citrus lakes likely reflect inputs from the surficial ground-water system that originated predominantly from agricultural fertilizers, soil amendments, and inorganic pesticides. A total of 20 pesticide compounds were detected in the lakes, of which 12 compounds exceeded the standardized reporting level of 0.06 ug/L (microgram per liter). Those most frequently detected above the 0.06-ug/L level were aldicarb sulfoxide, diuron, simazine degradates hydroxysimazine and didealkylatrazine (DDA), bromacil, norflurazon, and demethyl norflurazon which occurred at detection rates ranging from 25 to 86 percent of samples, respectively. Typically, pesticide concentrations in the lake samples were less than 1 microgram per liter. The number of targeted pesticide compounds detected per lake in the citrus areas ranged from 9 to 14 compared to 3 compounds detected at trace levels in the undeveloped lake. Consistent detections of parents and degradates in quarterly samples indicated the presence of pesticide compounds in the lakes many months or years (for example, bromacil) after their application, signaling the persistence of some pesticide compounds in the lakes and/or ground-water systems. Pesticide degradate concentrations frequently exceeded parent concentrations in the lakes. This study was the first in the Ridge citrus region to analyze for glyphosate - widely used in citrus - and its degradate aminomethylphosphonic acid (AMPA), neither of which were detected, as well as a number of triazine degradates, including hydroxysimazine, which were detected. The lake pesticide concentrations did not exceed current Federal aquatic-life benchmarks, available for 10 of the 20 detected pesticide compounds. Limited occurrences of bromacil, diuron, or norflurazon concentrations were within about 10 to 90 percent of benchmark guidelines for acute effects on nonvascular aquatic plants in one or two of the lakes. The lake pesticide concentrations for several targeted pesticides were relatively high compared to corresponding national stream-water percentiles, which is consistent with this region's vulnerability for pesticide leaching into water resources. Several factors were evaluated to gain insight into the processes controlling pesticide transport and fate, and to assess their utility for estimating th

Draft Test Guideline: Fish Acute Toxicity Mitigated By Humic Acid

EPA Pesticide Factsheets

The following draft test guideline is part of a series of test guidelines that have been developed by EPA for use in the testing of pesticides and toxic substances, and the development of test data for submission to the Agency for review.

76 FR 59906 - Fluazifop-P-butyl; Pesticide Tolerances

Federal Register 2010, 2011, 2012, 2013, 2014

2011-09-28

...: This regulation establishes and increases tolerances for residues of fluazifop-P-butyl in or on cotton, gin byproducts; cotton, refined oil; and cotton, undelinted seed. Syngenta Crop Protection requested...-(trifluoromethyl)-2- pyridinyl]oxy]phenoxy]propanoic acid, expressed as fluazifop, in or on cotton, undelinted seed...

Little Green Lies. The Environmental Miseducation of America's Children.

ERIC Educational Resources Information Center

Adler, Jonathan H.

1992-01-01

Critiques environmental education in elementary school and secondary school education by reviewing 10 myths that give children an incomplete understanding of environmental issues. Discusses recycling, plastics, garbage, pesticides, acid rain, consumption, overpopulation, air pollution, global warming, and the ozone layer. Offers suggestions to…

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-use areas. The results of this investigation are not necessarily representative of conditions throughout the remainder of Long Island, because these samples were collected in areas of known or suspected residues.

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 concentrations above the U.S. Environmental Protection Agency's Primary Maximum Contaminant Levels or Secondary Maximum Contaminant Levels for inorganic compounds and radionuclides. One sample out of 30 contained a concentration of nitrite plus nitrate above the U.S. Environmental Protection Agency's Primary Maximum Contaminant Level of 10 milligrams per liter as nitrogen. Iron and manganese concentrations above the U.S. Environmental Protection Agency's Secondary Maximum Contaminant Levels were found in 7 of 30 ground-water samples, most of them from Sussex County. In the 10 wells sampled for radionuclides, only one sample had detectable levels of radium-224 and -226, and another sample contained detectable levels of radium-228; both of these samples also had detectable gross-alpha and gross-beta activities. None of these activities were above the U.S. Environ-mental Protection Agency's Primary Maximum Contaminant Levels or Secondary Maximum Contaminant Levels. Radon was detected in all 10 samples, but was above the current U.S. Environmental Protection Agency's proposed Primary Maximum Contaminant Level of 300 picocuries per liter in only one sample.

78 FR 30213 - 1-Naphthaleneacetic acid; Pesticide Tolerances

Federal Register 2010, 2011, 2012, 2013, 2014

2013-05-22

... Industrial Classification System (NAICS) codes is not intended to be exhaustive, but rather provides a guide... filing. Based upon review of the data supporting the petition, EPA has revised the proposed tolerance on... for which there is reliable information.'' This includes exposure through drinking water and in...

77 FR 26954 - 1-Naphthaleneacetic acid; Pesticide Tolerances

Federal Register 2010, 2011, 2012, 2013, 2014

2012-05-08

... for which there is reliable information.'' This includes exposure through drinking water and in... exposure from drinking water. The Agency used screening level water exposure models in the dietary exposure analysis and risk assessment for NAA in drinking water. These simulation models take into account data on...

Relationships between past and present pesticide applications and pollution at a watershed outlet: The case of a horticultural catchment in Martinique, French West Indies.

PubMed

Mottes, Charles; Lesueur Jannoyer, Magalie; Le Bail, Marianne; Guéné, Mathilde; Carles, Céline; Malézieux, Eric

2017-10-01

The understanding of factors affecting pesticide transfers to catchment outlet is still at a very early stage in tropical context, and especially on tropical volcanic context. We performed on-farm pesticide use surveys during 87 weeks and monitored pesticides in water weekly during 67 weeks at the outlet of a small catchment in Martinique. We identified three types of pollution. First, we showed long-term chronic pollution by chlordecone, diuron and metolachlor resulting from horticultural practices applied 5-20 years ago (quantification frequency higher than 80%). Second, we showed peak pollution. High amounts of propiconazole and fosthiazate applied at low frequencies caused river pollution peaks for weeks following a single application. Low amounts of diquat and diazinon applied at low frequencies also caused pollution peaks. The high amounts of glyphosate applied at high frequency resulted into pollution peaks by glyphosate and aminomethylphosphonic acid (AMPA) in 6 and 20% of the weeks. Any intensification of their uses will result in higher pollution levels. Third, relatively low amounts of glufosinate-ammonium, difenoconazol, spinosad and metaldehyde were applied at high frequencies. Unexpectedly, such pesticides remained barely detected (<1.5%) or undetected in water samples. We showed that AMPA, fosthiazate and propiconazole have serious leaching potential. They might result in future chronic pollution of shallow aquifers alimenting surface water. We prove that to avoid the past errors and decrease the risk of long-term pollution of water resources, it is urgent to reduce or stop the use of pesticides with leaching potential by changing agricultural practices. Copyright © 2017 Elsevier Ltd. All rights reserved.

Surface Runoff of Pesticides from a Clay Loam Field in Sweden.

PubMed

Larsbo, Mats; Sandin, Maria; Jarvis, Nick; Etana, Ararso; Kreuger, Jenny

2016-07-01

Pesticides stored at or close to the soil surface after field application can be mobilized and transported off the field when surface runoff occurs. The objective of our study was to quantify the potential pesticide losses in surface runoff from a conventionally managed agricultural field in a Swedish climate. This was achieved by measuring surface runoff volumes and concentrations in runoff of six spring-applied pesticides and autumn-applied glyphosate and its metabolite aminomethylphosphonic acid (AMPA). Measurements were performed for 3 yr both during the growing seasons and during intervening winter snowmelt periods on a clay loam field close to Uppsala. During growing seasons, surface runoff was generated on only five occasions during one 25-d period in 2012 when the infiltration capacity of the soil may have been reduced by structural degradation due to large cumulative rainfall amounts after harrowing. Concentrations in surface runoff exceeded Swedish water quality standards in all samples during this growing season for diflufenican and pirimicarb. Surface runoff was generated during three snowmelt periods during the winter of 2012-2013. All of the applied pesticides were found in snowmelt samples despite incorporation of residues by autumn plowing, degradation, and leaching into the soil profile during the period between spraying and sampling. Concentrations of glyphosate ranged from 0.12 to 7.4 μg L, and concentrations of AMPA ranged from 0 to 2.7 μg L. Our results indicate that temporal changes in hydraulic properties during the growing season and when the soil freezes during winter affect pesticide losses through surface runoff. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

[Determination of 250 pesticide residues in vegetables using QuEChERS-ultra performance liquid chromatography-tandem mass spectrometry].

PubMed

Zhang, Aizhi; Wang, Quanlin; Cao, Lili; Li, Yu; Shen, Hao; Shen, Jian; Zhang, Shufen; Man, Zhengyin

2016-02-01

A multiresidue analytical method for the determination of 250 pesticide residues in vegetables was developed by using QuEChERS-ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The target compounds were extracted with acetonitrile containing 1% (v/v) acetic acid, purified by a mixed sorbent of MgSO4, primary secondary amine (PSA), graphitized carbon black (GCB) and C18, separated on a Waters ACQUITY™ UPLC BEH C18 column (100 mm x 2. 1 mm, 1.7 µm) and detected by UPLC-MS/MS. Anhydrous magnesium sulfate was used as a dewatering agent. The effects of the amounts of MgSO4, PSA, GCB and C18 added on the recoveries of 250 pesticides were investigated. The results showed that the purification effect was best when 300 mg MgSO4, 200 mg PSA, 10 mg GCB and 100 mg C18 in 2 mL of the extract were added. For the 250 pesticide residues, the limits of detection (LODs) of the method were from 0. 01 to 50. 00 g/kg. The recoveries obtained ranged from 60. 1% to 120% at three spiked levels in Chinese chives with the relative standard deviations between 3. 5% and 19. 5% using matrix matched external standard method. The results showed that the method is able to meet requirements of the multiresidue detection of the 250 pesticides in vegetable. The method has the advantages of rapidity, simplicity, high sensitivity and better purification effect. It is suitable for the rapid determination of the common pesticides in vegetables, and it provides a strong guarantee for the risk assessments of the quality and safety of vegetables.

Quantification and characterization of glyphosate use and loss in a residential area.

PubMed

Tang, Ting; Boënne, Wesley; Desmet, Nele; Seuntjens, Piet; Bronders, Jan; van Griensven, Ann

2015-06-01

Urban runoff can be a significant source of pesticides in urban streams. However, quantification of this source has been difficult because pesticide use by urban residents (e.g., on pavements or in gardens) is often unknown, particularly at the scale of a residential catchment. Proper quantification and characterization of pesticide loss via urban runoff require sound information on the use and occurrence of pesticides at hydrologically-relevant spatial scales, involving various hydrological conditions. We conducted a monitoring study in a residential area (9.5 ha, Flanders, Belgium) to investigate the use and loss of a widely-used herbicide (glyphosate) and its major degradation product (aminomethylphosphonic acid, AMPA). The study covered 13 rainfall events over 67 days. Overall, less than 0.5% of glyphosate applied was recovered from the storm drain outflow in the catchment. Maximum detected concentrations were 6.1 μg/L and 5.8 μg/L for glyphosate and AMPA, respectively, both of which are below the predicted no-effect concentration for surface water proposed by the Flemish environmental agency (10 μg/L), but are above the EU drinking water standard (0.1 μg/L). The measured concentrations and percentage loss rates can be attributed partially to the strong sorption capacity of glyphosate and low runoff potential in the study area. However, glyphosate loss varied considerably among rainfall events and event load of glyphosate mass was mainly controlled by rainfall amount, according to further statistical analyses. To obtain urban pesticide management insights, robust tools are required to investigate the loss and occurrence of pesticides influenced by various factors, particularly the hydrological and spatial factors. Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of Organic Diet Intervention on Pesticide Exposures in Young Children Living in Low-Income Urban and Agricultural Communities.

PubMed

Bradman, Asa; Quirós-Alcalá, Lesliam; Castorina, Rosemary; Aguilar Schall, Raul; Camacho, Jose; Holland, Nina T; Barr, Dana Boyd; Eskenazi, Brenda

2015-10-01

Recent organic diet intervention studies suggest that diet is a significant source of pesticide exposure in young children. These studies have focused on children living in suburban communities. We aimed to determine whether consuming an organic diet reduced urinary pesticide metabolite concentrations in 40 Mexican-American children, 3-6 years of age, living in California urban and agricultural communities. In 2006, we collected urine samples over 16 consecutive days from children who consumed conventionally grown food for 4 days, organic food for 7 days, and then conventionally grown food for 5 days. We measured 23 metabolites, reflecting potential exposure to organophosphorous (OP), pyrethroid, and other pesticides used in homes and agriculture. We used linear mixed-effects models to evaluate the effects of diet on urinary metabolite concentrations. For six metabolites with detection frequencies > 50%, adjusted geometric mean concentrations during the organic phase were generally lower for all children, and were significant for total dialkylphosphates (DAPs) and dimethyl DAPs (DMs; metabolites of OP insecticides) and 2,4-D (2,4-dichlorophenoxyacetic acid, a herbicide), with reductions of 40%, 49%, and 25%, respectively (p < 0.01). Chemical-specific metabolite concentrations for several OP pesticides, pyrethroids, and herbicides were either infrequently detected and/or not significantly affected by diet. Concentrations for most of the frequently detected metabolites were generally higher in Salinas compared with Oakland children, with DMs and metolachlor at or near significance (p = 0.06 and 0.03, respectively). An organic diet was significantly associated with reduced urinary concentrations of nonspecific dimethyl OP insecticide metabolites and the herbicide 2,4-D in children. Additional research is needed to clarify the relative importance of dietary and non-dietary sources of pesticide exposures to young children.

In vitro screening of 200 pesticides for agonistic activity via mouse peroxisome proliferator-activated receptor (PPAR){alpha} and PPAR{gamma} and quantitative analysis of in vivo induction pathway

DOE Office of Scientific and Technical Information (OSTI.GOV)

Takeuchi, Shinji; Matsuda, Tadashi; Kobayashi, Satoshi

2006-12-15

Peroxisome proliferator-activated receptors (PPARs) are ligand-dependent transcription factors and key regulators of lipid metabolism and cell differentiation. However, there have been few studies reporting on a variety of environmental chemicals, which may interact with these receptors. In the present study, we characterized mouse PPAR{alpha} and PPAR{gamma} agonistic activities of 200 pesticides (29 organochlorines, 11 diphenyl ethers, 56 organophosphorus pesticides, 12 pyrethroids, 22 carbamates, 11 acid amides, 7 triazines, 8 ureas and 44 others) by in vitro reporter gene assays using CV-1 monkey kidney cells. Three of the 200 pesticides, diclofop-methyl, pyrethrins and imazalil, which have different chemical structures, showed PPAR{alpha}-mediatedmore » transcriptional activities in a dose-dependent manner. On the other hand, none of the 200 pesticides showed PPAR{gamma} agonistic activity at concentrations {<=} 10{sup -5} M. To investigate the in vivo effects of diclofop-methyl, pyrethrins and imazalil, we examined the gene expression of PPAR{alpha}-inducible cytochrome P450 4As (CYP4As) in the liver of female mice intraperitoneally injected with these compounds ({<=} 300 mg/kg). RT-PCR revealed significantly high induction levels of CYP4A10 and CYP4A14 mRNAs in diclofop-methyl- and pyrethrins-treated mice, whereas imazalil induced almost no gene expressions of CYP4As. In particular, diclofop-methyl induced as high levels of CYP4A mRNAs as WY-14643, a potent PPAR{alpha} agonist. Thus, most of the 200 pesticides tested do not activate PPAR{alpha} or PPAR{gamma} in in vitro assays, but only diclofop-methyl and pyrethrins induce PPAR{alpha} agonistic activity in vivo as well as in vitro.« less

Superfund Record of Decision (EPA Region 5): Pristine, Inc. , Reading, OH. (First remedial action), March 1990. (Amendment). Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

The 2-acre Pristine site is in Reading, Hamilton County, Ohio. The site is bordered by industrial and residential areas, including a trailer park three hundred feet northeast of the site. In 1979, State investigations identified as many as 8,000 to 10,000 drums and several thousand gallons of liquid wastes onsite. Types of waste included acids, solvents, pesticides, and PCBs. From 1980 to 1983, EPA and Pristine removed onsite wastes including paint and solvent sludge, solvents, pesticides, organics, PCB-contaminated soil, and incinerator ash. The ROD amends the soil component remedy of the 1987 ROD from in-situ vitrification to incineration and soilmore » vapor extraction. The primary contaminants of concern affecting the soil, sediment, debris, and ground water are VOCs including benzene, PCE, TCE, and xylenes; other organics including dioxin and pesticides such as DDT; metals including lead, chromium, and arsenic; and other inorganics.« less

Determination of pesticides and pesticide degradates in filtered water by direct aqueous-injection liquid chromatography-tandem mass spectrometry

USGS Publications Warehouse

Sandstrom, Mark W.; Kanagy, Leslie K.; Anderson, Cyrissa A.; Kanagy, Christopher J.

2016-01-11

Mean recoveries of most analytes (223 of 229) were within data-quality objectives of 100±30 percent at spike concentrations above method detection levels (MDLs) in all four matrices. The calculated MDLs ranged from 1 to 103 nanograms per liter (ng/L) for 182 analytes analyzed in the ESI positive mode, and from 2 to 106 ng/L for 42 analytes analyzed in the ESI negative mode. Five analytes had MDLs between 100 and 250 ng/L. The stability studies in reagent water demonstrated that the largest number of the pesticide compounds (227 of 229) were stable after 14 days of storage at 4 degrees Celsius, so these were selected as the practical holding time and storage temperature for routine sample processing. The use of antimicrobial reagent citric acid to adjust the sample pH to about 4 also resulted in lower recoveries of some analytes, so it should not be used as a routine sample preservative.

Evaluation of two fast and easy methods for pesticide residue analysis in fatty food matrixes.

PubMed

Lehotay, Steven J; Mastovská, Katerina; Yun, Seon Jong

2005-01-01

Two rapid methods of sample preparation and analysis of fatty foods (e.g., milk, eggs, and avocado) were evaluated and compared for 32 pesticide residues representing a wide range of physicochemical properties. One method, dubbed the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method for pesticide residue analysis, entailed extraction of 15 g sample with 15 mL acetonitrile (MeCN) containing 1% acetic acid followed by addition of 6 g anhydrous magnesium sulfate and 1.5 g sodium acetate. After centrifugation, 1 mL of the buffered MeCN extract underwent a cleanup step (in a technique known as dispersive solid-phase extraction) using 50 mg each of C18 and primary secondary amine sorbents plus 150 mg MgSO4. The second method incorporated a form of matrix solid-phase dispersion (MSPD), in which 0.5 g sample plus 2 g C18 and 2 g anhydrous sodium sulfate was mixed in a mortar and pestle and added above a 2 g Florisil column on a vacuum manifold. Then, 5 x 2 mL MeCN was used to elute the pesticide analytes from the sample into a collection tube, and the extract was concentrated to 0.5 mL by evaporation. Extracts in both methods were analyzed concurrently by gas chromatography/mass spectrometry and liquid chromatography/tandem mass spectrometry. The recoveries of semi-polar and polar pesticides were typically 100% in both methods (except that basic pesticides, such as thiabendazole and imazalil, were not recovered in the MSPD method), but recovery of nonpolar pesticides decreased as fat content of the sample increased. This trend was more pronounced in the QuEChERS method, in which case the most lipophilic analyte tested, hexachlorobenzene, gave 27 +/- 1% recovery (n=6) in avocado (15% fat) with a<10 ng/g limit of quantitation.

Mineralization of isoproturon, mecoprop and acetochlor in a deep unsaturated limestone and sandy aquifer.

PubMed

Janniche, G S; Lindberg, E; Mouvet, C; Albrechtsen, H-J

2010-11-01

Isoproturon (N,N-dimethyl-N'-[4-(1-methylethyl)phenyl]urea), mecoprop (MCPP) (2-(4-chloro-2-methylphenoxy)propanoic acid) and acetochlor (2-chloro-N-(2-ethoxymethyl)-N-(2-ethyl-6-methylphenyl)acetamide) are agricultural pesticides that may leach through the vadose zone down to groundwater. Sediment samples were collected from intact sediment cores from 0 to 59 m below surface, including soil, unsaturated limestone and aquifer sand. In the unsaturated limestone, the initial pesticide concentrations (0.5-100 μg kg(-1)) did not systematically affect the proportion of mineralized pesticides or the kinetics. However, in the aquifer, mecoprop and to some degree isoproturon mineralization was found to increase with increasing initial concentration (0.5-100 μg L(-1) equivalent to 1-220 μg kg(-1)) demonstrating the importance of using environmentally relevant concentrations when predicting pesticide fate. The mineralization of isoproturon, mecoprop and acetochlor was studied in 40 samples at low concentrations (1-3 μg L(-1)) and specific pesticide-mineralizing bacteria were enumerated using 14C-MPN. Presence of the mineralizers documented a degradation potential of the pesticides within the catchment. The number of mineralizers varied from <0.18 to >16000 g(-1) and was not found to correlate with depth. Mecoprop, isoproturon and acetochlor were substantially mineralized in the soils (19-44% after 8months incubation at 1 μg kg(-1)), in sub-surface unsaturated limestone samples (≤2% for acetochlor, ≤21% for isoproturon and ≤31% for mecoprop) and in aquifer samples (4-28% for mecoprop, ≤4.7% for isoproturon and ≤5.6% for acetochlor). The finding of isoproturon and acetochlor mineralization in deep aquifers is novel and important for the evaluation of the fate of these pesticides, as even low mineralization rates can be important in aquifers exhibiting long residence times. Copyright © 2010 Elsevier Ltd. All rights reserved.

Simultaneous determination of multiclass pesticide residues in human plasma using a mini QuEChERS method.

PubMed

Srivastava, Anshuman; Rai, Satyajeet; Kumar Sonker, Ashish; Karsauliya, Kajal; Pandey, Chandra Prabha; Singh, Sheelendra Pratap

2017-06-01

Blood is one of the most assessable matrices for the determination of pesticide residue exposure in humans. Effective sample preparation/cleanup of biological samples is very important in the development of a sensitive, reproducible, and robust method. In the present study, a simple, cost-effective, and rapid gas chromatography-tandem mass spectrometry method has been developed and validated for simultaneous analysis of 31 multiclass (organophosphates, organochlorines, and synthetic pyrethroids) pesticide residues in human plasma by means of a mini QuEChERS (quick, easy, cheap, effective, rugged, and safe) method. We have adopted a modified version of the QuEChERS method, which is primarily used for pesticide residue analysis in food commodities. The QuEChERS method was optimized by use of different extraction solvents and different amounts and combinations of salts and sorbents (primary-secondary amines and C 18 ) for the dispersive solid-phase extraction step. The results show that a combination of ethyl acetate with 2% acetic acid, magnesium sulfate (0.4 g), and solid-phase extraction for sample cleanup with primary-secondary amines (50 mg) per 1-mL volume of plasma is the most suitable for generating acceptable results with high recoveries for all multiclass pesticides from human plasma. The mean recovery ranged from 74% to 109% for all the analytes. The limit of quantification and limit of detection of the method ranged from 0.12 to 13.53 ng mL -1 and from 0.04 to 4.10 ng mL -1 respectively. The intraday precision and the interday precision of the method were 6% or less and 11% or less respectively. This method would be useful for the analysis of a wide range of pesticides of interest in a small volume of clinical and/or forensic samples to support biomonitoring and toxicological applications. Graphical Abstract Pesticide residues analysis in human plasma using mini QuEChERS method.

Emissions from open burning of used agricultural pesticide containers.

PubMed

Gullett, Brian K; Tabor, Dennis; Touati, Abderrahmane; Kasai, Jeanne; Fitz, Nancy

2012-06-30

Emissions from simulated open burning of used agricultural pesticide containers were sampled for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs), polycyclic aromatic hydrocarbon compounds (PAHs), and particle matter (PM(10) and PM(2.5)). Clean high density polyethylene (HDPE) containers, containers with trace pesticide, and triple-rinsed containers were burned separately in an open combustion facility and their emissions compared. Two common chlorinated pesticides were used: 2,4-dichlorophenoxyacetic acid (2,4-D) and 1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine (atrazine). PCDD/PCDF emission factors ranged from 0.1 to 24ng toxic equivalents (TEQ)/kg C burned with a mean and median of 4.9 and 1.9ng TEQ/kgC burned, respectively. In a limited number of trials, the trace 2,4-D in the HDPE container led to a statistically significant increase in PCDD/PCDF formation compare to all other conditions. Residual atrazine did not lead to more PCDD/PCDF than the unrinsed 2,4-D container. Total (16 compounds) PAH emission factors varied from 1.5 to 6.7mg/kgC burned. These limited data suggest that rinsing the 2,4-D container prior to burning reduces both PCDD/PCDF and PAH emissions. Nine PM(2.5) emission factors ranged from 9 to 35mg/gC burned and ten PM(10) values ranged from 6 to 43mg/gC burned. Neither pesticide appeared to have any effect on PM concentration. Published by Elsevier B.V.

Modelling of Pesticide Transport During An Injection Experiment In A Physical and Geochemical Heterogeneous Aquifer

NASA Astrophysics Data System (ADS)

Hojberg, A. L.; Engesgaard, P.; Bjerg, P. L.

The fate of selected pesticides under natural groundwater conditions was studied by natural gradient short and long term injection experiments in a shallow uncon- fined aerobic aquifer. Bentazone, DNOC, MCPP, dichlorprop, isoproturon, and BAM (dichlobenil metabolite) were injected in aqueous solution with bromide as a nonre- active tracer. The Bromide and pesticide plumes were sampled during the initial 25 m of migration in a dense monitoring net of multilevel samplers. The aquifer was physical and geochemical heterogeneous, which affected transport of several of the pesticides. A 3D reactive transport code was developed including one- and two-site linear/nonlinear equilibrium/nonequilibrium sorption and first-order as well as single Monod degradation kinetic coupled to microbial growth. Model simulations demon- strated that microbial growth was likely supported by the phenoxy acids MCPP and dichlorprop, while degradation of DNOC was adequately described by first-order degradation with no initial lag time. An observed vertical increase in pH was observed at the site and implemented in the transport code. The numerical analysis indicated that degradation of the three degradable pesticides may have been affected by vertical pH variations. Spatial variability in observed DNOC sorption was similarly suspected to be an effect of varying pH. pH dependency on DNOC sorption was confirmed by the model recognized by a match to observed breakthrough at the individual sampling points, when pH variation was included in the simulations.

Detection of Several Classes of Pesticides and Metabolites in Meconium by Gas Chromatography-Mass Spectrometry.

PubMed

Bielawski, D; Ostrea, E; Posecion, N; Corrion, M; Seagraves, J

2005-01-01

A solid phase extraction method was developed to isolate multiple classes of parent pesticides from meconium. A methanolic/hydrochloric acid methyl ester derivatization with liquid-liquid extraction technique was also developed for the analysis of metabolites. Identification and quantitation was by electron impact gas chromatography-mass spectrometry. For the parent compounds and metabolites, recoveries in spiked meconium ranged between 72-109%, with coefficients of variation ranging from 1.55-16.92% and limits of detection between 0.01-4.15 μg g(-1). Meconium samples obtained from infants in the Philippines were assayed using these methods, and propoxur, cypermethrin, pretilachlor, malathion, 4,4'-dichlorodiphenyltrichloroethylene, bioallethrin, and cyfluthrin were detected.

Phyt'Eaux Cités: application and validation of a programme to reduce surface water contamination with urban pesticides.

PubMed

Botta, Fabrizio; Fauchon, Nils; Blanchoud, Hélène; Chevreuil, Marc; Guery, Bénédicte

2012-01-01

This paper presents first results of Phyt'Eaux Cités, a program put in place by the local water supply agency, the SEDIF (Syndicat des Eaux d'Ile-de-France), in collaboration with 73 local authorities, private societies and institutional offices (365 km(2)). The challenges included: measurement of the previous surface water contamination, control of urban pesticide applications, prevention of pesticide hazard on users and finally a overall reduction of surface water contamination. An inquiry on urban total pesticide amount was coupled with a surface water bi-weekly monitoring to establish the impact of more than 200 molecules upon the Orge River. For 2007, at least 4400 kg and 92 type of pesticides (essentially herbicides) were quantified for all urban users in the Phyt'Eaux Cités perimeter. At the outlet of the Orge River (bi-weekly sampling in 2007), 11 molecules were always detected above 0.1 μg L(-1). They displayed the mainly urban origin of pesticide surface water contamination. Amitrole, AMPA (Aminomethyl Phosphonic Acid), demethyldiuron, diuron, glyphosate and atrazine were quantified with a 100% of frequency in 2007 and 2008 at the Orge River outlet. During the year, peaks of contamination were also registered for MCCP, 2,4 MCPA, 2,4 D, triclopyr, dichlorprop, diflufènican, active substances used in large amount in the urban area. However, some other urban molecules, such as isoxaben or flazasulfuron, were detected with low frequency. During late spring and summer, contamination patterns and load were dominated by glyphosate, amitrole and diuron, essentially applied by cities and urban users. Both isoproturon and chlortoluron were quantified during autumn and winter months according to upstream agricultural practices. In conclusion, 3 years after the beginning of this programme, the cities reduced the use of 68% of the total pesticide amount. An improvement on surface water quality was found from 2008 and during 2009 for all pesticides. In particular, glyphosate showed a decrease of the load above 60% in 2008, partly related to the Phyt'Eaux Cités action. Copyright © 2011 Elsevier Ltd. All rights reserved.

Estimated annual agricultural pesticide use for counties of the conterminous United States, 2008-12

USGS Publications Warehouse

Baker, Nancy T.; Stone, Wesley W.

2015-01-01

Table 8: 2, 4-D through Chlorantraniliprole Table 9: Chlorethoxyfos through Diflufenzopyr Table 10: Dimethenamid through Gibberellic acid Table 11: Glufosinate through Metiram Table 12: Metolachlor through Propazine Table 13: Propiconazole through Triasulfuron Table 14: Tribenuron methyl through Zoxamide

75 FR 51055 - Propionic Acid and Salts, and Urea Sulfate; Registration Review Proposed Decisions; Notice of...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-18

... human health or the environment. Through this program, EPA is ensuring that each pesticide's registration is based on current scientific and other knowledge, including its effects on human health and the... range of stakeholders including environmental, human health, farm worker, and agricultural advocates...

75 FR 28155 - Acephate, Cacodylic acid, Dicamba, Dicloran et al.; Proposed Tolerance Actions

Federal Register 2010, 2011, 2012, 2013, 2014

2010-05-19

... (NAICS code 112). Food manufacturing (NAICS code 311). Pesticide manufacturing (NAICS code 32532). This..., including food service, manufacturing and processing establishments, such as restaurants, cafeterias... concentration shall be limited to a maximum of 1.0 percent active ingredient. Contamination of food or food...

Marine Security of Hazardous Chemical Cargo

DTIC Science & Technology

2005-08-26

Division 6.1 Poisonous liquids (by inhalation) Liquid pesticide 6 Division 4.2 Spont. combustible ( pyrophoric ) Barium alloys 7 Division 4.1 Flammable...25167-67-3 10,000 Fire 2.1 Carbon disulfide 75-15-0 20,000 Toxic 3 Carbon oxysulfide [Carbon oxide sulfide (COS)] 463-58-1 10,000 Fire 2.3 Chlorine...acid (conc 50% or greater) [Hydrofluoric acid] 7664-39-3 1,000 Toxic 8 Hydrogen selenide 7/5/7783 500 Toxic 2.3 Hydrogen sulfide 6/4/7783 10,000 Toxic

Exposure of small water bodies to pesticides and their transformation products in a lowland catchment

NASA Astrophysics Data System (ADS)

Ulrich, Uta; Fohrer, Nicola

2016-04-01

INTRODUCTION Based on the European Directive 2009/128/EC (2009), all member states were obliged to set up National Action Plans for the sustainable use of pesticides. In the German National Action Plan (GNAP), the status of small water bodies (swb) defined as water bodies with a catchment <10km² was stressed among other issues. Since the GNAP stated that knowledge and data base of pesticide contamination of swbs is insufficient, a monitoring of 10 swbs in the catchment of the lowland river Kielstau was carried out in summer and autumn 2015 for selected herbicides and their transformation products (TP). METHODS Grab samples of the water phase were collected once at the end of the spring/summer application period and a screening was carried out for 102 pesticides and 6 TPs. During autumn application, the rape herbicide metazachlor and the winter grain herbicide flufenacet as well as their TPs oxalic acid (OA) and sulfonic acid (ESA) were in the focus of the study. The sampling was carried out event based after the first and second relevant rainfall events after application. The third sample was collected four weeks after the second sampling to observe the occurrence of the TPs. The target compounds were quantified by LC-MSMSMS. RESULTS For all swbs, the pesticide screening after the spring application showed pesticide/TP concentrations below the quantification limits (0.01-0.05 μg L-1) except of the corn herbicdes metolachlor, terbuthylazine and its TP desethylterbuthylazine. These findings were independent from the time elapsed since the last application of these compounds took place which was partly 4 years ago. After autumn application, the samples were analyzed for the herbicides metazachlor, flufenacet and their TPs which were sprayed on the fields where the swb are located in. These results showed that TPs of both herbicides remained from the year before and reached concentrations up to 1.9 μg L-1 for metazachlor ESA, 0.55 μg L-1 for metazachlor OA, 0.16 μg L-1 for flufenacet OA and 0.04 μg L-1 for flufenacet ESA. After autumn application, maximum concentrations of the mother compounds were 0.62 μg L-1 for metazachlor after the second and 0.5 μg L-1 for flufenacet after the first relevant rainfall event. The TP concentrations after autumn application were up to 200 times higher than the mother compound (metazachlor and -ESA). Key words: small water bodies, transformation products, metazachlor, flufenacet, -OA, -ESA

Effects of Common Pesticides on Prostaglandin D2 (PGD2) Inhibition in SC5 Mouse Sertoli Cells, Evidence of Binding at the COX-2 Active Site, and Implications for Endocrine Disruption.

PubMed

Kugathas, Subramaniam; Audouze, Karine; Ermler, Sibylle; Orton, Frances; Rosivatz, Erika; Scholze, Martin; Kortenkamp, Andreas

2016-04-01

There are concerns that diminished prostaglandin action in fetal life could increase the risk of congenital malformations. Many endocrine-disrupting chemicals have been found to suppress prostaglandin synthesis, but to our knowledge, pesticides have never been tested for these effects. We assessed the ability of pesticides that are commonly used in the European Union to suppress prostaglandin D2 (PGD2) synthesis. Changes in PGD2 secretion in juvenile mouse Sertoli cells (SC5 cells) were measured using an ELISA. Coincubation with arachidonic acid (AA) was conducted to determine the site of action in the PGD2 synthetic pathway. Molecular modeling studies were performed to assess whether pesticides identified as PGD2-active could serve as ligands of the cyclooxygenase-2 (COX-2) binding pocket. The pesticides boscalid, chlorpropham, cypermethrin, cyprodinil, fenhexamid, fludioxonil, imazalil (enilconazole), imidacloprid, iprodione, linuron, methiocarb, o-phenylphenol, pirimiphos-methyl, pyrimethanil, and tebuconazole suppressed PGD2 production. Strikingly, some of these substances-o-phenylphenol, cypermethrin, cyprodinil, linuron, and imazalil (enilconazole)-showed potencies (IC50) in the range between 175 and 1,500 nM, similar to those of analgesics intended to block COX enzymes. Supplementation with AA failed to reverse this effect, suggesting that the sites of action of these pesticides are COX enzymes. The molecular modeling studies revealed that the COX-2 binding pocket can accommodate most of the pesticides shown to suppress PGD2 synthesis. Some of these pesticides are also capable of antagonizing the androgen receptor. Chemicals with structural features more varied than previously thought can suppress PGD2 synthesis. Our findings signal a need for in vivo studies to establish the extent of endocrine-disrupting effects that might arise from simultaneous interference with PGD2 signaling and androgen action. Kugathas S, Audouze K, Ermler S, Orton F, Rosivatz E, Scholze M, Kortenkamp A. 2016. Effects of common pesticides on prostaglandin D2 (PGD2) inhibition in SC5 mouse Sertoli cells, evidence of binding at the COX-2 active site, and implications for endocrine disruption. Environ Health Perspect 124:452-459; http://dx.doi.org/10.1289/ehp.1409544.

Effects of Common Pesticides on Prostaglandin D2 (PGD2) Inhibition in SC5 Mouse Sertoli Cells, Evidence of Binding at the COX-2 Active Site, and Implications for Endocrine Disruption

PubMed Central

Kugathas, Subramaniam; Audouze, Karine; Ermler, Sibylle; Orton, Frances; Rosivatz, Erika; Scholze, Martin; Kortenkamp, Andreas

2015-01-01

Background: There are concerns that diminished prostaglandin action in fetal life could increase the risk of congenital malformations. Many endocrine-disrupting chemicals have been found to suppress prostaglandin synthesis, but to our knowledge, pesticides have never been tested for these effects. Objectives: We assessed the ability of pesticides that are commonly used in the European Union to suppress prostaglandin D2 (PGD2) synthesis. Methods: Changes in PGD2 secretion in juvenile mouse Sertoli cells (SC5 cells) were measured using an ELISA. Coincubation with arachidonic acid (AA) was conducted to determine the site of action in the PGD2 synthetic pathway. Molecular modeling studies were performed to assess whether pesticides identified as PGD2-active could serve as ligands of the cyclooxygenase-2 (COX-2) binding pocket. Results: The pesticides boscalid, chlorpropham, cypermethrin, cyprodinil, fenhexamid, fludioxonil, imazalil (enilconazole), imidacloprid, iprodione, linuron, methiocarb, o-phenylphenol, pirimiphos-methyl, pyrimethanil, and tebuconazole suppressed PGD2 production. Strikingly, some of these substances—o-phenylphenol, cypermethrin, cyprodinil, linuron, and imazalil (enilconazole)—showed potencies (IC50) in the range between 175 and 1,500 nM, similar to those of analgesics intended to block COX enzymes. Supplementation with AA failed to reverse this effect, suggesting that the sites of action of these pesticides are COX enzymes. The molecular modeling studies revealed that the COX-2 binding pocket can accommodate most of the pesticides shown to suppress PGD2 synthesis. Some of these pesticides are also capable of antagonizing the androgen receptor. Conclusions: Chemicals with structural features more varied than previously thought can suppress PGD2 synthesis. Our findings signal a need for in vivo studies to establish the extent of endocrine-disrupting effects that might arise from simultaneous interference with PGD2 signaling and androgen action. Citation: Kugathas S, Audouze K, Ermler S, Orton F, Rosivatz E, Scholze M, Kortenkamp A. 2016. Effects of common pesticides on prostaglandin D2 (PGD2) inhibition in SC5 mouse Sertoli cells, evidence of binding at the COX-2 active site, and implications for endocrine disruption. Environ Health Perspect 124:452–459; http://dx.doi.org/10.1289/ehp.1409544 PMID:26359731

Longitudinal changes in microbial planktonic communities of a French river in relation to pesticide and nutrient inputs.

PubMed

Pesce, Stéphane; Fajon, Céline; Bardot, Corinne; Bonnemoy, Frédérique; Portelli, Christophe; Bohatier, Jacques

2008-02-18

To determine the effects of anthropic activities on river planktonic microbial populations, monthly water samples were collected for 11 months from two sampling sites characterized by differing nutrient and pesticide levels. The difference in trophic level between the two stations was particularly pronounced from May to November. Total pesticide concentrations were notably higher at the downstream station from April to October with a clear predominance of herbicide residues, especially the glyphosate metabolite aminomethylphosphonic acid (AMPA). From spring, algal biomass and density were favored by the high orthophosphate concentrations recorded at the downstream location. However, isolated drops in algal biomass were recorded at this sampling station, suggesting an adverse effect of herbicides on algal communities. No major difference was observed in bacterial heterotrophic production, density, or activity (CTC reduction) between the two sampling stations. No major variation was detected using the fluorescent in situ hybridization (FISH) method, but shifts in bacterial community composition were recorded by PCR-TTGE analysis at the downstream station following high nutrient and pesticide inputs. However, outside the main anthropic pollution period, the water's chemical properties and planktonic microbial communities were very similar at the two sampling sites, suggesting a high recovery potential for this lotic system.

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 agricultural pesticides among the target analytes for this study. No concentration of a pesticide or pesticide degradate exceeded any regulatory standard. Dieldrin, an insecticide that has been banned for several decades, was detected at a concentration that exceeded a non-regulatory health-based screening level of 0.002 micrograms per liter at nine sites. Volatile organic compounds (VOCs) were generally detected at concentrations of less than 1 microgram per liter, although 7 of the 31 detected VOCs had concentrations greater than 1 microgram per liter. There were no significant differences in VOC concentrations from 2000 to 2008; however, among the resampled wells, the mean number of VOCs detected per well was significantly different over the 8-year period. The number of VOCs detected per well decreased in 73 percent of the resampled wells; the decrease ranged from one to eight fewer detections in 2008 than in 2000. Chloroform and methyl tert-butyl ether were the most frequently detected VOCs, at 90 percent and 63 percent, respectively, among the 30 wells. Solvents were the most frequently detected class of VOCs. All measured concentrations of VOCs in groundwater were below established standards for drinking water and below other health-based guidelines. There were no significant differences in nutrient or major-ion concentrations between 2000 and 2008, however, the medians of two field measurements, pH and dissolved oxygen, were significantly higher in 2008 than in 2000 in the resampled wells. Although pH and dissolved oxygen were higher, water was still acidic and predominantly oxic. Nitrate was the predominant nutrient species in the Columbia aquifer, with a 90-percent detection frequency. The median nitrate concentration in groundwater was 4.88 milligrams per liter, which was slightly lower than, but not significantly different from, the median of 5.23 milligrams per liter for the 2000 samples. Concentrations of nitrate exceeded the U.S. Environmental Protection Agency's Maximum Contaminant Level or Federal drinking-water standard of 10 milligrams per liter as nitrogen in samples from two wells. Eight of the 30 wells sampled had iron or manganese concentrations that exceeded the U.S. Environmental Protection Agency's Secondary Maximum Contaminant Level; nine samples exceeded the Health Advisory Limit set by the Delaware Division of Public Health of 20 milligrams per liter for sodium in drinking water. Two radiochemical isotopes, radium-226 and radon-222, were detected in all nine groundwater samples analyzed; five samples had detectable levels of radium-228 activity. None of the samples exceeded the U.S Environmental Protection Agency's Maximum Contaminant Level for radium or radon in drinking water. Although radioactive elements were more frequently detected in 2008 than in 2000, this increased detection frequency is more likely due to lower detection levels in 2008 than 2000. The average age of groundwater entering the screens of the production wells sampled in 2008 ranged from 6 to 35 years, with a median groundwater age of 22 years. Groundwater age was positively correlated with well depth and negatively correlated with dissolved oxygen. Data from the 22 resampled wells indicate a significant positive difference in the average modeled groundwater-sample-age results. The average groundwater age from samples collected in 2008 was generally 7 years older than the average groundwater age from samples collected in 2000.

Identifying the metabolic perturbations in earthworm induced by cypermethrin using gas chromatography-mass spectrometry based metabolomics

PubMed Central

Ch, Ratnasekhar; Singh, Amit Kumar; Pandey, Pathya; Saxena, Prem Narain; Reddy Mudiam, Mohana Krishna

2015-01-01

Globally, cypermethrin is one of the most widely used synthetic pyrethroid for agricultural and domestic purposes. Most part of the pesticides used in the agriculture ends up as residues in the soil, making soil dwelling organisms, especially earthworms more susceptible to pesticide intoxication. Cypermethrin is known to be a neurotoxicant to many model organisms, including mammals and insects, but such type of toxicity evidence is not available for invertebrate systems like earthworms. In the present work, metabolomics based approach was utilized to identify the toxic mechanism of action of cypermethrin on earthworm (Metaphire posthuma) and these were exposed to sub-lethal concentrations of cypermethrin such as 2.5 mg/kg, 5 mg/kg, 10 mg/kg and 20 mg/kg (1/40th, 1/20th, 1/10th and 1/5th of LC50, respectively) for fourteen days. The results revealed that 22 metabolites (mainly fatty acids, sugars and amino acids) were shown significant responses in the exposed earthworms and these responses are dose dependent. It is proposed that mainly carbohydrate and fatty acids in neural system metabolism was disturbed. Overall, the results provided that metabolomics can be an effective tool to understand the effects of cypermethrin on the metabolic responses of earthworm Metaphire posthuma. PMID:26514086

Organochlorine pesticide contamination of ground water in the city of Hyderabad.

PubMed

Shukla, Gangesh; Kumar, Anoop; Bhanti, Mayank; Joseph, P E; Taneja, Ajay

2006-02-01

Organochlorine pesticides are ubiquitous and persistent organic pollutants used widely throughout the world. Due to the extensive use in agriculture, organic environmental contaminants such as HCH, DDT along with other organochlorine pesticides are distributed globally by transport through air and water. The main aim of present study is to determine contamination levels of organochlorine pesticides in the ground water of Hyderabad City. Water samples were collected from 28 domestic well supplies of the city. For this study, random sampling technique was applied, all the samples were collected in high purity glass bottles and refrigerated at 4 degrees C until analysis. Solid Phase Extraction (SPE) is used for the extraction of organochlorine pesticide residues in water sample. The collected water samples were pre-filtered through a 0.45 microg glass fiber filter (Wattman GF/F) to remove particulate matter and were acidified with hydrochloric acid (6N) to pH 2.5. Methanol modifier (BDH, for pesticide residue analysis, 10 mL) was added to water sample for better extraction. SPE using pre-packed reversed phase octadecyl (C-18 bonded silica) contained in cartridges was used for sample preparation. Prior to the extraction, the C-18 bonded phase, which contains 500 mg of bonded phase, was washed with 20 mL methanol. The sample was mixed well and allowed to percolate through the cartridges with flow rate of 10-15 mL/min under vacuum. After sample extraction, suction continued for 15 min to dry the packing material and pesticides trapped in the C-18 bonded phases were eluted by passing 10 mL hexane and fraction was evaporated in a gentle steam of Nitrogen. In all samples pesticide residues were analyzed by GC (Chemito-8510) with Ni63 ECD detector. Helium was used as carrier gas and nitrogen was used as make up gas. The injection technique was split/split less. All the samples analyzed were found to be contaminated with four pesticides i.e. DDT, beta-Endosulfan, alpha-Endosulfan and Lindane. DDT was found to range between 0.15 and 0.19 microg L(-1), beta-Endosulfan ranges between 0.21 and 0.87 microg L(-1), alpha-Endosulfan ranges between 1.34 and 2.14 microg L(-1) and Lindane ranges between 0.68 and 1.38 microg L(-1) respectively. These concentrations of pesticides in the water samples were found to be above their respective Acceptable Daily Intake (ADI) values for Humans.

Development of biofilters to treat the pesticides wastes from spraying applications.

PubMed

Pigeon, O; de Vleeschouwer, C; Cors, F; Weickmans, B; de Ryckel, B; Pussemier, L; Debongnie, Ph; Culot, M

2005-01-01

Several studies carried out in Europe showed the importance of direct losses to the contamination of surface water by pesticides. These pesticides losses can occur at the farm site when the sprayer equipment is filled with the pesticide formulation (spills, overflowing, leaking) and during the clean-up (rinsing) of the sprayer after the treatment. In Belgium studies are carried out on biofilters to treat in an efficient way effluents containing pesticides. The biofilter substrate is elaborated from a homogenised mixture of local soil, chopped straw and peat or composted material, able to absorb or degrade the active substances. Biofilters consist in systems of 2 or 3 units depending on the spray equipment of the farmer and on the configuration of the farmyard. Each unit is made from a 1 m3 plastic container and the different units are stacked in a vertical pile and connected between them using plastic valves and pipes. Eight pilot systems were installed in March 2002 in seven farms and in one agricultural school, all selected in the loamy region of Belgium specialised in arable crops such as cereals, sugar beets and vegetables. The efficacy (yield) of the systems was determined by measuring the balance of the inputs and outputs of the pesticides. Results were expressed in percent of pesticide retained on the biofilters. The results obtained after two years with 5 tracer pesticides (atrazine, carbofuran, diuron, lenacil and simazine) brought on the biofilter installations are very satisfactory since the percentage of retention is generally higher than 95% of the amount applied. In the beginning of 2004, ten new pilot biofilters were installed in several farms or agricultural technical centres (producing cereals, sugar beets, potatoes, vegetables, fruits or ornamental plants), and in a municipal maintenance service. Some biofilters were installed in duplicate in order to compare the efficacy of different substrates. The efficacy of the biofilters was studied for the 5 classical tracer pesticides but also for other chemical classes of herbicides (sulfonylurea, aryloxyalcanoic acids, chloroacetanilides), insecticides (pyrethroids, carbamates) and fungicides (dicarboximides, phenylamides, triazoles and strobilurines). To monitor these pesticides in elutes and substrates, two analytical methods were developed, optimised and validated : the first one by Gas Chromatography with Mass Spectrometry Detection (GC-MS), and the second one by High Performance Liquid Chromatography with UV Diode Array Detection (HPLC-DAD). The micro-organisms activity in the substrate was also measured in some situations.

A review of agricultural pesticide incidents in man in England and Wales, 1952-71

PubMed Central

Hearn, C. E. D.

1973-01-01

Hearn, C. E. D. (1973).British Journal of Industrial Medicine,30, 253-258. A review of agricultural pesticide incidents in man in England and Wales, 1952-71. An analysis was carried out of the poisoning incidents attributed to pesticides in England and Wales investigated by the Safety Inspectorate of the Pesticides Branch of the Ministry of Agriculture, Fisheries, and Food from 1952 to 1971. All poisoning incidents attributed to pesticides which are reported to the Safety Inspectorate are recorded and separated into reported and confirmed incidents. The confirmed incidents are classified into fatal and non-fatal. The non-fatal incidents are subdivided into four categories, systemic poisoning, eye injuries, dermatitis, and chemical burns. There were nine fatal cases of poisoning due to pesticides between 1952 and 1971, of which only three were occupational in origin. The remaining six were non-occupational but were investigated by the Safety Inspectorate only because the incident happened to arise on, or in connection with, a farm. The details of all the cases are recorded. There were 222 non-fatal confirmed incidents during the period, affecting a total of 296 persons. There has been an increased frequency of incidents since 1966 largely attributable to more complete and comprehensive recording by the Safety Inspectorate. Out of a total of 250 recorded pesticide effects, 121 (48·5%) were systemic poisoning, 57 (22·8%) were eye injuries, 54 (21·6%) were dermatitis, and 18 (7·1%) were chemical burns. Of the 121 incidents of non-fatal systemic poisoning, usually of a mild character, 34 were due to organophosphates, 26 to a single incident involving chloropicrin, 15 to arsenites, eight to dinitro compounds, three to nicotine, two to fungicides, one to cyanide, and one to an organomercury compound. Thirty-one incidents were not classified because the symptoms were non-specific in character and the worker had been exposed to a large number of different chemicals. In some instances the relationship of the symptoms to previous exposure to pesticides was extremely uncertain. Eye injuries and dermatitis were attributable to a wide variety of different chemicals and in the majority of instances were mild. Sulphuric acid, used for potato haulm destruction, was the commonest recorded cause of chemical burns. The main problems in the use of pesticides in England and Wales today are (1) the illicit decanting of concentrate from the manufacturer's labelled containers, (2) the hoarding of incompletely used containers, (3) the disposal of empty containers, and (4) the importation of pesticides in inadequately labelled containers. These defined practical problems of safety in application and accident control are perhaps of greater importance than the long-term theoretical toxicological effects of pesticides which may be attracting too much attention today. PMID:4737427

High Performance Liquid Chromatography

NASA Astrophysics Data System (ADS)

Talcott, Stephen

High performance liquid chromatography (HPLC) has many applications in food chemistry. Food components that have been analyzed with HPLC include organic acids, vitamins, amino acids, sugars, nitrosamines, certain pesticides, metabolites, fatty acids, aflatoxins, pigments, and certain food additives. Unlike gas chromatography, it is not necessary for the compound being analyzed to be volatile. It is necessary, however, for the compounds to have some solubility in the mobile phase. It is important that the solubilized samples for injection be free from all particulate matter, so centrifugation and filtration are common procedures. Also, solid-phase extraction is used commonly in sample preparation to remove interfering compounds from the sample matrix prior to HPLC analysis.

A COMPUTATIONAL CHEMISTRY STUDY OF THE ENVIRONMENTALLY IMPORTANT ACID-CATALYZED HYDROLYSIS OF ATRAZINE AND RELATED 2-CHLORO-S-TRIAZINES

EPA Science Inventory

Many chlorine-containing pesticides, for example 2-chloro-s-triazines, are of great concern both environmentally and toxicologically. As a result, ascertaining or predicting the fate and transport of these compounds in soils and water is of current interest. Transformation pathwa...

76 FR 77709 - Butyl acrylate-methacrylic acid-styrene polymer; Tolerance Exemption

Federal Register 2010, 2011, 2012, 2013, 2014

2011-12-14

... result of pesticide use in residential settings. If EPA is able to determine that a finite tolerance is... integral part of its composition the atomic elements carbon, hydrogen, and oxygen. 3. The polymer does not contain as an integral part of its composition, except as impurities, any element other than those listed...

Titration and HPLC Characterization of Kombucha Fermentation: A Laboratory Experiment in Food Analysis

ERIC Educational Resources Information Center

Miranda, Breanna; Lawton, Nicole M.; Tachibana, Sean R.; Swartz, Natasja A.; Hall, W. Paige

2016-01-01

Quantification of the many constituents that make up our food, whether they are desirable (vitamins, antioxidants, nutrients) or undesirable (pesticides, toxins), is one of the most practical applications of chemistry. In this study, kombucha, a popular fermented tea beverage, was analyzed using acid-base titration and high-performance liquid…

Functional Profiling Discovers the Dieldrin Organochlorinated Pesticide Affects Leucine Availability in Yeast

PubMed Central

Vulpe, Chris D.

2013-01-01

Exposure to organochlorinated pesticides such as dieldrin has been linked to Parkinson’s and Alzheimer’s diseases, endocrine disruption, and cancer, but the cellular and molecular mechanisms of toxicity behind these effects remain largely unknown. Here we demonstrate, using a functional genomics approach in the model eukaryote Saccharomyces cerevisiae, that dieldrin alters leucine availability. This model is supported by multiple lines of congruent evidence: (1) mutants defective in amino acid signaling or transport are sensitive to dieldrin, which is reversed by the addition of exogenous leucine; (2) dieldrin sensitivity of wild-type or mutant strains is dependent upon leucine concentration in the media; (3) overexpression of proteins that increase intracellular leucine confer resistance to dieldrin; (4) leucine uptake is inhibited in the presence of dieldrin; and (5) dieldrin induces the amino acid starvation response. Additionally, we demonstrate that appropriate negative regulation of the Ras/protein kinase A pathway, along with an intact pyruvate dehydrogenase complex, is required for dieldrin tolerance. Many yeast genes described in this study have human orthologs that may modulate dieldrin toxicity in humans. PMID:23358190

Impact of pesticide exposure misclassification on estimates of relative risks in the Agricultural Health Study.

PubMed

Blair, Aaron; Thomas, Kent; Coble, Joseph; Sandler, Dale P; Hines, Cynthia J; Lynch, Charles F; Knott, Charles; Purdue, Mark P; Zahm, Shelia Hoar; Alavanja, Michael C R; Dosemeci, Mustafa; Kamel, Freya; Hoppin, Jane A; Freeman, Laura Beane; Lubin, Jay H

2011-07-01

The Agricultural Health Study (AHS) is a prospective study of licensed pesticide applicators and their spouses in Iowa and North Carolina. We evaluate the impact of occupational pesticide exposure misclassification on relative risks using data from the cohort and the AHS Pesticide Exposure Study (AHS/PES). We assessed the impact of exposure misclassification on relative risks using the range of correlation coefficients observed between measured post-application urinary levels of 2,4-dichlorophenoxyacetic acid (2,4-D) and a chlorpyrifos metabolite and exposure estimates based on an algorithm from 83 AHS pesticide applications. Correlations between urinary levels of 2,4-D and a chlorpyrifos metabolite and algorithm estimated intensity scores were about 0.4 for 2,4-D (n=64), 0.8 for liquid chlorpyrifos (n=4) and 0.6 for granular chlorpyrifos (n=12). Correlations of urinary levels with kilograms of active ingredient used, duration of application, or number of acres treated were lower and ranged from -0.36 to 0.19. These findings indicate that a priori expert-derived algorithm scores were more closely related to measured urinary levels than individual exposure determinants evaluated here. Estimates of potential bias in relative risks based on the correlations from the AHS/PES indicate that non-differential misclassification of exposure using the algorithm would bias estimates towards the null, but less than that from individual exposure determinants. Although correlations between algorithm scores and urinary levels were quite good (ie, correlations between 0.4 and 0.8), exposure misclassification would still bias relative risk estimates in the AHS towards the null and diminish study power.

Mobilization of pesticides on an agricultural landscape flooded by a torrential storm.

PubMed

Donald, David B; Hunter, Fraser G; Sverko, Ed; Hill, Bernard D; Syrgiannis, Jim

2005-01-01

Mobilization of pesticides into surface waters of flooded agricultural landscapes following extreme precipitation events has not been previously investigated. After receiving 96 mm of rain in the previous 45 d, the Vanguard area of southeastern Saskatchewan, Canada, was subjected to a torrential storm on July 3, 2000, that produced as much as 375 mm of rain in 8 h. The majority of herbicides, but no insecticides, would have been applied to crops in the Vanguard area during the four weeks preceding the storm. After the storm, 19 herbicides and insecticides were detected in flooded wetlands, with 14 of them detected in 50% or more of wetlands. Average concentrations ranged from 0.43 ng/L (endosulfan) to 362 ng/L (2,4-dichlorophenoxyacedic acid). The pesticides probably were from long-range transport, followed by deposition in rain, and from herbicides applied to crops within the area subjected to the storm (1,700 km2). In the following year, when only 62 mm of rain fell in the same 45 d, only five pesticides were detected in 50% or more of wetlands. We estimated that for the 1,700-km2 storm zone, 278 kg of herbicide were mobilized into rain and by runoff into surface waters, and 105 kg were removed from the Vanguard area by discharge into Notukeu Creek. Significant quantities of herbicides are mobilized to aquatic environments when prairie agricultural landscapes are subjected to torrential storms. In these circumstances, flooded wells and small municipal reservoirs used as sources of drinking water may be compromised by 10 or more pesticides, some at relatively high concentrations.

Construction of a controlled-release delivery system for pesticides using biodegradable PLA-based microcapsules.

PubMed

Liu, Baoxia; Wang, Yan; Yang, Fei; Wang, Xing; Shen, Hong; Cui, Haixin; Wu, Decheng

2016-08-01

Conventional pesticides usually need to be used in more than recommended dosages due to their loss and degradation, which results in a large waste of resources and serious environmental pollution. Encapsulation of pesticides in biodegradable carriers is a feasible approach to develop environment-friendly and efficient controlled-release delivery system. In this work, we fabricated three kinds of polylactic acid (PLA) carriers including microspheres, microcapsules, and porous microcapsules for controlled delivery of Lambda-Cyhalothrin (LC) via premix membrane emulsification (PME). The microcapsule delivery system had better water dispersion than the other two systems. Various microcapsules with a high LC contents as much as 40% and tunable sizes from 0.68 to 4.6μm were constructed by manipulating the process parameters. Compared with LC technical and commercial microcapsule formulation, the microcapsule systems showed a significantly sustained release of LC for a longer period. The LC release triggered by LC diffusion and matrix degradation could be optimally regulated by tuning LC contents and particle sizes of the microcapsules. This multi-regulated release capability is of great significance to achieve the precisely controlled release of pesticides. A preliminary bioassay against plutella xylostella revealed that 0.68μm LC-loaded microcapsules with good UV and thermal stability exhibited an activity similar to a commercial microcapsule formulation. These results demonstrated such an aqueous microcapsule delivery system had a great potential to be further explored for developing an effective and environmentally friendly pesticide-release formulation. Copyright © 2016 Elsevier B.V. All rights reserved.

Efficiency of a bagasse substrate in a biological bed system for the degradation of glyphosate, malathion and lambda-cyhalothrin under tropical climate conditions.

PubMed

de Roffignac, Laure; Cattan, Philippe; Mailloux, Julie; Herzog, David; Le Bellec, Fabrice

2008-12-01

After the rinsing of spray equipment, the rinsing water contains polluting products. One way to avoid pollution is to bring the rinsing water over a purification system, a biological bed. The system consists of an impermeable tub filled with a biomix substrate that facilitates biodegradation of pesticides. Usually, straw is one component of the biomix. The objective of this study was to assess the efficiency of an unusual substrate, bagasse, a residue of sugar cane, for the degradation of three pesticides, glyphosate, malathion and lambda-cyhalothrin. Results showed that more than 99% of malathion and glyphosate were degraded in 6 months. In the biological bed, the DT(50) value for malathion was 17 days, for glyphosate 33 days and for lambda-cyhalothrin 43 days. The degradation rate of aminomethylphosphonic acid (AMPA) residues from the degradation of glyphosate was slower than that of the other pesticides (DT(50) 69 days). Finally, the innocuousness of the biomix after 6 months of degradation was confirmed by biological tests. Although the degradation rates of the three pesticides in the present bagasse-based system were similar to those under temperate conditions, the degradation conditions were improved by comparison with those in soil under the given tropical conditions. Further benefits of this system are pesticide confinement, to avoid their dispersion in the environment by liquids or solids, and a lower overall cost. Finally, possibilities for optimising the bagasse-based system (e.g. management of the water content and nature of the biomix) are discussed.

Occurrence of pesticides in water and sediment collected from amphibian habitats located throughout the United States, 2009-10

USGS Publications Warehouse

Smalling, Kelly L.; Orlando, James L.; Calhoun, Daniel; Battaglin, William A.; Kuivila, Kathryn

2012-01-01

Water and bed-sediment samples were collected by the U.S. Geological Survey (USGS) in 2009 and 2010 from 11 sites within California and 18 sites total in Colorado, Georgia, Idaho, Louisiana, Maine, and Oregon, and were analyzed for a suite of pesticides by the USGS. Water samples and bed-sediment samples were collected from perennial or seasonal ponds located in amphibian habitats in conjunction with research conducted by the USGS Amphibian Research and Monitoring Initiative and the USGS Toxic Substances Hydrology Program. Sites selected for this study in three of the states (California, Colorado, and Orgeon) have no direct pesticide application and are considered undeveloped and remote. Sites selected in Georgia, Idaho, Louisiana, and Maine were in close proximity to either agricultural or suburban areas. Water and sediment samples were collected once in 2009 during amphibian breeding seasons. In 2010, water samples were collected twice. The first sampling event coincided with the beginning of the frog breeding season for the species of interest, and the second event occurred 10-12 weeks later when pesticides were being applied to the surrounding areas. Additionally, water was collected during each sampling event to measure dissolved organic carbon, nutrients, and the fungus, Batrachochytrium dendrobatidis, which has been linked to amphibian declines worldwide. Bed-sediment samples were collected once during the beginning of the frog breeding season, when the amphibians are thought to be most at risk to pesticides. Results of this study are reported for the following two geographic scales: (1) for a national scale, by using data from the 29 sites that were sampled from seven states, and (2) for California, by using data from the 11 sampled sites in that state. Water samples were analyzed for 96 pesticides by using gas chromatography/mass spectrometry. A total of 24 pesticides were detected in one or more of the 54 water samples, including 7 fungicides, 10 herbicides, 4 insecticides, 1 synergist, and 2 pesticide degradates. On a national scale, aminomethylphosphonic acid (AMPA), the primary degradate of the herbicide glyphosate, which is the active ingredient in Roundup®, was the most frequently detected pesticide in water (16 of 54 samples) followed by glyphosate (8 of 54 samples). The maximum number of pesticides observed at a single site was nine compounds in a water sample from a site in Louisiana. The maximum concentration of a pesticide or degradate observed in water was 2,880 nanograms per liter of clomazone (a herbicide) at a site in Louisiana. In California, a total of eight pesticides were detected among all of the low and high elevation sites; AMPA was the most frequently detected pesticide, but glyphosate was detected at the highest concentrations (1.1 micrograms per liter). Bed-sediment samples were analyzed for 94 pesticides by using accelerated solvent extraction, gel permeation chromatography for sulfur removal, and carbon/alumina stacked solid-phase extraction cartridges to remove interfering sediment matrices. In bed sediment, 22 pesticides were detected in one or more of the samples, including 9 fungicides, 3 pyrethroid insecticides, p,p'-dichlorodiphenyltrichloroethane (p,p'-DDT) and its major degradates, as well as several herbicides. Pyraclostrobin, a strobilurin fungicide, and bifenthrin, a pyrethroid insecticide, were detected most frequently. Maximum pesticide concentrations ranged from less than their respective method detection limits to 1,380 micrograms per kilogram (tebuconazole in California). The number of pesticides detected in samples from each site ranged from zero to six compounds. The sites with the greatest number of pesticides were in Maine and Oregon with six pesticides detected in one sample from each state, followed by Georgia with four pesticides in one sample. For California, a total of 10 pesticides were detected among all sites, and 4 pesticides were detected at both low and high elevation sites; tebuconazole and pyraclostrobin were the two most frequently detected pesticides in California. For the other six selected states, the most frequently detected pesticides in bed sediment were pyraclostrobin (detected in 17 of 42 samples), bifenthrin (detected in 14 of 42 samples), and tebuconazole (detected in 10 of 42 samples). The fungus, Batrachochytrium dendrobatidis (Bd), was detected in water samples in sites from four of the seven states during 2009 and 2010, and the number of zoospore equivalents per liter of water in samples where Bd was detected ranged from 1.6 to 343. Bd was not detected in water samples from sites in Georgia, Louisiana, and Oregon.

Water and UV degradable lactic acid polymers

DOEpatents

Bonsignore, Patrick V.; Coleman, Robert D.

1996-01-01

A water and UV light degradable copolymer of monomers of lactic acid and a modifying monomer selected from the class consisting of ethylene glycol, propylene glycol, P-dioxanone, 1,5 dioxepan-2-one, 1,4-oxathialan-2-one, 1,4-dioxide and mixtures thereof. These copolymers are useful for waste disposal and agricultural purposes. Also disclosed is a water degradable blend of polylactic acid or modified polylactic acid and high molecular weight polyethylene oxide wherein the high molecular weight polyethylene oxide is present in the range of from about 2 by weight to about 50% by weight, suitable for films. A method of applying an active material selected from the class of seeds, seedlings, pesticides, herbicides, fertilizers and mixtures thereof to an agricultural site is also disclosed.

Determination of dissociation constants of compounds with potential cognition enhancing activity by capillary zone electrophoresis.

PubMed

Lisková, Anna; Krivánková, Ludmila

2005-12-01

Accurate determination of pK(a) values is important for proper characterization of newly synthesized molecules. In this work we have used CZE for determination of pK(a) values of new compounds prepared from intermediates, 2, 3 and 4-(2-chloro-acetylamino)-phenoxyacetic acids, by substituting chloride for 2-oxo-pyrrolidine, 2-oxo-piperidine or 2-oxo-azepane. These substances are expected to have a cognition enhancing activity and free radicals scavenging effect. Measurements were performed in a polyacrylamide-coated fused-silica capillary of 0.075 mm ID using direct UV detection at 254 nm. Three electrolyte systems were used for measurements to eliminate effects of potential interactions between tested compounds and components of the BGE. In the pH range 2.7-5.4, chloride, formate, acetate and phosphate were used as BGE co-ions, and sodium, beta-alanine and epsilon-aminocaproate as counterions. Mobility standards were measured simultaneously with the tested compounds for calculations of correct electrophoretic mobilities. Several approaches for the calculation of the pK(a) values were used. The values of pK(a) were determined by standard point-to-point calculation using Henderson-Hasselbach equation. Mobility and pH data were also evaluated by using nonlinear regression. Three parameter sigmoidal function fitted the experimental data with correlation coefficients higher than 0.99. Results from CZE measurements were compared with spectrophotometric measurements performed in sodium formate buffer solutions and evaluated at wavelength where the highest absorbance difference for varying pH was recorded. The experimental pK(a) values were compared with corresponding values calculated by the SPARC online calculator. Results of all three used methods were in good correlation.

Use and occurrence of pesticides in the Apalachicola-Chattahoochee-Flint River basin, Georgia, Alabama, and Florida, 1960-91

USGS Publications Warehouse

Stell, Susan M.; Hopkins, Evelyn H.; Buell, Gary R.; Hippe, Daniel J.

1995-01-01

The Apalachicola-Chattahoochee-Flint (ACF) River basin was one of the first 20 study units selected in 1991 by the U.S. Geological Survey for its National Water-Quality Assessment (NAWQA) program. Because pesticide contamination of surface water and ground water is a concern nationwide, a major emphasis of the NAWQA program is to examine the occurrence and distribution of pesticides in the water resources of these study unit basins. An understanding of the types and distribution of land uses; pesticide properties, pest-control practices, and pesticide use; and an evaluation of the occurrence and distribution of pesticides in the water resources of the ACF are necessary to meet this objective of the NAWQA program. This report describes land use and pesticide use at a county level, and the occurrence and distribution of pesticides in the water resources of the ACF River basin on the basis of previously-collected data. About 33 percent of the ACF River basin is used for agriculture, 16 percent is used for silviculture, and about 5 percent of the basin is in urban and suburban settings; primarily the Columbus, Albany, and Atlanta Metropolitan areas. The remainder is in wetlands and non-silvicultural forest. A broad range of synthetic-organic herbicides, insecticides, and fungicides are applied to land in agricultural, silvicultural, urban, and suburban areas. The period of intensive pesticide applications extends from March to October. Pesticide data available for the period from 1971 through 1989 in the U.S. Geological Survey National Water Information System (NWIS) and for the period from 1960 through 1991 in the U.S. Environmental Protection Agency Storage and Retrieval System (STORET) were analyzed to describe the occurrence and distribution of pesticides in water resources of the ACF River basin. Collectively, the NWIS and STORET databases contain about 19,600 individual analyses for pesticide concentration in the ACF River basin. Pesticide concentrations were at or above a minimum reporting level in about five percent of all analyses. Most of the pesticide analyses and most of the analyses having concentrations above minimum reporting levels in these databases are for organochlorine insecticides in samples collected five or more years before this study. With few exceptions, most of organochlorine insecticides are now banned from use in the United States. Concentrations of currently (1991) used pesticides were at or above a minimum reporting level in about 0.3 percent of the analyses. The geographic patterns in the occurrence and distribution of pesticides in the ACF River basin (as defined by data collected during 1960-91) are, as expected, somewhat defined by land-use patterns. DDT (together with DDD and DDE) were detected in wide distribution in the sediments and aquatic biota of primarily mainstem and reservoir sites in the Chattahoochee, Flint, and Apalachicola drainages. DDT was used through 1973 as an insecticide on cotton, fruits, and vegetables; and for mosquito control, so its widespread occurrence in both urban and agricultural settings is consistent with its use. Chlordane, heptachlor, dieldrin, and related compounds were agriculturally used through 1974, but predominantly as termiticides through the late 1980?s. Compounds in these groups have been found in the sediments and aquatic biota of tributary streams draining the Atlanta Metropolitan area and of mainstem reaches and reservoirs of the Chattahoochee River downstream from the Atlanta and Columbus, Ga., Metropolitan areas. The phenoxy-acid herbicides are widely used in residential, commercial/industrial, agricultural, and silvicultural areas of the ACF River basin. Detectable concentrations of 2,4-D were found in most of the surface-waters sampled in the Atlanta Metropolitan area. It is unfortunate that only limited inference can be drawn on temporal patterns. Many of the Federal and State agency pesticide-monitoring programs have been targeted

Hydropower reservoirs: cytotoxic and genotoxic assessment using the Allium cepa root model.

PubMed

Rambo, Cassiano Lazarotto; Zanotelli, Patrícia; Dalegrave, Daniela; De Nez, Dinara; Szczepanik, Jozimar; Carazek, Fábio; Franscescon, Francini; Rosemberg, Denis Broock; Siebel, Anna Maria; Magro, Jacir Dal

2017-03-01

Hydropower offers a reliable source of electricity in several countries, and Brazil supplies its energy needs almost entirely through hydropower plants. Nevertheless, hydropower plants comprise large buildings and water reservoirs and dams, resulting in huge ecological disruptions. Here, we analyzed the impact of four hydropower reservoirs construction in metals and pesticides incidence and the cytotoxic and genotoxic potential of sediment elutriate of rivers from southern Brazil. Our analyses have evidenced the elevated incidence of different metals (lead, iron, cadmium, and chrome) and pesticides (methyl parathion, atrazine, and 2,4-dichlorophenoxyacetic acid). We showed that Allium cepa exposed to sediment elutriates did not change the seed germination rate and mitotic index. However, roots from Allium cepa exposed to reservoirs sediment elutriates showed increased occurrence of chromosomal aberrations and nuclear abnormalities. Therefore, the results obtained in our study indicate that sediment from reservoirs present elevated concentration of metals and pesticides and a significant genotoxic potential. Taken together, our data support that hydropower reservoirs represent an environmental scenario that could impact surrounding wildlife and population.

[Microbial degradation of 3-phenoxybenzoic acid--A review].

PubMed

Deng, Weiqin; Liu, Shuliang; Yao, Kai

2015-09-04

3-phenoxybenzoic acid (3-PBA) with estrogen toxicity is one of the intermediate products of most pyrethroid pesticides. 3-PBA is difficult to degrade in the natural environment, and threatens food safety and human health. Microbial degradation of pyrethroids and their intermediate product (3-PBA) has become a hot topic in recent years. Here, we reviewed microbial species, degrading enzymes and degradation genes, degradation pathways of 3-PBA degrading and the application of 3-PBA degradation strains. This article provides references for the study of 3-PBA degradation by microorganisms.

Toxico-pathological effects in rats induced by lambda-cyhalothrin.

PubMed

Dahamna, S; Harzallah, D; Guemache, A; Sekfali, N

2009-01-01

Pesticides are widely used chemicals making human exposure to pesticides a realistic possibility. Biomonitoring is a common and useful tool for assessing human exposure to pesticides. Pyrethroids are effective insecticides that are often used in household sprays, aerosol bombs, insect repellents, pet shampoos, and lice treatments. Using products containing these compounds will expose people to these chemicals. Since these compounds frequently are used on crOPs, they are often detected in fruits and vegetables. Biomonitoring of exposure is a useful tool for assessing exposure to pesticides. Biomonitoring involves the measurement of the parent pesticide, its metabolite or reaction product in biological media, typically blood or urine, to determine if an exposure has occurred and the extent of that exposure. Although not without its limitations, biomonitoring has great utility in integrating all routes of exposure allowing for one exposure measurement. Pesticides have much shorter environmental half-lives and tend not to bioaccumulate. In fact, from humans within 24 hr as the parent pesticide, a mercapturic acid detoxification product, oxidative or dealkylation metabolites, and/or glucuronide or sulphate-bound metabolites. However, because of the heavy agricultural and residential use of these chemicals, humans are continually exposed to many of these chemicals. The objective of the present study was to explore modification in toxico-pathological responses of rats treated with lambda-cyhalothrin (commercially called karate). Rats (250 g weight), were gavaged by 1/100 LD50 for 4 weeks (one dose every week). Blood was collected before dosing and after 48 hours from the treatment. Enzyme activities were assayed in the plasma samples obtained. Glutamate oxaloacetate transaminase (GOT), Glutamate pyruvate transaminase (GPT), Alkaline phosphatase (ALPH) and Glucose. The results showed a decrease in RBC; WBC and Hb. This probably explained by the effect of lambda cyhalothrin on the erythropoiesis and the destruction of cells. An increase of plasma enzyme activities in GOT and GPT were recorded, explain a high energy-generating product. The histopathological results showed alteration on the target organs such as liver and kidney, these biochemical and histological modifications are probably due to the effect of lambda cyhalothrin or their metabolites.

Zebrafish seizure model identifies p,p -DDE as the dominant contaminant of fetal California sea lions that accounts for synergistic activity with domoic acid.

PubMed

Tiedeken, Jessica A; Ramsdell, John S

2010-04-01

Fetal poisoning of California sea lions (CSLs; Zalophus californianus) has been associated with exposure to the algal toxin domoic acid. These same sea lions accumulate a mixture of persistent environmental contaminants including pesticides and industrial products such as polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). Developmental exposure to the pesticide dichlorodiphenyltrichloroethane (DDT) and its stable metabolite 1,1-bis-(4-chlorophenyl)-2,2-dichloroethene (p,p -DDE) has been shown to enhance domoic acid-induced seizures in zebrafish; however, the contribution of other co-occurring contaminants is unknown. We formulated a mixture of contaminants to include PCBs, PBDEs, hexachlorocyclohexane (HCH), and chlordane at levels matching those reported for fetal CSL blubber to determine the impact of co-occurring persistent contaminants with p,p -DDE on chemically induced seizures in zebrafish as a model for the CSLs. Embryos were exposed (6-30 hr postfertilization) to p,p -DDE in the presence or absence of a defined contaminant mixture prior to neurodevelopment via either bath exposure or embryo yolk sac microinjection. After brain maturation (7 days postfertilization), fish were exposed to a chemical convulsant, either pentylenetetrazole or domoic acid; resulting seizure behavior was then monitored and analyzed for changes, using cameras and behavioral tracking software. Induced seizure behavior did not differ significantly between subjects with embryonic exposure to a contaminant mixture and those exposed to p,p -DDE only. These studies demonstrate that p,p -DDE--in the absence of PCBs, HCH, chlordane, and PBDEs that co-occur in fetal sea lions--accounts for the synergistic activity that leads to greater sensitivity to domoic acid seizures.

Review of Pesticide Urinary Biomarker Measurements from Selected US EPA Children’s Observational Exposure Studies

PubMed Central

Egeghy, Peter P.; Cohen Hubal, Elaine A.; Tulve, Nicolle S.; Melnyk, Lisa J.; Morgan, Marsha K.; Fortmann, Roy C.; Sheldon, Linda S.

2011-01-01

Children are exposed to a wide variety of pesticides originating from both outdoor and indoor sources. Several studies were conducted or funded by the EPA over the past decade to investigate children’s exposure to organophosphate and pyrethroid pesticides and the factors that impact their exposures. Urinary metabolite concentration measurements from these studies are consolidated here to identify trends, spatial and temporal patterns, and areas where further research is required. Namely, concentrations of the metabolites of chlorpyrifos (3,5,6-trichloro-2-pyridinol or TCPy), diazinon (2-isopropyl-6-methyl-4-pyrimidinol or IMP), and permethrin (3-phenoxybenzoic acid or 3-PBA) are presented. Information on the kinetic parameters describing absorption and elimination in humans is also presented to aid in interpretation. Metabolite concentrations varied more dramatically across studies for 3-PBA and IMP than for TCPy, with TCPy concentrations about an order of magnitude higher than the 3-PBA concentrations. Temporal variability was high for all metabolites with urinary 3-PBA concentrations slightly more consistent over time than the TCPy concentrations. Urinary biomarker levels provided only limited evidence of applications. The observed relationships between urinary metabolite levels and estimates of pesticide intake may be affected by differences in the contribution of each exposure route to total intake, which may vary with exposure intensity and across individuals. PMID:21655147

Interactions between amino-phosphonates pesticides and titanium dioxide nanoparticle in water: consequences on their mobility

NASA Astrophysics Data System (ADS)

Ilina, Svetlana; Baran, Nicole; Slomberg, Danielle; Devau, Nicolas; Pariat, Anne; Sani-Kast, Nicole; Scheringer, Martin; Labille, Jérôme; Ollivier, patrick

2017-04-01

Water quality is increasingly monitored worldwide, where various levels of nitrate and pesticide and/or metabolite contamination have been confirmed. Glyphosate [N-(phosphonomethyl)glycine] is probably the most widely used herbicide in the world. AMPA [aminomethylphosphonic acid] is its main degradation product. Although glyphosate mobility in the environment is supposed to be limited because of its high adsorption capacity in soils several studies show that glyphosate may reach both surface and ground-waters either by transport in dissolved form, or particle bonded onto soil colloids. At the same time, in recent years, rapid development of new technologies has resulted in a significant increase in the production and uses of products containing nanoparticles, notably dioxide titanium nanoparticles. This enthusiasm for nanotechnology is however accompanied by awareness about the potential release and impact of the nanoparticles in the environment. The aim of the study is to increase the knowledge on pesticide and nanoparticles interactions that may be present as contaminant cocktail in waters. Thanks to lab-experiments conducted with glyphosate or AMPA and rutile or anatase under different water chemistry conditions (pH, ionic strength, presence and concentrations of mono- and bivalent cations), we were able to describe the colloidal stability of nanoparticles that control their mobility and to characterize the sorption of pesticide on these nanoparticles and their transformation.

Budding trends in integrated pest management using advanced micro- and nano-materials: Challenges and perspectives.

PubMed

Khandelwal, Neha; Barbole, Ranjit S; Banerjee, Shashwat S; Chate, Govind P; Biradar, Ankush V; Khandare, Jayant J; Giri, Ashok P

2016-12-15

One of the most vital supports to sustain human life on the planet earth is the agriculture system that has been constantly challenged in terms of yield. Crop losses due to insect pest attack even after excessive use of chemical pesticides, are major concerns for humanity and environment protection. By the virtue of unique properties possessed by micro and nano-structures, their implementation in Agri-biotechnology is largely anticipated. Hence, traditional pest management strategies are now forestalling the potential of micro and nanotechnology as an effective and viable approach to alleviate problems pertaining to pest control. These technological innovations hold promise to contribute enhanced productivity by providing novel agrochemical agents and delivery systems. Application of these systems engages to achieve: i) control release of agrochemicals, ii) site-targeted delivery of active ingredients to manage specific pests, iii) reduced pesticide use, iv) detection of chemical residues, v) pesticide degradation, vi) nucleic acid delivery and vii) to mitigate post-harvest damage. Applications of micro and nano-technology are still marginal owing to the perception of low economic returns, stringent regulatory issues involving safety assessment and public awareness over their uses. In this review, we highlight the potential application of micro and nano-materials with a major focus on effective pest management strategies including safe handling of pesticides. Copyright © 2016 Elsevier Ltd. All rights reserved.

Simultaneous enantioselective determination of six pesticides in aqueous environmental samples by chiral liquid chromatography with tandem mass spectrometry.

PubMed

Zhao, Pengfei; Lei, Shuo; Xing, Mingming; Xiong, Shihang; Guo, Xingjie

2018-03-01

A robust and sensitive method was developed for the enantiomeric analysis of six chiral pesticides (including metalaxyl, epoxiconazole, myclobutanil, hexaconazole, napropamide, and isocarbophos) in aquatic environmental samples. The optimized chromatographic conditions for the quantification of all the 12 enantiomers were performed with Chiralcel OD-RH column using mobile phase consisting of 0.1% aqueous formic acid and acetonitrile operated under reversed-phase conditions and then analyzed using liquid chromatography with tandem mass spectrometry. Twelve enantiomers were detected in multiple reaction monitoring mode. Solid-phase extraction and dispersive liquid-liquid microextraction were employed in this study. Response surface methodology was applied to assist in the dispersive liquid-liquid microextraction optimization. Under the optimum conditions, recoveries of pesticides enantiomers varied from 83.0 to 103.2% at two spiked levels with relative standard deviation less than 11.5%. The concentration factors were up to 1000 times. Method detection and quantification limits varied from 0.11 to 0.48 ng/L and from 0.46 to 1.49 ng/L, respectively. Finally, this method was used to determination of the enantiomers composition of the six pesticides in environmental aqueous matrices, which will help better understand the behavior of individual enantiomer and make accurate risk assessment to ecosystems. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemoproteomic Profiling of Acetanilide Herbicides Reveals Their Role in Inhibiting Fatty Acid Oxidation.

PubMed

Counihan, Jessica L; Duckering, Megan; Dalvie, Esha; Ku, Wan-Min; Bateman, Leslie A; Fisher, Karl J; Nomura, Daniel K

2017-03-17

Acetanilide herbicides are among the most widely used pesticides in the United States, but their toxicological potential and mechanisms remain poorly understood. Here, we have used chemoproteomic platforms to map proteome-wide cysteine reactivity of acetochlor (AC), the most widely used acetanilide herbicide, in vivo in mice. We show that AC directly reacts with >20 protein targets in vivo in mouse liver, including the catalytic cysteines of several thiolase enzymes involved in mitochondrial and peroxisomal fatty acid oxidation. We show that the fatty acids that are not oxidized, due to impaired fatty acid oxidation, are instead diverted into other lipid pathways, resulting in heightened free fatty acids, triglycerides, cholesteryl esters, and other lipid species in the liver. Our findings show the utility of chemoproteomic approaches for identifying novel mechanisms of toxicity associated with environmental chemicals like acetanilide herbicides.

pH dependence and unsuitability of fluorescein dye as a tracer for pesticide mobility studies in acid soil

Treesearch

Chris Peterson

2009-01-01

The mobility of fluorescein and bromide used as tracers in packed soil columns was investigated.Five different soils were used in two application methods: soil surface application and soil incorporation, both of which simulate accepted methods of soil application of termiticides to prevent structural infestation. The...

75 FR 52269 - Acetic Acid Ethenyl Ester, Polymer With Oxirane; Tolerance Exemption

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-25

... result of pesticide use in residential settings. If EPA is able to determine that a finite tolerance is... contain as an integral part of its composition the atomic elements carbon, hydrogen, and oxygen. 3. The polymer does not contain as an integral part of its composition, except as impurities, any element other...

40 CFR 180.1110 - 3-Carbamyl-2,4,5-trichloro-benzoic acid; exemption from the requirement of a tolerance.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 23 2010-07-01 2010-07-01 false 3-Carbamyl-2,4,5-trichloro-benzoic... Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR...) and (b) and/or as an inadvertent residue resulting from the soil metabolism of chlorothalonil when...

Exposures of 129 preschool children to organochlorines, organophosphates, pyrethroids, and acid herbicides at their homes and daycares in North Carolina

EPA Science Inventory

Few data exist on the concurrent exposures of young children to past-use and current-use pesticides in their everyday environments. In this further analysis of study data, we quantified the potential exposures and intake doses of 129 preschool children, ages 20 to 66 months, to 1...

Prioritizing Chemicals for Risk Assessment Using Chemoinformatics: Examples from the IARC Monographs on Pesticides.

PubMed

Guha, Neela; Guyton, Kathryn Z; Loomis, Dana; Barupal, Dinesh Kumar

2016-12-01

Identifying cancer hazards is the first step towards cancer prevention. The International Agency for Research on Cancer (IARC) Monographs Programme, which has evaluated nearly 1,000 agents for their carcinogenic potential since 1971, typically selects agents for hazard identification on the basis of public nominations, expert advice, published data on carcinogenicity, and public health importance. Here, we present a novel and complementary strategy for identifying agents for hazard evaluation using chemoinformatics, database integration, and automated text mining. To inform selection among a broad range of pesticides nominated for evaluation, we identified and screened nearly 6,000 relevant chemical structures, after which we systematically compiled information on 980 pesticides, creating network maps that allowed cluster visualization by chemical similarity, pesticide class, and publicly available information concerning cancer epidemiology, cancer bioassays, and carcinogenic mechanisms. For the IARC Monograph meetings that took place in March and June 2015, this approach supported high-priority evaluation of glyphosate, malathion, parathion, tetrachlorvinphos, diazinon, p,p'-dichlorodiphenyltrichloroethane (DDT), lindane, and 2,4-dichlorophenoxyacetic acid (2,4-D). This systematic approach, accounting for chemical similarity and overlaying multiple data sources, can be used by risk assessors as well as by researchers to systematize, inform, and increase efficiency in selecting and prioritizing agents for hazard identification, risk assessment, regulation, or further investigation. This approach could be extended to an array of outcomes and agents, including occupational carcinogens, drugs, and foods. Citation: Guha N, Guyton KZ, Loomis D, Barupal DK. 2016. Prioritizing chemicals for risk assessment using chemoinformatics: examples from the IARC Monographs on Pesticides. Environ Health Perspect 124:1823-1829; http://dx.doi.org/10.1289/EHP186.

Prioritizing Chemicals for Risk Assessment Using Chemoinformatics: Examples from the IARC Monographs on Pesticides

PubMed Central

Guha, Neela; Guyton, Kathryn Z.; Loomis, Dana; Barupal, Dinesh Kumar

2016-01-01

Background: Identifying cancer hazards is the first step towards cancer prevention. The International Agency for Research on Cancer (IARC) Monographs Programme, which has evaluated nearly 1,000 agents for their carcinogenic potential since 1971, typically selects agents for hazard identification on the basis of public nominations, expert advice, published data on carcinogenicity, and public health importance. Objectives: Here, we present a novel and complementary strategy for identifying agents for hazard evaluation using chemoinformatics, database integration, and automated text mining. Discussion: To inform selection among a broad range of pesticides nominated for evaluation, we identified and screened nearly 6,000 relevant chemical structures, after which we systematically compiled information on 980 pesticides, creating network maps that allowed cluster visualization by chemical similarity, pesticide class, and publicly available information concerning cancer epidemiology, cancer bioassays, and carcinogenic mechanisms. For the IARC Monograph meetings that took place in March and June 2015, this approach supported high-priority evaluation of glyphosate, malathion, parathion, tetrachlorvinphos, diazinon, p,p′-dichlorodiphenyltrichloroethane (DDT), lindane, and 2,4-dichlorophenoxyacetic acid (2,4-D). Conclusions: This systematic approach, accounting for chemical similarity and overlaying multiple data sources, can be used by risk assessors as well as by researchers to systematize, inform, and increase efficiency in selecting and prioritizing agents for hazard identification, risk assessment, regulation, or further investigation. This approach could be extended to an array of outcomes and agents, including occupational carcinogens, drugs, and foods. Citation: Guha N, Guyton KZ, Loomis D, Barupal DK. 2016. Prioritizing chemicals for risk assessment using chemoinformatics: examples from the IARC Monographs on Pesticides. Environ Health Perspect 124:1823–1829; http://dx.doi.org/10.1289/EHP186 PMID:27164621

Rapid and Simultaneous Analysis of 360 Pesticides in Brown Rice, Spinach, Orange, and Potato Using Microbore GC-MS/MS.

PubMed

Lee, Jonghwa; Kim, Leesun; Shin, Yongho; Lee, Junghak; Lee, Jiho; Kim, Eunhye; Moon, Joon-Kwan; Kim, Jeong-Han

2017-04-26

A multiresidue method for the simultaneous and rapid analysis of 360 pesticides in representative agricultural produce (brown rice, orange, spinach, and potato) was developed using a modified QuEChERS procedure combined with gas chromatography-tandem mass spectrometry (GC-MS/MS). Selected reaction monitoring transition parameters (e.g., collision energy, precursor and product ions) in MS/MS were optimized to achieve the best selectivity and sensitivity for a wide range of GC-amenable pesticides. A short (20 m) microbore (0.18 mm i.d.) column resulted in better signal-to-noise ratio with reduced analysis time than a conventional narrowbore column (30 m × 0.25 mm i.d.). The priming injection dramatically increased peak areas by masking effect on a new GC liner. The limit of quantitation was <0.01 mg/kg, and the correlation coefficients (r 2 ) of matrix-matched standards were >0.99 within the range of 0.0025-0.1 mg/kg. Acetonitrile with 0.1% formic acid without additional buffer salts was used for pesticide extraction, whereas only primary-secondary amine (PSA) was used for dispersive solid phase extraction (dSPE) cleanup, to achieve good recoveries for most of the target analytes. The recoveries ranged from 70 to 120% with relative standard deviations of ≤20% at 0.01 and 0.05 mg/kg spiking levels (n = 6) in all samples, indicating acceptable accuracy and precision of the method. Seventeen real samples from local markets were analyzed by using the optimized method, and 14 pesticides in 11 incurred samples were found at below the maximum residue limits.

Persistence in and Release of 2,4-D and Azoxystrobin from Turfgrass Clippings.

PubMed

Jeffries, Matthew D; Yelverton, Fred H; Ahmed, Khalied A; Gannon, Travis W

2016-11-01

Research has shown that pesticide residue in clippings from previously treated turfgrass may become bioavailable as grass decomposes, adversely affecting off-target organisms. We conducted a field study to quantify 2,4-D (2,4-dichlorophenoxyacetic acid) and azoxystrobin (methyl(E)-2-{2[6-(2-cyanophenoxy)pyrmidin-4-yloxy]phenyl}-3-methoxyacrylate) residues in turfgrass clippings collected from hybrid bermudagrass [ (L.) Pers. × Burtt-Davy], tall fescue [ (Schreb.) S.J. Darbyshire], and zoysiagrass ( Steud.). A subsequent greenhouse experiment was conducted to measure pesticide release from clippings into water. 2,4-D (1.6 kg a.i. ha) and azoxystrobin (0.6 kg a.i. ha) were applied to field plots at 32, 16, 8, 4, 2, 1, or 0 d before collection of the clippings. Clippings were collected from each experimental unit to quantify pesticide release from clippings into water. Both 2,4-D and azoxystrobin were detected when turfgrass was treated over the 32-d experimental period, suggesting that clipping management should be implemented for an extended period of time after application. Pesticide residue was detected in all water samples collected, confirming 2,4-D and azoxystrobin release from turfgrass clippings; however, pesticide release varied between compounds. Two days after clippings were incorporated in water, 39 and 10% of 2,4-D and azoxystrobin were released from clippings, respectively. Our research supports the currently recommended practice of returning clippings to the turfgrass stand when mowing because removal of 2,4-D and azoxystrobin in clippings may reduce pest control and cause adverse off-target impacts. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Cross-sectional biomonitoring study of pesticide exposures in Queensland, Australia, using pooled urine samples.

PubMed

Heffernan, A L; English, K; Toms, Lml; Calafat, A M; Valentin-Blasini, L; Hobson, P; Broomhall, S; Ware, R S; Jagals, P; Sly, P D; Mueller, J F

2016-12-01

A range of pesticides are available in Australia for use in agricultural and domestic settings to control pests, including organophosphate and pyrethroid insecticides, herbicides, and insect repellents, such as N,N-diethyl-meta-toluamide (DEET). The aim of this study was to provide a cost-effective preliminary assessment of background exposure to a range of pesticides among a convenience sample of Australian residents. De-identified urine specimens stratified by age and sex were obtained from a community-based pathology laboratory and pooled (n = 24 pools of 100 specimens). Concentrations of urinary pesticide biomarkers were quantified using solid-phase extraction coupled with isotope dilution high-performance liquid chromatography-tandem mass spectrometry. Geometric mean biomarker concentrations ranged from <0.1 to 36.8 ng/mL for organophosphate insecticides, <0.1 to 5.5 ng/mL for pyrethroid insecticides, and <0.1 to 8.51 ng/mL for all other biomarkers with the exception of the DEET metabolite 3-diethylcarbamoyl benzoic acid (4.23 to 850 ng/mL). We observed no association between age and concentration for most biomarkers measured but noted a "U-shaped" trend for five organophosphate metabolites, with the highest concentrations observed in the youngest and oldest age strata, perhaps related to age-specific differences in behavior or physiology. The fact that concentrations of specific and non-specific metabolites of the organophosphate insecticide chlorpyrifos were higher than reported in USA and Canada may relate to differences in registered applications among countries. Additional biomonitoring programs of the general population and focusing on vulnerable populations would improve the exposure assessment and the monitoring of temporal exposure trends as usage patterns of pesticide products in Australia change over time.

Water and UV degradable lactic acid polymers

DOEpatents

Bonsignore, P.V.; Coleman, R.D.

1994-11-01

A water and UV light degradable copolymer of monomers of lactic acid and a modifying monomer were selected from the class consisting of ethylene and polyethylene glycols, propylene and polypropylene glycols, P-dioxanone, 1,5 dioxepan-2-one, 1,4 -oxathialan-2-one, 1,4-dioxide and mixtures. These copolymers are useful for waste disposal and agricultural purposes. Also disclosed is a water degradable blend of polylactic acid or modified polylactic acid and high molecular weight polyethylene oxide where the high molecular weight polyethylene oxide is present in the range of from about 2% by weight to about 50% by weight, suitable for films. A method of applying an active material selected from the class of seeds, seedlings, pesticides, herbicides, fertilizers and mixtures to an agricultural site is also disclosed.

Water and UV degradable lactic acid polymers

DOEpatents

Bonsignore, P.V.; Coleman, R.D.

1996-10-08

A water and UV light degradable copolymer is described made from monomers of lactic acid and a modifying monomer selected from the class consisting of ethylene glycol, propylene glycol, P-dioxanone, 1,5 dioxepan-2-one, 1,4-oxathialan-2-one, 1,4-dioxide and mixtures thereof. These copolymers are useful for waste disposal and agricultural purposes. Also disclosed is a water degradable blend of polylactic acid or modified polylactic acid and high molecular weight polyethylene oxide wherein the high molecular weight polyethylene oxide is present in the range of from about 2 by weight to about 50% by weight, suitable for films. A method of applying an active material selected from the class of seeds, seedlings, pesticides, herbicides, fertilizers and mixtures thereof to an agricultural site is also disclosed.

Water and UV degradable lactic acid polymers

DOEpatents

Bonsignore, Patrick V.; Coleman, Robert D.

1994-01-01

A water and UV light degradable copolymer of monomers of lactic acid and a modifying monomer selected from the class consisting of ethylene and polyethylene glycols, propylene and polypropylene glycols, P-dioxanone, 1,5 dioxepan-2-one, 1,4 -oxathialan-2-one, 1,4-dioxide and mixtures thereof. These copolymers are useful for waste disposal and agricultural purposes. Also disclosed is a water degradable blend of polylactic acid or modified polylactic acid and high molecular weight polyethylene oxide wherein the high molecular weight polyethylene oxide is present in the range of from about 2% by weight to about 50% by weight, suitable for films. A method of applying an active material selected from the class of seeds, seedlings, pesticides, herbicides, fertilizers and mixtures thereof to an agricultural site is also disclosed.

Surface-water-quality assessment of the Yakima River basin, Washington; distribution of pesticides and other organic compounds in water, sediment, and aquatic biota, 1987-91; with a section on dissolved organic carbon in the Yakima River basin

USGS Publications Warehouse

Rinella, Joseph F.; McKenzie, Stuart W.; Crawford, J. Kent; Foreman, William T.; Fuhrer, Gregory J.; Morace, Jennifer L.; Aiken, George R.

1999-01-01

During 1987-91, chemical data were collected for pesticides and other organic compounds in surface water, streambed sediment, suspended sediment, agricultural soil, and aquatic biota to determine the occurrence, distribution, transport, and fate of organic compounds in the Yakima River basin in Washington. The report describes the chemical and physical properties of the compounds most frequently detected in the water column; organochlorine compounds including DDT, organophosphorus compounds, thiocarbamate and sulfite compounds, acetamide and triazine compounds, and chlorophenoxy-acetic acid and benzoic compounds. Concentrations are evaluated relative to chronic-toxicity water quality criteria and guidelines for the protection of human health and freshwater aquatic life.

Quantitative carbon detector for enhanced detection of molecules in foods, pharmaceuticals, cosmetics, flavors, and fuels.

PubMed

Beach, Connor A; Krumm, Christoph; Spanjers, Charles S; Maduskar, Saurabh; Jones, Andrew J; Dauenhauer, Paul J

2016-03-07

Analysis of trace compounds, such as pesticides and other contaminants, within consumer products, fuels, and the environment requires quantification of increasingly complex mixtures of difficult-to-quantify compounds. Many compounds of interest are non-volatile and exhibit poor response in current gas chromatography and flame ionization systems. Here we show the reaction of trimethylsilylated chemical analytes to methane using a quantitative carbon detector (QCD; the Polyarc™ reactor) within a gas chromatograph (GC), thereby enabling enhanced detection (up to 10×) of highly functionalized compounds including carbohydrates, acids, drugs, flavorants, and pesticides. Analysis of a complex mixture of compounds shows that the GC-QCD method exhibits faster and more accurate analysis of complex mixtures commonly encountered in everyday products and the environment.

Input dynamics of pesticide transformation products into surface water

NASA Astrophysics Data System (ADS)

Kern, Susanne; Singer, Heinz; Hollender, Juliane; Schwarzenbach, René P.; Fenner, Kathrin

2010-05-01

Some pesticide transformation products have been observed to occur in higher concentrations and more frequently than the parent active pesticide in surface water and groundwater. These products are often more mobile and sometimes more stable than the parent pesticide. If they also represent the major product into which the parent substance is transformed, these transformation products may dominate observed pesticide occurrences in surface water and groundwater. Their potential contribution to the overall risk to the aquatic environment caused by the use of the parent pesticide should therefore not be neglected in chemical risk and water quality assessments. The same is true for transformation products of other compound classes that might reach the soil environment, such as veterinary pharmaceuticals. However, the fate and input pathways of transformation products of soil-applied chemicals into surface water are not yet well understood, which largely prevents their appropriate inclusion into chemical risk and water quality assessments. Here, we studied whether prioritization methods based on available environmental fate data from pesticide registration dossiers in combination with basic fate models could help identify transformation products which can be found in relevant concentrations in surface and groundwater and which should therefore be included into monitoring programs. A three-box steady state model containing air, soil, and surface water compartments was used to predict relative inputs of pesticide transformation products into surface waters based on their physico-chemical and environmental fate properties. The model predictions were compared to monitoring data from a small Swiss river located in an intensely agricultural catchment (90 km2) which was flow-proportionally sampled from May to October 2008 and screened for 74 pesticides as well as 50 corresponding transformation products. Sampling mainly occurred during high discharge, but additional samples during baseflow conditions were also taken. The analytical measurements included solid phase extraction, liquid chromatography and high resolution mass spectrometry (SPE-LC-HR-MS/MS). Quantification was achieved using reference standards and internal standards. Besides the well-known transformation products of triazine and chloroacetanilide herbicides, transformation products of other compound classes such as azoxystrobin acid (from azoxystrobin, strobilurin fungicide), chloridazon-desphenyl and chloridazon-methyl-desphenyl (from chloridazon, pyridazinone herbicide), and metamitron-desamino (from metamitron, triazinone herbicide) were analyzed in surface water. For a selection of widely used pesticides in the catchment, modelled ratios of transformation product versus parent pesticide concentrations were compared to the measured concentration ratios in the river for the application period and for two 2-month periods following application. Concentration ratios agreed within a factor of 10 for all pairs of parent pesticides and transformation products, and for all seasons, with a single exception. The ratio of chloridazon-desphenyl to chloridazon was under-predicted by a factor of approximately 20. The data revealed that chloridazon-desphenyl was also found in elevated concentrations in all baseflow samples, indicating its presence in the groundwater component of the catchment. The same was true for other transformation products (e.g., metamitron-desamino, chloridazon-methly-desphenyl, metolachlor-ESA), but to a lesser degree. Based on baseflow separation of the hydrograph, the concentration ratio estimation model was supplemented with an additional baseflow component. The concentrations in the baseflow component were estimated with a simple leaching relationship that was compared against measured baseflow concentrations and groundwater findings in Switzerland. The final model yielded good agreement for all compounds and is therefore deemed suitable for prioritization of transformation products with a relevant exposure potential. It also clearly indicated the contribution of groundwater to the overall occurrence of pesticides and their transformation products in Swiss surface waters.

Repeated pulse exposures to lambda-cyhalothrin affect the behavior, physiology, and survival of the damselfly larvae Ischnura graellsii (Insecta; Odonata).

PubMed

Finotello, Simone; Feckler, Alexander; Bundschuh, Mirco; Johansson, Frank

2017-10-01

Damselflies form an essential part of the aquatic and terrestrial food web. Pesticides may, however, negatively affect their behavior, physiology, and survival. To assess this, a 42-day-lasting bioassay was conducted, during which damselfly larvae (Ischnura graellsii; n = 20) were repeatedly exposed to lambda-cyhalothrin (3 days at; 0, 10, 50, 250, 1250, and 6250ng LCH L -1 ), followed by recovery phases (4 days) in pesticide-free medium for six weeks. This exposure design was used to simulate frequent runoff events in the field. Variables related to the behavior (strikes against prey and capture success), growth, physiology (lipid content and fatty acid composition), as well as mortality were assessed throughout the experiment. The two highest LCH concentrations induced 100% mortality within the first 48h, whereas 85% of the test organisms survived 28 days under control conditions. The number of strikes against prey was not affected by LCH. In contrast, prey capture success decreased significantly (up to ~50% at 250ng LCH L -1 , for instance, after the third pulse exposure) following LCH-exposures compared to the control. This difference was not observed after recovery phases, however, which did not counteract the enhanced energy demand for detoxification and defense mechanisms indicated by a lower growth rate (up to ~20%) and lipid content (up to ~30%) of damselflies at 50 and 250ng LCH L -1 . In addition, two essential fatty acids (eicosapentaenoic acid and arachidonic acid) and two precursors (linolenic acid and α-linolenic acid) decreased in their concentrations upon exposure towards 250ng LCH L -1 . Thus the results of this study indicate that long-term exposure towards LCH pulses can affect damselfly behavior, physiology and survival. Given the essential role of damselflies in food web dynamics, these effects may potentially translate into local population impairments with subsequent bottom-up directed effects within and across ecosystem boundaries. Copyright © 2017 Elsevier Inc. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thompson, C.Y.

During second quarter 1992, samples from the six FAC monitoring wells at the F-Area Acid/Caustic Basin were analyzed for herbicides, indicator parameters, major ions, pesticides, radionuclides, turbidity, volatile organic compounds, and other constituents. Monitoring results that exceeded the US Environmental Protection Agency`s Primary Drinking Water Standards (PDWS) or the Savannah River Site flagging criteria or turbidity standards during the quarter are the focus of this report.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thompson, C.Y.

During second quarter 1992, samples from the six FAC monitoring wells at the F-Area Acid/Caustic Basin were analyzed for herbicides, indicator parameters, major ions, pesticides, radionuclides, turbidity, volatile organic compounds, and other constituents. Monitoring results that exceeded the US Environmental Protection Agency's Primary Drinking Water Standards (PDWS) or the Savannah River Site flagging criteria or turbidity standards during the quarter are the focus of this report.

75 FR 50926 - 2-propenoic acid, 2-methyl-, C12-16-alkyl esters, telomers with 1-dodecanethiol, polyethylene...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-18

... result of pesticide use in residential settings. If EPA is able to determine that a finite tolerance is... of its composition the atomic elements carbon, hydrogen, and oxygen. 3. The polymer does not contain as an integral part of its composition, except as impurities, any element other than those listed in...

77 FR 20314 - 2-Propenoic Acid, 2-Methyl-, 2-Ethylhexyl Ester, Telomer With 1-Dodecanethiol, Ethenylbenzene and...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-04-04

... result of pesticide use in residential settings. If EPA is able to determine that a finite tolerance is... composition the atomic elements carbon, hydrogen, and oxygen. 3. The polymer does not contain as an integral part of its composition, except as impurities, any element other than those listed in 40 CFR 723.250(d...

In-Silico Design, Synthesis and Evaluation of a Nanostructured Hydrogel as a Dimethoate Removal Agent.

PubMed

Avila-Salas, Fabian; Marican, Adolfo; Villaseñor, Jorge; Arenas-Salinas, Mauricio; Argandoña, Yerko; Caballero, Julio; Durán-Lara, Esteban F

2018-01-04

This study describes the in-silico design, synthesis, and evaluation of a cross-linked PVA hydrogel (CLPH) for the absorption of organophosphorus pesticide dimethoate from aqueous solutions. The crosslinking effectiveness of 14 dicarboxilic acids was evaluated through in-silico studies using semiempirical quantum mechanical calculations. According to the theoretical studies, the nanopore of PVA cross-linked with malic acid (CLPH-MA) showed the best interaction energy with dimethoate. Later, using all-atom molecular dynamics simulations, three hydrogels with different proportions of PVA:MA (10:2, 10:4, and 10:6) were used to evaluate their interactions with dimethoate. These results showed that the suitable crosslinking degree for improving the affinity for the pesticide was with 20% ( W %) of the cross-linker. In the experimental absorption study, the synthesized CLPH-MA20 recovered 100% of dimethoate from aqueous solutions. Therefore, the theoretical data were correlated with the experimental studies. Surface morphology of CLPH-MA20 by Scanning Electron Microscopy (SEM) was analyzed. In conclusion, the ability of CLPH-MA20 to remove dimethoate could be used as a technological alternative for the treatment of contaminated water.

In-Silico Design, Synthesis and Evaluation of a Nanostructured Hydrogel as a Dimethoate Removal Agent

PubMed Central

Avila-Salas, Fabian; Marican, Adolfo; Villaseñor, Jorge; Argandoña, Yerko

2018-01-01

This study describes the in-silico design, synthesis, and evaluation of a cross-linked PVA hydrogel (CLPH) for the absorption of organophosphorus pesticide dimethoate from aqueous solutions. The crosslinking effectiveness of 14 dicarboxilic acids was evaluated through in-silico studies using semiempirical quantum mechanical calculations. According to the theoretical studies, the nanopore of PVA cross-linked with malic acid (CLPH-MA) showed the best interaction energy with dimethoate. Later, using all-atom molecular dynamics simulations, three hydrogels with different proportions of PVA:MA (10:2, 10:4, and 10:6) were used to evaluate their interactions with dimethoate. These results showed that the suitable crosslinking degree for improving the affinity for the pesticide was with 20% (W%) of the cross-linker. In the experimental absorption study, the synthesized CLPH-MA20 recovered 100% of dimethoate from aqueous solutions. Therefore, the theoretical data were correlated with the experimental studies. Surface morphology of CLPH-MA20 by Scanning Electron Microscopy (SEM) was analyzed. In conclusion, the ability of CLPH-MA20 to remove dimethoate could be used as a technological alternative for the treatment of contaminated water. PMID:29300312

A study of the degradation of organophosphorus pesticides in river waters and the identification of their degradation products by chromatography coupled with mass spectrometry.

PubMed

Zhao, Xueheng; Hwang, Huey-Min

2009-05-01

The degradation of selected organophosphorus pesticides (OPs), i.e., malathion and parathion, in river water, has been studied with solar simulator irradiation. The degradation of OPs and formation of degradation products were determined by chromatography coupled with mass spectrometry analysis. The effect of a photosensitizer, i.e., riboflavin, on the photolysis of OPs in a river-water environment was examined. There was no significant increase in the degradation rate in the presence of the photosensitizer. Degradation products of the OPs were identified with gas chromatography coupled with mass spectrometry (GC-MS) after derivatization by pentafluorobenzyl bromide (PFBB) and with high-performance liquid chromatography-mass spectrometry (HPLC-MS) with electrospray (ESI) or atomospheric pressure chemical ionization (APCI). Malaoxon, paraoxon, 4-nitrophenol, aminoparathion, O,O-dimethylthiophosphoric acid, and O,O-dimethyldithiophosphoric acid, have been separated and identified as the degradation products of malathion and parathion after photolysis in river water. Based on the identified transformation products, a rational degradation pathway in river water for both OPs is proposed. The identities of these products can be used to evaluate the toxic effects of the OPs and their transformation products on natural environments.

Adsorption of humic acids and trace metals in natural waters

NASA Technical Reports Server (NTRS)

Leung, W. H.

1982-01-01

Studies concerning the interactions between suspended hydrous iron oxide and dissolved humic acids and trace metals are reported. As a major component of dissolved organic matters and its readiness for adsorption at the solid/water interface, humic acids may play a very important role in the organometallic geochemistry of suspended sediments and in determining the fate and distribution of trace metals, pesticides and anions in natural water systems. Most of the solid phases in natural waters contain oxides and hydroxides. The most simple promising theory to describe the interactions of hydrous iron oxide interface is the surface complex formation model. In this model, the adsorptions of humic acids on hydrous iron oxide may be interpreted as complex formation of the organic bases (humic acid oxyanions) with surface Fe ions. Measurements on adsorptions were made in both fresh water and seawater. Attempts have been made to fit our data to Langmuir adsorption isotherm. Adsorption equilibrium constants were determined.

The acid/base profile of agrochemicals.

PubMed

Manallack, D T

2017-08-01

Drug-likeness has long been studied in the pursuit of finding new medicines. Similarly, in the agrochemical field there is value in exploring the properties of the chemicals involved. Patterns that emerge can potentially influence future discovery campaigns to improve the probability of commercial success. In this study we investigate the acid/base properties and physicochemical characteristics of three classes of compounds: fungicides, herbicides and insecticides. In comparison with FDA-approved drugs, it was noted that the pesticides were generally smaller, possessed a neutral charge state and were more lipophilic. The results are discussed in the light of their intended targets.

Organochlorine pesticides in fish from Taihu Lake, China, and associated human health risk assessment.

PubMed

Wang, Deqing; Yu, Yingxin; Zhang, Xinyu; Zhang, Dongping; Zhang, Shaohuan; Wu, Minghong

2013-12-01

Because contaminants and nutrients always coexist in fish, the risk from contaminants and the benefit from nutrients, such as eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) are also concomitant via fish consumption. To investigate the risk and benefit via fish consumption, concentrations of dichlorodiphenyltrichloroethane and its metabolites (DDTs), and hexachlorocyclohexanes (HCHs) in the whole- and portion-muscles of fish from Taihu Lake, China, were measured. Based on the contaminant data and nutrients from our previous study, and the associated risk and benefit via fish consumption were estimated. The concentrations of DDTs and HCHs in the whole-muscles ranged from 7.8 × 10² to 3.4×10³ pg g⁻¹ ww, and from 67.3 to 300 pg g⁻¹ ww, respectively. Of DDTs and HCHs measured, p,p'-DDE and β-HCH were respectively the most abundant pesticides. The composition profiles of DDTs and HCHs suggested that the pesticides were mainly historical residues. The benefit-risk quotient (BRQ) of EPA+DHA vs. POPs (persistent organic pollutants including data of DDTs, HCHs, and those of polychlorinated biphenyls and polybrominated diphenyl ethers cited from our previous study) via consumption of fish from Taihu Lake was calculated. As a result, to achieve the recommended EPA+DHA intake of 250 mg d⁻¹ for a healthy adult, the consumption of most fish species from the lake can cause cancer and non-cancer risks. However, the fish consumption at the rates of 44.9 g d⁻¹ by Chinese would not lead to the risks for most of the species. The results also suggested that the risk of consuming silver carp was generally lower than other fish species, and those of dorsal muscles were lower than ventral and tail muscles. Copyright © 2013 Elsevier Inc. All rights reserved.

Leaching of glyphosate and amino-methylphosphonic acid from Danish agricultural field sites.

PubMed

Kjaer, Jeanne; Olsen, Preben; Ullum, Marlene; Grant, Ruth

2005-01-01

Pesticide leaching is an important process with respect to contamination risk to the aquatic environment. The risk of leaching was thus evaluated for glyphosate (N-phosphonomethyl-glycine) and its degradation product AMPA (amino-methylphosphonic acid) under field conditions at one sandy and two loamy sites. Over a 2-yr period, tile-drainage water, ground water, and soil water were sampled and analyzed for pesticides. At a sandy site, the strong soil sorption capacity and lack of macropores seemed to prevent leaching of both glyphosate and AMPA. At one loamy site, which received low precipitation with little intensity, the residence time within the root zone seemed sufficient to prevent leaching of glyphosate, probably due to degradation and sorption. Minor leaching of AMPA was observed at this site, although the concentration was generally low, being on the order of 0.05 microg L(-1) or less. At another loamy site, however, glyphosate and AMPA leached from the root zone into the tile drains (1 m below ground surface [BGS]) in average concentrations exceeding 0.1 microg L(-1), which is the EU threshold value for drinking water. The leaching of glyphosate was mainly governed by pronounced macropore flow occurring within the first months after application. AMPA was frequently detected more than 1.5 yr after application, thus indicating a minor release and limited degradation capacity within the soil. Leaching has so far been confined to the depth of the tile drains, and the pesticides have rarely been detected in monitoring screens located at lower depths. This study suggests that as both glyphosate and AMPA can leach through structured soils, they thereby pose a potential risk to the aquatic environment.

Biodegradation of malathion, α- and β-endosulfan by bacterial strains isolated from agricultural soil in Veracruz, Mexico.

PubMed

Jimenez-Torres, Catya; Ortiz, Irmene; San-Martin, Pablo; Hernandez-Herrera, R Idalia

2016-12-01

The objective of this study was to evaluate the capacity of two bacterial strains isolated, cultivated, and purified from agricultural soils of Veracruz, Mexico, for biodegradation and mineralisation of malathion (diethyl 2-(dimethoxyphosphorothioyl) succinate) and α- and β-endosulfan (6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6-9-methano-2,4,3-benzodioxathiepine-3-oxide). The isolated bacterial strains were identified using biochemical and morphological characterization and the analysis of their 16S rDNA gene, as Enterobacter cloacae strain PMM16 (E1) and E. amnigenus strain XGL214 (M1). The E1 strain was able to degrade endosulfan, whereas the M1 strain was capable of degrading both pesticides. The E1 strain degraded 71.32% of α-endosulfan and 100% of β-endosulfan within 24 days. The absence of metabolites, such as endosulfan sulfate, endosulfan lactone, or endosulfan diol, would suggest degradation of endosulfan isomers through non-oxidative pathways. Malathion was completely eliminated by the M1 strain. The major metabolite was butanedioic acid. There was a time-dependent increase in bacterial biomass, typical of bacterial growth, correlated with the decrease in pesticide concentration. The CO 2 production also increased significantly with the addition of pesticides to the bacterial growth media, demonstrating that, under aerobic conditions, the bacteria utilized endosulfan and malathion as a carbon source. Here, two bacterial strains are shown to metabolize two toxic pesticides into non-toxic intermediates.

Organophosphorus pesticide mixture removal from environmental matrices by a soil Streptomyces mixed culture.

PubMed

Briceño, Gabriela; Vergara, Karen; Schalchli, Heidi; Palma, Graciela; Tortella, Gonzalo; Fuentes, María Soledad; Diez, María Cristina

2017-07-26

The current study aimed to evaluate the removal of a pesticide mixture composed of the insecticides chlorpyrifos (CP) and diazinon (DZ) from liquid medium, soil and a biobed biomixture by a Streptomyces mixed culture. Liquid medium contaminated with 100 mg L -1 CP plus DZ was inoculated with the Streptomyces mixed culture. Results indicated that microorganisms increased their biomass and that the inoculum was viable. The inoculum was able to remove the pesticide mixture with a removal rate of 0.036 and 0.015 h -1 and a half-life of 19 and 46 h -1 for CP and DZ, respectively. The sterilized soil and biobed biomixture inoculated with the mixed culture showed that Streptomyces was able to colonize the substrates, exhibiting an increase in population determined by quantitative polymerase chain reaction (q-PCR), enzymatic activity dehydrogenase (DHA) and acid phosphatase (APP). In both the soil and biomixture, limited CP removal was observed (6-14%), while DZ exhibited a removal rate of 0.024 and 0.060 day -1 and a half-life of 29 and 11 days, respectively. Removal of the organophosphorus pesticide (OP) mixture composed of CP and DZ from different environmental matrices by Streptomyces spp. is reported here for the first time. The decontamination strategy using a Streptomyces mixed culture could represent a promising alternative to eliminate CP and DZ residues from liquids as well as to eliminate DZ from soil and biobed biomixtures.

Sorption of estrogens and pesticides from aqueous solution by a humic acid and raw and processed plant materials

NASA Astrophysics Data System (ADS)

Loffredo, Elisabetta; Taskin, Eren

2016-04-01

The huge number of organic contaminants released in water as a consequence of anthropogenic activities have detrimental effects to environmental systems and human health. Industrial products and byproducts, pharmaceuticals, pesticides, detergents and so on impose increasing costs for wastewater decontamination. Adsorption techniques can be successfully used for the treatment of wastewaters to remove contaminants of various nature. Humic acids (HA) have well-known adsorptive capacities towards hydrophilic and, especially, hydrophobic compounds. In the recent years, alternative low-cost adsorbents, especially originated from agricultural wastes and food industries residues, such as wood chips, almond and coconut shells, peanut and rice husks, are under investigation. Biochar is also considered a promising and relatively low-cost adsorbent, even if there are still knowledge gaps about the influence of feedstock type, pyrolysis conditions, physical and chemical properties on its potential and safe use. In the present work, a HA from a green compost was used along with three other materials of plant origin to remove two estrogens, 4-tert-octylphenol and 17-β-estradiol, and two pesticides, carbaryl and fenuron, from an aqueous solution. The four molecules were spiked in water each at a concentration of 1 mg L-1. The materials were: a biochar obtained from 100% red spruce pellet pyrolysed at 550 °C, spent coffee grounds and spent tea leaves. Kinetics curves and adsorption isotherms studies were performed using a batch equilibrium method. Adsorption data obtained for each compound were fitted to a linear equation and non-linear Freundlich and Langmuir models. Kinetics data of the four compounds onto all adsorbents showed an initial very rapid adsorption which was completed in few hours when it reached equilibrium. The two estrogens were adsorbed onto all materials more quickly than the two less hydrophobic pesticides. Significant differences among adsorbents and the compounds concerned both the model of adsorption and quantitative aspects. Biochar demonstrated an optimum adsorption capability for both estrogens and pesticides, which was comparable to that of HA or even higher. The trend of adsorption varied with the model and the compound, approximately it was: biochar ≥ HA > spent coffee grounds > spent tea leaves. A marked adsorption efficiency (high values of the sorption constants) was shown by all materials for the contaminants. That suggests a valuable and cost effective exploitation of such materials for the removal of hazardous contaminants from aqueous wastes before their worthwhile recycle.

Irreversibility of 2,4-Dichlorophenoxyacetic Acid Sorption onto a Volcanic Ash Soil

NASA Astrophysics Data System (ADS)

Mon, E.; Kawamoto, K.; Komatsu, T.; Moldrup, P.

2008-12-01

Pesticide sorption and desorption in soils are key processes governing fate and transport of pesticides in the soil environment. The irreversibility (or hysteresis) in the processes of pesticide sorption and desorption needs to be known to accurately predict behavior of pesticides in soil systems. 2,4-dichlorophenoxyacetic acid (2,4-D) is a widely used pesticide in agriculture fields. However, only few studies of 2,4-D adsorption onto Andosols (volcanic ash soils) have been published, and the knowledge of 2,4-D desorption onto Andosols is very limited. In this study, a volcanic ash soil sampled from a pasture site in Nishi-Tokyo, Japan was used as a sorbent in order to investigate the irreversibility of 2,4-D sorption. For comparison, a pure clay mineral (kaolinite) obtained from Clay Science Society of Japan (CSSJ) was also used. 2,4-D solutions with three concentrations (0.011, 0.022 and 0.045 mmol/L) were prepared in artificial rain water (ARW= 0.085mM NaCl + 0.015mM CaCl2) to simulate field conditions. To prepare the sample solutions, the solid mass/liquid volume ratio of 1:10 was used for both sorbents (volcanic ash soil and kaolinite). The experiments were conducted in triplicate using a batch method under different pH conditions to examine the effect of pH. Desorption was measured during a equilibration procedure: After removal of 7 mL of supernatant in the sorption step, 7 mL of ARW excluding 2,4-D was added to the sample solution after which, it was equilibrated and centrifuged. The procedure was performed sequentially three or four times to obtain a desorption isotherm. Sorption and desorption generally followed Freundlich isotherms. The results showed markedly effects of pH on 2,4-D sorption and desorption in both the soil and kaolinite, with the percentage of sorption increasing with decreasing pH whereas the percentage of desorption decreased. There was a larger adsorption-desorption hysteresis in the volcanic ash soil as compared to kaolinite. Moreover, the largest hysteresis was found under the lowest pH condition indicating that the hysteretic effect likely depended on the variation of pH. In summary, the volcanic ash soil exhibited higher sorption coefficients and hysteresis than kaolinite, likely due to soil properties such as high organic matter content and the presence of different clay minerals.

Electrospun nanofibres in agriculture and the food industry: a review.

PubMed

Noruzi, Masumeh

2016-11-01

The interesting characteristics of electrospun nanofibres, such as high surface-to-volume ratio, nanoporosity, and high safety, make them suitable candidates for use in a variety of applications. In the recent decade, electrospun nanofibres have been applied to different potential fields such as filtration, wound dressing, drug delivery, etc. and a significant number of review papers have been published in these fields. However, the use of electrospun nanofibres in agriculture is comparatively novel and is still in its infancy. In this paper, the specific applications of electrospun nanofibres in agriculture and food science, including plant protection using pheromone-loaded nanofibres, plant protection using encapsulation of biocontrol agents, preparation of protective clothes for farm workers, encapsulation of agrochemical materials, deoxyribonucleic acid extraction in agricultural research studies, pre-concentration and measurement of pesticides in crops and environmental samples, preparation of nanobiosensors for pesticide detection, encapsulation of food materials, fabrication of food packaging materials, and filtration of beverage products are reviewed and discussed. This paper may help researchers develop the use of electrospun nanofibres in agriculture and food science to address some serious problems such as the intensive use of pesticides. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Multi-class methodology to determine pesticides and mycotoxins in green tea and royal jelly supplements by liquid chromatography coupled to Orbitrap high resolution mass spectrometry.

PubMed

Martínez-Domínguez, Gerardo; Romero-González, Roberto; Garrido Frenich, Antonia

2016-04-15

A multi-class methodology was developed to determine pesticides and mycotoxins in food supplements. The extraction was performed using acetonitrile acidified with formic acid (1%, v/v). Different clean-up sorbents were tested, and the best results were obtained using C18 and zirconium oxide for green tea and royal jelly, respectively. The compounds were determined using ultra high performance liquid chromatography (UHPLC) coupled to Exactive-Orbitrap high resolution mass spectrometry (HRMS). The recovery rates obtained were between 70% and 120% for most of the compounds studied with a relative standard deviation <25%, at three different concentration levels. The calculated limits of quantification (LOQ) were <10 μg/kg. The method was applied to green tea (10) and royal jelly (8) samples. Nine (eight of green tea and one of royal jelly) samples were found to be positive for pesticides at concentrations ranging from 10.6 (cinosulfuron) to 47.9 μg/kg (paclobutrazol). The aflatoxin B1 (5.4 μg/kg) was also found in one of the green tea samples. Copyright © 2015 Elsevier Ltd. All rights reserved.

Characterization of preservative and pesticide as potential of bio oil compound from pyrolisis of cocoa shell using gas chromatography

NASA Astrophysics Data System (ADS)

Mashuni, Jahiding, M.; Kurniasih, I.; Zulkaidah

2017-03-01

Cocoa shell is one of the plant waste that has not been widely used. Cocoa shell is potential as a producer of bio oil because it contains lignocellulose. The bio oil of Liquid volatile matter (LVM) is the products of smoke condensation from the pyrolysis reactor. The bio oil of cocoa shell from pyrolysis process can be made as raw materials for the application of pesticide and preservative. The aims of this research were to produce bio oil from cocoa shell by pyrolysis and analyzing the content using Gas Chromatography (GC). Bio oil production was done by pyrolysis with variations of temperature, i.e. 400, 500, 600 and 700 °C. Pyrolysis reaction generates three products: gas, liquid and solid. The yield of bio oil with variations of pyrolisis temperature, i.e. 400, 500, 600 and 700 °C were obtained i.e. 46, 45, 44 and 40% (v/w), respectively. The chromatogram results showed the chemical components of bio oil from the cocoa shell were ammonia, hexane, alcohol, ketone, acid and phenolic compounds which can be used as material of preservative and pesticide.

Adsorption of 1-naphthyl methyl carbamate in water by utilizing a surface molecularly imprinted polymer

NASA Astrophysics Data System (ADS)

So, Juhyok; Pang, Cholho; Dong, Hongxing; Jang, Paeksan; U, Juhyok; Ri, Kumchol; Yun, Cholyong

2018-05-01

Surface molecularly imprinting polymer (SMIP) was utilized in the removal of a residual pesticide (carbaryl (CBL)) in water and simulated fruit juice. Being the crosslinking agent, ethylene glycol dimethacrylate (EGDMA) was copolymerized with the monomer, methacrylic acid (MAA) and CBL as the template molecules on the surface of the silica gel particles to produce the SMIP adsorbents. The SMIP adsorbents showed good selectivity and good adsorption capacity for CBL in the competitive adsorptions with two structurally related carbamate pesticides. The effect of the pretreatment solvents on the adsorption capacity of the SMIP adsorbent was investigated with the results of the numerical simulations. The adsorption isotherms and the adsorption kinetics were well described by the Freundlich equilibrium model and the pseudo-second-order kinetic model, respectively. Scatchard plot analysis revealed that there were two classes of binding sites populated in the SMIP adsorbents. In addition, the good selective adsorption of CBL by the SMIP adsorbent in a simulated fruit juice containing vitamin C and fructose indicated the great potential of the SMIP adsorbents to remove residual pesticide in food industry and processing industry for agricultural products.

Bioconcentration, bioaccumulation, and metabolism of pesticides in aquatic organisms.

PubMed

Katagi, Toshiyuki

2010-01-01

The ecotoxicological assessment of pesticide effects in the aquatic environment should normally be based on a deep knowledge of not only the concentration of pesticides and metabolites found but also on the influence of key abiotic and biotic processes that effect rates of dissipation. Although the bioconcentration and bioaccumulation potentials of pesticides in aquatic organisms are conveniently estimated from their hydrophobicity (represented by log K(ow), it is still indispensable to factor in the effects of key abiotic and biotic processes on such pesticides to gain a more precise understanding of how they may have in the natural environment. Relying only on pesticide hydrophobicity may produce an erroneous environmental impact assessment. Several factors affect rates of pesticide dissipation and accumulation in the aquatic environment. Such factors include the amount and type of sediment present in the water and type of diet available to water-dwelling organisms. The particular physiological behavior profiles of aquatic organisms in water, such as capacity for uptake, metabolism, and elimination, are also compelling factors, as is the chemistry of the water. When evaluating pesticide uptake and bioconcentration processes, it is important to know the amount and nature of bottom sediments present and the propensity that the stuffed aquatic organisms have to absorb and process xenobiotics. Extremely hydrophobic pesticides such as the organochlorines and pyrethroids are susceptible to adsorb strongly to dissolved organic matter associated with bottom sediment. Such absorption reduces the bioavailable fraction of pesticide dissolved in the water column and reduces the probable ecotoxicological impact on aquatic organisms living the water. In contrast, sediment dweller may suffer from higher levels of direct exposure to a pesticide, unless it is rapidly degraded in sediment. Metabolism is important to bioconcentration and bioaccumulation processes, as is detoxification and bioactivation. Hydrophobic pesticides that are expected to be highly stored in tissues would not be bioconcentrated if susceptible to biotic transformation by aquatic organisms to more rapidly metabolized to hydrophilic entities are generally less toxic. By analogy, pesticides that are metabolized to similar entities by aquatic species surely are les ecotoxicologically significant. One feature of fish and other aquatic species that makes them more relevant as targets of environmental studies and of regulation is that they may not only become contaminated by pesticides or other chemicals, but that they constitute and important part of the human diet. In this chapter, we provide an overview of the enzymes that are capable of metabolizing or otherwise assisting in the removal of xenobiotics from aquatic species. Many studies have been performed on the enzymes that are responsible for metabolizing xenobiotics. In addition to the use of conventional biochemical methods, such studies on enzymes are increasingly being conducted using immunochemical methods and amino acid or gene sequences analysis. Such studies have been performed in algae, in some aquatic macrophytes, and in bivalva, but less information is available for other aquatic species such as crustacea, annelids, aquatic insecta, and other species. Although their catabolizing activity is often lower than in mammals, oxidases, especially cytochrome P450 enzymes, play a central role in transforming pesticides in aquatic organisms. Primary metabolites, formed from such initial enzymatic action, are further conjugated with natural components such as carbohydrates, and this aids removal form the organisms. The pesticides that are susceptible to abiotic hydrolysis are generally also biotically degraded by various esterases to from hydrophilic conjugates. Reductive transformation is the main metabolic pathway for organochlorine pesticides, but less information on reductive enzymology processes is available. The information on aquatic species, other than fish, that pertains to bioconcentration factors, metabolism, and elimination is rather limited in the literature. The kinds of basic information that is unavailable but is needed on important aquatic species includes biochemistry, physiology, position in food web, habitat, life cycle, etc. such information is very important to obtaining improved ecotoxicology risk assessments for many pesticides and other chemicals. More research attention on the behavior of pesticides in, and affect on many standard aquatic test species (e.g., daphnids, chironomids, oligochaetes and some bivalves) would particularly be welcome. In addition to improving ecotoxicology risk assessments on target species, such information would also assist in better delineating affects on species at higher trophic levels that are predaceous on the target species. There is also need for designing and employing more realistic approaches to measure bioconcentration and bioaccumulation, and ecotoxicology effects of pesticides in natural environment. The currently employed steady-state laboratory exposure studies are insufficient to deal with the complexity of parameters that control the contrasts to the abiotic processes of pesticide investigated under the strictly controlled conditions, each process is significantly affected in the natural environment not only by the site-specific chemistry of water and sediment but also by climate. From this viewpoint, ecotoxicological assessment should be conducted, together with the detailed analyses of abiotic processes, when higher-tier mesocosm studies are performed. Moreover, in-depth investigation is needed to better understand the relationship between pesticide residues in organisms and associated ecotoxicological endpoints. The usual exposure assessment is based on apparent (nominal) concentrations fo pesticides, and the residues of pesticides or their metabolites in the organisms are not considered in to the context of ecotoxicological endpoints. Therefore, more metabolic and tissue distribution information for terminal pesticide residues is needed for aquatic species both in laboratory settings and in higher-tier (microcosm, mesocosm) studies.

Condensation nucleation light scattering detection with ion chromatography for direct determination of glyphosate and its metabolite in water.

PubMed

You, Jing; Koropchak, John A

2003-03-14

An ion chromatography-condensation nucleation light scattering detection (IC-CNLSD) method was successfully used to directly analyze glyphosate, a polar pesticide, and aminomethylphosaphonic acid, the major metabolite of glyphosate, in water without need of pre-treatment or derivatization. CNLSD gave a LOD of 53 ng/ml for glyphosate, which is much lower than the maximum contaminant level of 700 ng/ml for drinking water issued by the US Environmental Protection Agency. Spiked analytes in different matrixes were tested. A diluted commercial herbicide containing glyphosate was also evaluated. Compared to other reported methods, the IC-CNLSD method has no need of sample derivatization, pre-concentration, and mobile phase conductivity suppression. It is simple, fast and inexpensive. IC-CNLSD is an ideal direct detection technique for such pesticides without chromophores or fluorophores.

Predicting bioavailability and accumulation of organochlorine pesticides by Japanese medaka in the presence of humic acid and natural organic matter using passive sampling membranes.

PubMed

Ke, Runhui; Luo, Jianping; Sun, Liwei; Wang, Zijian; Spear, Philip A

2007-10-01

Adsorption to dissolved organic matter (DOM) may significantly decrease the freely dissolved concentration of many hydrophobic organic compounds and, hence, result in reduced bioavailability to aquatic organisms. Here, the suitability of using triolein-embedded cellulose acetate membrane (TECAM) as a biomimetic surrogate to assess the bioavailability of organochlorine pesticides (OCPs) in water in the presence of DOM was explored. The accumulation of OCPs was measured in TECAM and pelagic Japanese medaka (Oryzias latipes) in the laboratory after 12 h exposure to water containing different levels of Aldrich humic acid. Further, OCP uptake by TECAM and medaka in real aqueous environments was evaluated after 30 d exposures in two sites. Laboratory results showed that OCP uptake by medaka consistently decreased with increasing levels of humic acid in the range of 0-15 mg C/L in sample solutions. This tendency was closely mimicked by OCP accumulation in TECAM under the same conditions. Field results showed that TECAM accumulated similar OCP patterns as medaka (r2 = 0.92 for site 1 and r2 = 0.94 for site 2), although comparison of the in-field eight OCP concentrations in TECAM to those in medaka yielded approximately a factor of 3 (on a wet weight basis). These results suggest that the TECAM method can be used as a simple and useful tool to predict the bioavailability and bioaccumulation potential of poorly biotransformed organic compounds in pelagic fish in aqueous environment.

Pesticides in surface water in the lower Illinois River basin, 1996-98

USGS Publications Warehouse

King, Robin B.

2003-01-01

Surface-water quality samples were collected from April 1996 to September 1998 from eight locations in the Lower Illinois River Basin, a study unit of the U.S. Geological Survey?s National Water-Quality Assessment program. The study area is approximately 15,600 square miles and encompasses most of central and western Illinois. The dominant land use is agricultural and most land is used for the production of corn and soybeans. About 6.9 million acres of corn and soybeans are planted annually in the lower Illinois River Basin. Conservation tillage, defined as mulch-till and no-till, is used on about 40 percent of the cropland in the study area, similar to the statewide average. Nearly 90 percent of the samples for pesticide analyses were collected at four sites: the Illinois River at Ottawa, the Illinois River at Valley City, the La Moine River at Colmar, and the Sangamon River at Monticello. Two hundred fifty-eight samples were collected and analyzed for various herbicides, insecticides, and herbicide transformation products (also referred to as degradates). Thirty-one pesticides were detected at concentrations above their respective method detection limit: 23 herbicides and 8 insecticides. An additional set of 34 samples was collected in the summer of 1998 for the analysis of herbicide transformation products. Nine herbicide transformation products were detected, all belonging to the chloroacetanilide or the triazine chemical class. Two herbicides, atrazine and cyanazine, exceeded the associated human health drinking-water criteria and the aquatic health-criteria. Atrazine was detected in all samples. Sixty percent of the samples (48 of 80) collected in the months of May and June had atrazine concentrations that exceeded the clean drinking- water standard of 3 micrograms per liter (mg/L). The average atrazine concentration in the May to June samples was about 7.0 mg/L. The maximum atrazine concentrations were 110 mg/L in the La Moine River at Colmar and 32 mg/L in the Sangamon River at Monticello. The maximum atrazine concentration in the lower Illinois River was 20 mg/L, measured at Valley City, although most of the relatively elevated concentrations in the Illinois River sites were in the range from 5 to 8 mg/L. The concentrations of the herbicide cyanazine exceeded the health advisory guideline of 1 mg/L in about 19 percent (15 of 80) of the May to June samples. The pesticides chlorpyrifos, diazinon, metolachlor, and 2,4-D exceeded aquatic health guidelines at various times from May to August. Three dominant factors that affect the presence of pesticides in streams are identified: the pesticide usage, the time-of-year (or season), and the flow condition. The pesticides with the highest usage--atrazine, metolachlor, cyanazine, and acetochlor--generally were the pesticides detected most frequently and at the highest concentrations. Notable exceptions to this general observation are alachlor and simazine, which did not have high usage but were detected frequently. The elevated pesticide concentrations were most affected by seasonality--most of these elevated concentrations were observed across all flow conditions during May to June. Flow conditions also affect pesticide concentrations, but not as much as seasonality. The maximum pesticide loads were observed between March and July on the Illinois River. The net contribution of pesticides applied in the study area to net increases in load indicates that only about 1-2 percent of the pesticides applied exit the basin through the Illinois River at Valley City. The chloroacetanilide-class transformation products observed in samples collected in summer 1998 persistently contained elevated concentrations relative to the associated parent pesticide compound at all locations and for all streamflow conditions. The concentration of the transformation product metolachlor ethane sulfonic acid (ESA) usually was about 10 times higher than the parent compound in the mainstem of the lower

AUTOMATED ANALYSIS OF AQUEOUS SAMPLES CONTAINING PESTICIDES, ACIDIC/BASIC/NEUTRAL SEMIVOLATILES AND VOLATILE ORGANIC COMPOUNDS BY SOLID PHASE EXTRACTION COUPLED IN-LINE TO LARGE VOLUME INJECTION GC/MS

EPA Science Inventory

Data is presented on the development of a new automated system combining solid phase extraction (SPE) with GC/MS spectrometry for the single-run analysis of water samples containing a broad range of organic compounds. The system uses commercially available automated in-line 10-m...

75 FR 4292 - 2-Propenoic acid, 2-ethylhexyl ester, polymer with ethenylbenzene and 2-methylpropyl 2-methyl-2...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-01-27

... of pesticide use in residential settings. If EPA is able to determine that a finite tolerance is not... elements carbon, hydrogen, and oxygen. 3. The polymer does not contain as an integral part of its composition, except as impurities, any element other than those listed in 40 CFR 723.250(d)(2)(ii). 4. The...

Utilization of useless pesticides in a plasma reactor

NASA Astrophysics Data System (ADS)

Lozhechnik, A. V.; Mossé, A. L.; Savchin, V. V.; Skomorokhov, D. S.; Khvedchin, I. V.

2011-09-01

Investigations on destruction of isophene C14H18O7N2 and the butyl ether of 2,4-dichlorophenoxyacetic acid (Cl2C6H3OCH2COOCH2CH(CH3)2) are performed. The plasma treatment of toxic waste is implemented in a plasma reactor with a three-jet mixing chamber. Air is used as the plasma-forming gas.

75 FR 11740 - S-Abscisic Acid, (S)-5-(1-hydroxy-2,6,6-trimethyl-4-oxo-1-cyclohex-2-enyl)-3-methyl-penta-(2Z,4E...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-03-12

... present in all vascular plants, algae, and some fungi. It is naturally present in fruits and vegetables at... potentially affected by this action if you are an agricultural producer, food manufacturer, or pesticide manufacturer. Potentially affected entities may include, but are not limited to: Crop production (NAICS code...

Installation Restoration Program. Phase 1. Records Search, England AFB, Louisiana

DTIC Science & Technology

1983-05-01

compound shown on Figure 4.3. No herbicides, expired DDT or other pesticides were stored at this site. Some battery acid was stored in plastic boxes...Union Carbide Corporation, Chemicals and Plastics Divi- sion, Environomental Engineering Department. As a pro- cess/project engineer performed...paper mill waste treatment facility. Project Manager on Solid and Hazardous Waste study for a diverse chemicals and plastics production facility

Effects of maternal diet and environmental exposure to organochlorine pesticides on newborn weight in Southern Spain.

PubMed

Monteagudo, C; Mariscal-Arcas, M; Heras-Gonzalez, L; Ibañez-Peinado, D; Rivas, A; Olea-Serrano, F

2016-08-01

An appropriate eating pattern is essential during childbearing years and pregnancy to ensure a healthy pregnancy and newborn. Our group developed a Mediterranean Diet Score for Pregnancy (MDS-P) based on the MD and the specific need of pregnant women for Fe, Ca, and folic acid. Humans are daily exposed to endocrine disruptors, which may alter body weight and hormone system regulation. This study analyzed the relationship of maternal diet and in utero exposure to organochlorine pesticides (OCPs) with newborn weight in mothers and newborns from Southern Spain. Higher MDS-P score, folic acid supplementation, and greater in utero exposure to endosulfan-diol and endosulfan-1 were related to higher newborn weight. MDS-P score was not associated with maternal weight gain during pregnancy (above or below 12 Kg). Residues from one or more OCPs were detected in 96.5% of umbilical cord serum samples from 320 newborns. The most frequent residues were endosulfans (96.5%). The presence of endosulfan-diol, endosulfan-I, p-p´DDT, folic acid supplementation, and a higher MDS-P (>8) were predictive factors for newborn overweight (>3500 g). Conversely, smoking during pregnancy, shorter gestation time (32-36 vs. 37-39 weeks), and lesser maternal weight gain during pregnancy predicted lower newborn weight (<2500 g). These results indicate prenatal exposure to OCPs in Southern Spain and its possible impact on the weight of healthy full-term newborns. Further studies are warranted to interpret the consequences of this exposure and identify preventive measures. Adherence to the MD and folic acid supplementation during pregnancy emerged as predictive factors for overweight in newborns. Copyright © 2016 Elsevier Ltd. All rights reserved.

Sorption of polar herbicides and herbicide metabolites by biochar-amended soil.

PubMed

Dechene, Annika; Rosendahl, Ingrid; Laabs, Volker; Amelung, Wulf

2014-08-01

Biochar-amended soil has been proven to possess superior sorption capacities for several environmental pollutants compared with pure soil. However, the role of biochar in the immobilization of polar pesticides and their metabolites has hardly been tested. The aim of this study was therefore to investigate the effect of a soil amendment with biochar on the sorption of selected polar herbicides and herbicide metabolites (log Kow 0.3-<2). To simulate worst-case sorption, a sandy soil (1.7% organic matter) was amended with 1.5% biochar (fresh or composted) to determine sorption/desorption isotherms of the test compounds. One herbicide (imazamox) and three herbicide metabolites (methyl-desphenyl-chloridazon, metazachlor oxalic acid, metazachlor sulfonic acid) were tested, i.e. three anionic and one neutral polar compound. The results showed that the presence of biochar increased the sorption capacity of the soil only in the case of the uncharged compound methyl-desphenyl-chloridazon, for which the average distribution coefficients in biochar-amended soils were higher than in pure soil by a factor of 2.1-2.5. However, this effect rather seemed to reflect the increased soil organic carbon content after the addition of biochar than a preferred sorption of methyl-desphenyl-chloridazon to biochar. In the case of the three anionic compounds imazamox, metazachlor oxalic acid and metazachlor sulfonic acid, biochar amendment did not increase the sorption capacity of the soil for these compounds, presumably as a result of its negative net charge. Similarly, desorption experiments did not show any significant effect of the biochar amendment on desorption. This suggests that the potential of using biochar to mitigate the leaching of the tested polar pesticides or metabolites is limited. Copyright © 2014 Elsevier Ltd. All rights reserved.

Transport of Organic Compounds Through Porous Systems Containing Humic Acids.

PubMed

Smilek, Jiri; Sedlacek, Petr; Lastuvkova, Marcela; Kalina, Michal; Klucakova, Martina

2017-03-01

Soil pollution by the presence of different contaminants (e.g. heavy metal ions or pesticides) is one of the biggest problems worldwide. The positive affinity of natural humic acids towards these contaminants might contribute to the soil and ground water protection; therefore it is necessary to study the reactivity and barrier properties of humic acids. An original reactivity-mapping tool based on diffusion techniques designed to study the reactivity and barrier properties of polyelectrolytes was developed and tested on humic acids. The results of diffusion experiments demonstrate that the electrostatic interactions between humic acids functioning as a polyelectrolyte interpenetrated in a supporting hydrogel matrix (agarose) and cationic dye (methylene blue) as a model solute have a crucial impact on the rate of diffusion processes and on the barrier properties of hydrogels. The intensity of interactions was evaluated by fundamental diffusion parameters (effective diffusion coefficients and breakthrough time). The impact of modification of humic acids was also studied by means of diffusion experiments conducted on two types of standard humic acids (Leonardite 1S104H) and humic acids with selectively methylated carboxylic groups.

Ecological and ecotoxicological responses in the assessment of the ecological status of freshwater systems: A case-study of the temporary stream Brejo of Cagarrão (South of Portugal).

PubMed

Palma, P; Matos, C; Alvarenga, P; Köck-Schulmeyer, M; Simões, I; Barceló, D; López de Alda, M J

2018-09-01

The objective of the study was to assess the integrated use of macroinvertebrate indexes and ecotoxicological parameters in the evaluation of the ecological status of a temporary stream with a strong agricultural influence. Water quality was analysed at two sampling sites along the stream, considering: chemical supporting parameters; hazardous substances (pesticides); benthic macroinvertebrate communities, through quality (Iberian Biological Monitoring Working Party and Iberian Average Score Per Taxon) and multi-metric indices (Southern Portuguese Index of Invertebrates and Ecological Quality Ratio); and ecotoxicological responses using lethal and sub-lethal bioassays. The water chemical characterization showed high levels of organic matter and nutrients, mainly in the dry period ((biochemical oxygen demand (BOD 5 ): 18.5-25.5mgL -1 , chemical oxygen demand (COD): 60.8-193.7mgL -1 ; total phosphorus (TP): 0.17-0.33mgL -1 )), which may compromise the support of biological life. In accordance with the physicochemical results, the stream had an ecological status less than good. Of the 25 pesticides analysed, only five, namely terbuthylazine, 2-methyl-chlorophenoxyacetic acid, bentazone, mecoprop and metolachlor were quantified. In general, the concentrations of pesticides detected were low, except at the source of the stream in January 2012 (sum of pesticides 2.29μgL -1 ), mainly due to the concentration of bentazone (1.77μgL -1 ), both values surpassing the European Commission threshold values. The analysis of benthic macroinvertebrates showed low levels of abundance and family diversity, with communities dominated by resistant groups to organic pollution and pesticides, such as the Chironomidae family. In general, the reproduction ecotoxicological results showed a very marked decrease in the number of juveniles per female. The Spearman correlation identified pesticides, namely MCPA (R=-0.89; p<0.05), as the main responsible for the observed effect. The results showed the linearity and complementarity of the two groups of biological responses, allowing to cover the interactions between the ecosystem's species and the different types of pollutants. Copyright © 2018 Elsevier B.V. All rights reserved.

Metabolome disruption of pregnant rats and their offspring resulting from repeated exposure to a pesticide mixture representative of environmental contamination in Brittany.

PubMed

Bonvallot, Nathalie; Canlet, Cécile; Blas-Y-Estrada, Florence; Gautier, Roselyne; Tremblay-Franco, Marie; Chevolleau, Sylvie; Cordier, Sylvaine; Cravedi, Jean-Pierre

2018-01-01

The use of pesticides exposes humans to numerous harmful molecules. Exposure in early-life may be responsible for adverse effects in later life. This study aimed to assess the metabolic modifications induced in pregnant rats and their offspring by a pesticide mixture representative of human exposure. Ten pregnant rats were exposed to a mixture of eight pesticides: acetochlor (246 μg/kg bw/d) + bromoxynil (12 μg/kg bw/d) + carbofuran (22.5 μg/kg bw/d) + chlormequat (35 μg/kg bw/d) + ethephon (22.5 μg/kg bw/d) + fenpropimorph (15.5 μg/kg bw/d) + glyphosate (12 μg/kg bw/d) + imidacloprid (12.5 μg/kg bw/d) representing the main environmental pesticide exposure in Brittany (France) in 2004. Another group of 10 pregnant rats served as controls. Females were fed ad libitum from early pregnancy, which is from gestational day (GD) 4 to GD 21. Urine samples were collected at GD 15. At the end of the exposure, mothers and pups were euthanized and blood, liver, and brain samples collected. 1H NMR-based metabolomics and GC-FID analyses were performed and PCA and PLS-DA used to discriminate between control and exposed groups. Metabolites for which the levels were significantly modified were then identified using the Kruskal-Wallis test, and p-values were adjusted for multiple testing correction using the False Discovery Rate. The metabolomics analysis revealed many differences between dams of the two groups, especially in the plasma, liver and brain. The modified metabolites are involved in TCA cycle, energy production and storage, lipid and carbohydrate metabolism, and amino-acid metabolism. These modifications suggest that the pesticide mixture may induce oxidative stress associated with mitochondrial dysfunction and the impairment of glucose and lipid metabolism. These observations may reflect liver dysfunction with increased relative liver weight and total lipid content. Similar findings were observed for glucose and energy metabolism in the liver of the offspring, and oxidative stress was also suggested in the brains of male offspring.

Hybridization of the natural antibiotic, cinnamic acid, with layered double hydroxides (LDH) as green pesticide.

PubMed

Park, Man; Lee, Chang-Il; Seo, Young Jin; Woo, Sang Ryung; Shin, Dongill; Choi, Jyung

2010-01-01

Heavy application of highly toxic synthetic pesticides has been committed to protect crops against insects and diseases, which have brought about serious environmental problems. Thus, an inevitable and fundamental issue has been how to protect crops without harmful effects on nature. As a fascinating nature-compatible approach, we have attempted to hybridize soil-compatible layered double hydroxides (LDHs) with natural antibiotic substances. Only a few of natural antibiotic substances are available for pest control mainly because of their inherent properties such as easy degradability, high minimum inhibition concentration for practical application, and often extremely low availability, whereas LDHs exhibit unique properties such as anion exchange capacity, acid lability, and high affinity to ubiquitous carbonate ion which make them an excellent inorganic matrix to carry labile biomolecules in soils. This study focuses on the behavior of cinnamate-LDH hybrid in soils and the evaluation of its potentials as a green pesticide. The cinnamate-LDH hybrid was synthesized by a typical coprecipitation method. Cinnamic acid was analyzed by high performance liquid chromatography which was operated at 280 nm with C18 column. Its controlled release property was evaluated in a cultivated soil as well as a simulated soil solution. Its antifungal activity was examined against the growth of Phytophyhora capsici in a potato dextrose agar medium and a red pepper seedling, respectively. Structural characterization by X-ray diffraction, infra-red, and thermal analysis indicates that cinnamate molecules are safely intercalated into the interlayer space of inorganic layers of LDH by the electrostatic interaction to have an empirical formula of Mg(3)Al(OH)(8).CAN . 3.1H(2)O. The overall release pattern of the intercalated cinnamate in the soil solution could be best described by the power-function equation [Formula: see text]. This suggests that diffusion-controlled processes besides simple ion-exchange process play an important role in release of the intercalated cinnamate. Furthermore, its behavior in a cultivated soil clearly shows that hybridization leads to protection of cinnamate against the degradation as well as to a controlled release in soils. Its antifungal activity against the growth of P. capsici in a potato dextrose agar medium and a red pepper seedling definitely shows that the hybrid is very effective in controlling the root rot of red pepper. This study demonstrates that the hybridization of natural antibiotic substances with layered double hydroxides could be a fascinating alternative for green formulation of pesticides. This unique hybrid system leads to the salient features such as protection of the substances against chemical and microbial degradations, controlled release, and nature compatibility. This study suggests one of the sound strategies to make a breakthrough in the formulation of green pesticides. Hybridization with inorganic matrixes not only enables the natural antibiotic substances to replace the synthetic ingredients but also adjuvants to be excluded from the formulations. Furthermore, the resulting hybrid exhibits a controlled release of the intercalated substances. Although substantiated further, this study is expected to attract a great deal of attention to reliable application of natural antibiotic substances in green protection of crops and agricultural products.

[Effects of controlling specific dangerous pesticides on prevention of acute pesticide poisoning in rural area].

PubMed

Zhang, Ping; Zhao, Jiang-xia; Chang, Xiu-li; Zhou, Zhi-jun

2010-09-01

To investigate the effects of controlling the specific dangerous pesticides on prevention of acute pesticide poisoning in rural area. The data of reported cases of pesticide poisoning were analyzed to find out the specific dangerous pesticide in acute pesticide poisoning. Then the occurrence of occupational pesticide poisoning and fatality of non-occupational pesticide poisoning were estimated under the hypothesis of removing the specific dangerous pesticides. The data indicated that parathion (including methyl parathion) was the specific dangerous pesticide inducing occupational pesticide poisoning. After removing the use of parathion, the hazard of pesticides which caused occupational pesticide poisoning would be significantly decreased (P < 0.01). Parathion was also the most dangerous pesticide which caused non-occupational pesticide poisoning, with its fatality up to 15.8%. If parathion was well controlled, the fatality of non-occupational pesticide poisoning would be declined from 9.4% to 7.4%. The analyses of related literatures also revealed the similar results. The occurrence of occupational pesticide poisoning and fatality of non-occupational pesticide poisoning may decrease if the most dangerous pesticides are well supervised.

Toxic impact of aldrin on acid and alkaline phosphatase activity of penaeid prawn, Metapenaeus monoceros: In vitro study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reddy, M.S.; Jayaprada, P.; Rao, K.V.R.

1991-03-01

The increasing contamination of the aquatic environment by the indiscriminate and widespread use of different kinds of pesticides is a serious problem for environmental biologists. Organochlorine insecticides are more hazardous since they are not only more toxic but also leave residues in nature. The deleterious effects of aldrin on several crustaceans have been studied. But studies concerning the impact of aldrin on biochemical aspects of crustaceans are very much limited. The present study is aimed at probing the in vitro effects of aldrin on the acid and alkaline phosphatase activity levels in selected tissues of penaeid prawn, Metapenaeus monoceros (Fabricius).

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.

Modelling fate and transport of glyphosate and AMPA in the Meuse catchment to assess the contribution of different pollution sources

NASA Astrophysics Data System (ADS)

Desmet, Nele; Seuntjens, Piet

2013-04-01

Large river basins have multiple sources of pesticides and usually the pollution sources are spread over the entire catchment. The cumulative effect of pesticides entering the river system in upstream areas and the formation of persistent degradation products can compromise downstream water use e.g. raw water quality for drinking water abstractions. For assessments at catchment scale pesticide fluxes coming from different sources and sub basins need to be taken into account. To improve management strategies, a sound understanding of the sources, emission routes, transport, environmental fate and conversion of pesticides is needed. In the Netherlands, the Meuse river basin is an important source for drinking water production. The river suffers from elevated concentrations of glyphosate and aminomethylphosphonic acid (AMPA). For AMPA it is rather unclear to what extent the pollution is related to glyphosate degradation and what is the contribution of other sources, especial phosphonates in domestic and industrial waste water. Based on the available monitoring data only it is difficult to distinguish between AMPA sources in such a large river basin. This hampers interpretation and decision making for water quality management in the Meuse catchment. Here, application of water quality models is very useful to obtain complementary information and insights. Modelling allows accounting for temporal and spatial variability in discharge and concentrations as well as distinguishing the contribution from conversion processes. In this study, a model for the river Meuse was developed and applied to assess the contribution of tributary and transnational influxes, glyphosate degradation and other sources to the AMPA pollution.

The dissipation of three fungicides in a biobed organic substrate and their impact on the structure and activity of the microbial community.

PubMed

Marinozzi, Maria; Coppola, Laura; Monaci, Elga; Karpouzas, Dimitrios G; Papadopoulou, Evangelia; Menkissoglu-Spiroudi, Urania; Vischetti, Costantino

2013-04-01

Biopurification systems (BPS) have been introduced to minimise the risk for point source contamination of natural water resources by pesticides. Their depuration efficiency relies mostly on the high biodegradation of their packing substrate (biomixture). Despite that, little is known regarding the interactions between biomixture microflora and pesticides, especially fungicides which are expected to have a higher impact on the microbial community. This study reports the dissipation of the fungicides azoxystrobin (AZX), fludioxonil (FL) and penconazole (PC), commonly used in vineyards, in a biomixture composed of pruning residues and straw used in vineyard BPS. The impact of fungicides on the microbial community was also studied via microbial biomass carbon, basal respiration and phospholipid fatty acid analysis. AZX dissipated faster (t1/2 = 30.1 days) than PC (t1/2 = 99.0 days) and FL (t1/2 = 115.5 days). Fungicides differently affected the microbial community. PC showed the highest adverse effect on both the size and the activity of the biomixture microflora. A significant change in the structure of the microbial community was noted for PC and FL, and it was attributed to a rapid inhibition of the fungal fraction while bacteria showed a delayed response which was attributed to indirect effects by the late proliferation of fungi. All effects observed were transitory and a full recovery of microbial indices was observed 60 days post-application. Overall, no clear link between pesticide persistence and microbial responses was observed stressing the complex nature of interactions between pesticides in microflora in BPS.

Primary and complex stressors in polluted mediterranean rivers: Pesticide effects on biological communities

NASA Astrophysics Data System (ADS)

Ricart, Marta; Guasch, Helena; Barceló, Damià; Brix, Rikke; Conceição, Maria H.; Geiszinger, Anita; José López de Alda, Maria; López-Doval, Julio C.; Muñoz, Isabel; Postigo, Cristina; Romaní, Anna M.; Villagrasa, Marta; Sabater, Sergi

2010-03-01

SummaryWe examined the presence of pesticides in the Llobregat river basin (Barcelona, Spain) and their effects on benthic biological communities (invertebrates and diatoms). The Llobregat river is one of Barcelona's major drinking water resources. It has been highly polluted by industrial, agricultural, and urban wastewaters, and—as a typical Mediterranean river—is regularly subjected to periodic floods and droughts. Water scarcity periods result in reduced water flow and dilution capacity, increasing the potential environmental risk of pollutants. Seven sites were selected, where we analysed the occurrence of 22 pesticides (belonging to the classes of triazines, organophosphates, phenylureas, anilides, chloroacetanilides, acidic herbicides and thiocarbamates) in the water and sediment, and the benthic community structure. Biofilm samples were taken to measure several metrics related to both the algal and bacterial components of fluvial biofilms. Multivariate analyses revealed a potential relationship between triazine-type herbicides and the distribution of the diatom community, although no evidence of disruption in the invertebrate community distribution was found. Biofilm metrics were used as response variables rather than abundances of individual species to identify possible cause-effect relationships between pesticide pollution and biotic responses. Certain effects of organophosphates and phenylureas in both structural and functional aspects of the biofilm community were suggested, but the sensitivity of each metric to particular stressors must be assessed before we can confidently assign causality. Complemented with laboratory experiments, which are needed to confirm causality, this approach could be successfully incorporated into environmental risk assessments to better summarise biotic integrity and improve the ecological management.

Can Coffee Chemical Compounds and Insecticidal Plants Be Harnessed for Control of Major Coffee Pests?

PubMed

Green, Paul W C; Davis, Aaron P; Cossé, Allard A; Vega, Fernando E

2015-11-04

Pests and pathogens threaten coffee production worldwide and are difficult to control using conventional methods, such as insecticides. We review the literature on the chemistry of coffee, concentrating on compounds most commonly reported from Coffea arabica and Coffea canephora. Differences in chemistry can distinguish coffee species and varieties, and plants grown under different biogeographic conditions exhibit different chemotypes. A number of chemical groups, such as alkaloids and caffeoylquinic acids, are known to be insecticidal, but most studies have investigated their effects on coffee quality and flavor. More research is required to bridge this gap in knowledge, so that coffee can be bred to be more resistant to pests. Furthermore, we report on some pesticidal plants that have been used for control of coffee pests. Locally sourced pesticidal plants have been underutilized and offer a sustainable alternative to conventional insecticides and could be used to augment breeding for resilience of coffee plants.

Structure-Guided Engineering of Molinate Hydrolase for the Degradation of Thiocarbamate Pesticides

PubMed Central

Paiva, Ana M.; Ferreira-da-Silva, Frederico; Matias, Pedro M.; Nunes, Olga C.; Gales, Luís

2015-01-01

Molinate is a recalcitrant thiocarbamate used to control grass weeds in rice fields. The recently described molinate hydrolase, from Gulosibacter molinativorax ON4T, plays a key role in the only known molinate degradation pathway ending in the formation of innocuous compounds. Here we report the crystal structure of recombinant molinate hydrolase at 2.27 Å. The structure reveals a homotetramer with a single mononuclear metal-dependent active site per monomer. The active site architecture shows similarities with other amidohydrolases and enables us to propose a general acid-base catalysis mechanism for molinate hydrolysis. Molinate hydrolase is unable to degrade bulkier thiocarbamate pesticides such as thiobencarb which is used mostly in rice crops. Using a structural-based approach, we were able to generate a mutant (Arg187Ala) that efficiently degrades thiobencarb. The engineered enzyme is suitable for the development of a broader thiocarbamate bioremediation system. PMID:25905461

An Evaluation of the Eclox Chemiluminescence Test, Hach Pesticide/Nerve Agent Test Strips, and Agri-Screen Test Tickets

DTIC Science & Technology

2010-06-30

Interference Testing Our testing shows that it is unlikely that the Eclox Chemiluminescence Test will respond to the common disinfectant chloramine ...common disinfectants (chlorine and chloramine ), cyanobacterial byproducts (geosmin and MIB) or water quality parameters (humic/fulvic acids or water...toxicity sensor testing Table 2-2: Interferences Test Chemicals Concentration (mg/L) Chlorine 10 Chloramines 10 Geosmin 0.0001 Methyl-isoborneol

Installation Restoration General Environmental Technology Development. Task 3. Guidelines for In-Place Closure of Dry Lagoons. Volume 2. Evaluation of In-Place Closure Technologies.

DTIC Science & Technology

1984-01-01

fac- turs are described as follows: (a) Basil stability -- Determination of horizontal movement in the slurry wall or the ground behind the wall...SG-l.2) M Acid mine drainage (FeSO4 pH 3) N Liqnin (in Ca++ solution) N Orqanic residues trom pesticide manutacture N Alcohol M/H asiqnificant

Human health and ecological risk assessments for SmartStax PRO (MON 89034 x TC1507 x MON 87411 x DAS-59122-7), a plant-incorporated protectant intended to control corn rootworm through ribonucleic acid (RNA) interference

EPA Science Inventory

The use of RNA interference (RNAi) gene silencing technology, particularly RNAi for pesticidal purposes to control macroorganism pests, is a relatively recent innovation. Post-transcriptional silencing of gene function is a very rapid process where double-stranded RNA (dsRNA) dir...

Sublethal toxicity of chlorpyrifos to salmonid olfaction after hypersaline acclimation.

PubMed

Maryoung, Lindley A; Blunt, Brian; Tierney, Keith B; Schlenk, Daniel

2015-04-01

Salmonid habitats can be impacted by several environmental factors, such as salinization, which can also affect salmonid tolerance to anthropogenic stressors, such as pesticides. Previous studies have shown that hypersaline acclimation enhances the acute toxicity of certain organophosphate and carbamate pesticides to euryhaline fish; however, sublethal impacts have been far less studied. The current study aims to determine how hypersaline acclimation and exposure to the organophosphate chlorpyrifos (CPF) impact salmonid olfaction. Combined acclimation and exposure to CPF was shown to impact rainbow trout olfaction at the molecular, physiological, and behavioral levels. Concurrent exposure to hypersalinity and 0.5μg/L CPF upregulated four genes (chloride intracellular channel 4, G protein zgc:101761, calcium calmodulin dependent protein kinase II delta, and adrenergic alpha 2C receptor) that inhibit olfactory signal transduction. At the physiological level, hypersalinity and chlorpyrifos caused a decrease in sensory response to the amino acid l-serine and the bile salt taurocholic acid. Combined acclimation and exposure also negatively impacted behavior and reduced the avoidance of a predator cue (l-serine). Thus, acclimation to hypersaline conditions and exposure to environmentally relevant concentrations of chlorpyrifos caused an inhibition of olfactory signal transduction leading to a decreased response to odorants and impairment of olfactory mediated behaviors. Copyright © 2015 Elsevier B.V. All rights reserved.

Study of different HILIC, mixed-mode, and other aqueous normal-phase approaches for the liquid chromatography/mass spectrometry-based determination of challenging polar pesticides.

PubMed

Vass, Andrea; Robles-Molina, José; Pérez-Ortega, Patricia; Gilbert-López, Bienvenida; Dernovics, Mihaly; Molina-Díaz, Antonio; García-Reyes, Juan F

2016-07-01

The aim of the study was to evaluate the performance of different chromatographic approaches for the liquid chromatography/mass spectrometry (LC-MS(/MS)) determination of 24 highly polar pesticides. The studied compounds, which are in most cases unsuitable for conventional LC-MS(/MS) multiresidue methods were tested with nine different chromatographic conditions, including two different hydrophilic interaction liquid chromatography (HILIC) columns, two zwitterionic-type mixed-mode columns, three normal-phase columns operated in HILIC-mode (bare silica and two silica-based chemically bonded columns (cyano and amino)), and two standard reversed-phase C18 columns. Different sets of chromatographic parameters in positive (for 17 analytes) and negative ionization modes (for nine analytes) were examined. In order to compare the different approaches, a semi-quantitative classification was proposed, calculated as the percentage of an empirical performance value, which consisted of three main features: (i) capacity factor (k) to characterize analyte separation from the void, (ii) relative response factor, and (iii) peak shape based on analytes' peak width. While no single method was able to provide appropriate detection of all the 24 studied species in a single run, the best suited approach for the compounds ionized in positive mode was based on a UHPLC HILIC column with 1.8 μm particle size, providing appropriate results for 22 out of the 24 species tested. In contrast, the detection of glyphosate and aminomethylphosphonic acid could only be achieved with a zwitterionic-type mixed-mode column, which proved to be suitable only for the pesticides detected in negative ion mode. Finally, the selected approach (UHPLC HILIC) was found to be useful for the determination of multiple pesticides in oranges using HILIC-ESI-MS/MS, with limits of quantitation in the low microgram per kilogram in most cases. Graphical Abstract HILIC improves separation of multiclass polar pesticides.

Urinary Metabolites of Organophosphate and Pyrethroid Pesticides and Behavioral Problems in Canadian Children

PubMed Central

Oulhote, Youssef

2013-01-01

Background: Exposure to organophosphate pesticides has been associated with neurobehavioral deficits in children, although data on low levels of exposure experienced by the general population are sparse. Pyrethroids are insecticides rapidly gaining popularity, and epidemiological evidence on their potential effects is lacking. Objective: We examined the association between exposure to organophosphate and pyrethroid pesticides, indicated by urinary metabolites, and parentally reported behavioral problems in children. Methods: We used data on children 6–11 years of age from the Canadian Health Measures Survey (2007–2009). We used logistic regressions to estimate odds ratios (ORs) for high scores on the Strengths and Difficulties Questionnaire (SDQ), which may indicate behavioral problems, in association with concentrations of pyrethroid and organophosphate metabolites in the urine of 779 children, adjusting for covariates (sex, age, race/ethnicity, income, parental education, blood lead levels, maternal smoking during pregnancy, and others). Results: At least one urinary metabolite for organophosphates was detected in 91% of children, and for pyrethroids in 97% of children. Organophosphate metabolites were not significantly associated with high SDQ scores. The pyrethroid metabolite cis-DCCA [3-(2,2-dichlorovinyl)-2,2-dimethylycyclopropane carboxylic acid] was significantly associated with high scores for total difficulties on the SDQ (OR for a 10-fold increase = 2.0; 95% CI: 1.1, 3.6), and there was a nonsignificant association with trans-DCCA (OR = 1.6; 95% CI: 0.9, 3.0). Conclusion: In contrast with previous studies, we did not observe an association between exposure to organophosphate pesticides and behavioral scores in children. However, some pyrethroid urinary metabolites were associated with a high level of parent-reported behavioral problems. Longitudinal studies should be conducted on the potential risks of pyrethroids. Citation: Oulhote Y, Bouchard MF. 2013. Urinary metabolites of organophosphate and pyrethroid pesticides and behavioral problems in Canadian children. Environ Health Perspect 121:1378–1384; http://dx.doi.org/10.1289/ehp.1306667 PMID:24149046

A multi-residue method for pesticides analysis in green coffee beans using gas chromatography-negative chemical ionization mass spectrometry in selective ion monitoring mode.

PubMed

Pizzutti, Ionara R; de Kok, Andre; Dickow Cardoso, Carmem; Reichert, Bárbara; de Kroon, Marijke; Wind, Wouter; Weber Righi, Laís; Caiel da Silva, Rosselei

2012-08-17

In this study, a new gas chromatography-mass spectrometry (GC-MS) method, using the very selective negative chemical ionization (NCI) mode, was developed and applied in combination with a modified acetonitrile-based extraction method (QuEChERS) for the analysis of a large number of pesticide residues (51 pesticides, including isomers and degradation products) in green coffee beans. A previously developed integrated sample homogenization and extraction method for both pesticides and mycotoxins analysis was used. An homogeneous slurry of green milled coffee beans and water (ratio 1:4, w/w) was prepared and extracted with acetonitrile/acetic acid (1%), followed by magnesium sulfate addition for phase separation. Aliquots from this extract could be used directly for LC-MS/MS analysis of mycotoxins and LC-amenable pesticides. For GC-MS analysis, a further clean-up was necessary. C18- and PSA-bonded silica were tested as dispersive solid-phase extraction (d-SPE) sorbents, separate and as a mixture, and the best results were obtained using C18-bonded silica. For the optimal sensitivity and selectivity, GC-MS detection in the NCI-selected ion monitoring (SIM) mode had to be used to allow the fast analysis of the difficult coffee bean matrix. The validation was performed by analyzing recovery samples at three different spike concentrations, 10, 20 and 50 μg kg(-1), with 6 replicates (n=6) at each concentration. Linearity (r(2)) of calibration curves, estimated instrument and method limits of detection and limits of quantification (LOD(i), LOD(m), LOQ(i) and LOQ(m), respectively), accuracy (as recovery %), precision (as RSD%) and matrix effects (%) were determined for each individual pesticide. From the 51 analytes (42 parent pesticides, 4 isomers and 5 degradation products) determined by GC-MS (NCI-SIM), approximately 76% showed average recoveries between 70-120% and 75% and RSD ≤ 20% at the lowest spike concentration of 10 μg kg(-1), the target method LOQ. For the spike concentrations of 20 and 50 μg kg(-1), the recoveries and RSDs were even better. The validated LOQ(m) was 10, 20 and 50 μg kg(-1) for respectively 33, 3 and 6 of the analytes studied. For five compounds, the European Union method performance requirements for the validation of a quantitative method (average recoveries between 70-120% and repeatability RSD ≤ 20%) were not achieved and 4 problematic pesticides (captan, captafol, folpet and dicofol) could not be detected as their parent compound, but only via their degradation products. Although the matrix effect (matrix-enhanced detector response) was high for all pesticides studied, the matrix interference was minimal, due to the high selectivity obtained with the GC-NCI-MS detection. Matrix-matched calibration for applying the method in routine analysis is recommended for reliable quantitative results. Copyright © 2012 Elsevier B.V. All rights reserved.

Effects on grape amino acid concentration through foliar application of three different elicitors.

PubMed

Gutiérrez-Gamboa, G; Portu, J; Santamaría, P; López, R; Garde-Cerdán, T

2017-09-01

Elicitors play an important role in the defense against pathogens as an alternative to chemical pesticides by increasing secondary metabolites. Their effect on grape amino acid has been little investigated. Thus, the aim of this research was to study the influence of methyl jasmonate (MeJ), chitosan (CHT), and a yeast extract (YE) on grape amino acid composition, through foliar applications to grapevines. The must amino acid concentration was analyzed by HPLC. The results showed that CHT and YE treatments decreased the must concentration of several amino acids, affecting total amino acid content (from 2364 to 1961, and 1818mg/L, respectively). However, MeJ treatment had a slight effect on grape amino acid content, increasing the concentration of Met (from 8.95 to 12.13mg/L) and Phe (from 7.96 to 9.29mg/L). It seems to be that, the resistance induction through CHT and YE treatments results in physiological costs to grapevines associated with a decrease on grape amino acid concentration. Consequently, MeJ applications, as a viticultural practice, could be a better tool than CHT and YE treatments, because did not affect grape amino acid concentration. Copyright © 2017 Elsevier Ltd. All rights reserved.

Simultaneous Removal of Lindane, Lead and Cadmium from Soils by Rhamnolipids Combined with Citric Acid.

PubMed

Wan, Jinzhong; Meng, Die; Long, Tao; Ying, Rongrong; Ye, Mao; Zhang, Shengtian; Li, Qun; Zhou, Yan; Lin, Yusuo

2015-01-01

This study investigated the performance of rhamnolipids-citric acid mixed agents in simultaneous desorption of lindane and heavy metals from soils. The capacity of the mixed agents to solubilize lindane, lead and cadmium in aqueous solution was also explored. The results showed that the presence of citric acid greatly enhanced the solubilization of lindane and cadmium by rhamnolipids. A combined effect of the mixed agents on lindane and heavy metals removal from soils was observed. The maximum desorption ratios for lindane, cadmium and lead were 85.4%, 76.4% and 28.1%, respectively, for the mixed agents containing 1% rhamnolipidsand 0.1 mol/L citric acid. The results also suggest that the removal efficiencies of lead and cadmium were strongly related to their speciations in soils, and metals in the exchangeable and carbonate forms were easier to be removed. Our study suggests that the combining use of rhamnolipids and citric acid is a promising alternative to simultaneously remove organochlorine pesticides and heavy metals from soils.

Simultaneous Removal of Lindane, Lead and Cadmium from Soils by Rhamnolipids Combined with Citric Acid

PubMed Central

Long, Tao; Ying, Rongrong; Ye, Mao; Zhang, Shengtian; Li, Qun; Zhou, Yan; Lin, Yusuo

2015-01-01

This study investigated the performance of rhamnolipids-citric acid mixed agents in simultaneous desorption of lindane and heavy metals from soils. The capacity of the mixed agents to solubilize lindane, lead and cadmium in aqueous solution was also explored. The results showed that the presence of citric acid greatly enhanced the solubilization of lindane and cadmium by rhamnolipids. A combined effect of the mixed agents on lindane and heavy metals removal from soils was observed. The maximum desorption ratios for lindane, cadmium and lead were 85.4%, 76.4% and 28.1%, respectively, for the mixed agents containing 1% rhamnolipidsand 0.1 mol/L citric acid. The results also suggest that the removal efficiencies of lead and cadmium were strongly related to their speciations in soils, and metals in the exchangeable and carbonate forms were easier to be removed. Our study suggests that the combining use of rhamnolipids and citric acid is a promising alternative to simultaneously remove organochlorine pesticides and heavy metals from soils. PMID:26087302

Pesticides and brain cancer linked in orchard farmers of Kashmir.

PubMed

Bhat, Abdul Rashid; Wani, Muhammed Afzal; Kirmani, A R; Raina, T H

2010-10-01

The atmosphere of valley of Kashmir is ideal for fresh and dry fruit production. Millions of tons of pesticides, insecticides and fungicides (chemicals like chlorpyriphos, mancozeb, captan, dimethoate, phosalone, etc.) are being used by the orchard farmers to spray the plants, fruits and the leaves every year. The increasing trend in the incidence of primary malignant brain tumors in orchard farmers of Kashmir is alarming. To determine the relationship between the patients of primary malignant brain tumors and their occupation. Retrospectively case files along with death certificates of 432 patients of primary malignant brain tumors and 457 controls (non-tumor neurologic diseases), admitted for treatment simultaneously over a period of 4 years from January 2005 to December 2008, to the Department of Neurosurgery, Sher-I-Kashmir Institute of Medical Sciences (SKIMS), Kashmir, were studied. Follow-up and family contact was established. The serum cholinesterase activity was measured by kinetic/DGKC calorimetric method and ethylenediaminetetraacetic acid (EDTA) samples were sent to the laboratory. The results are expressed in U/l which is U/l×1000. The laboratory at SKIMS, Srinagar, and Dr Lal PathLabs at New Delhi used a reference range for serum cholinesterase as 3167-6333 U/l. Analysis revealed that 90.04% (389 out of 432) patients were orchard-farm workers, orchard residents and orchard playing children exposed to the high levels of multiple types of neurotoxic and carcinogenic (chlorpyriphos, dimethoate, mancozeb and captan) chemicals for more than 10-20 years. About 31.9% (124 out of 389) of these from both sexes were younger than 40 years beginning exposure at an early age and had higher (<6334 U/l) serum cholinesterase (SCE) levels. The 9.96% (43 out of 432) patients were not exposed to pesticides. On the other hand, only 119 patients out of 457 controls had recorded history of pesticide exposure and 338 were unrelated to pesticides. Out of 389 patients, 71.7% (279 out of 389) were males and 28.3% (110 out of 389) including 7 members of three families, 6 were females and 1 male. All orchard-related 389 patients had high grade tumors as compared to the non-pesticide tumors. Mortality in pesticide exposed tumors was 12%. Higher levels of SCE were found in 31.9% (124 out of 389) patients and decreased levels in only 45.3% (176 out of 389) orchard-related patients. The significantcase/control odds ratio (OR) of 0.28, hospital control SCE OR of 1.1 and family control SCE OR of 1.5, points the finger of suspicion toward the link between pesticides and brain cancer.

Pesticides and brain cancer linked in orchard farmers of Kashmir

PubMed Central

Bhat, Abdul Rashid; Wani, Muhammed Afzal; Kirmani, A. R.; Raina, T. H.

2010-01-01

Background: The atmosphere of valley of Kashmir is ideal for fresh and dry fruit production. Millions of tons of pesticides, insecticides and fungicides (chemicals like chlorpyriphos, mancozeb, captan, dimethoate, phosalone, etc.) are being used by the orchard farmers to spray the plants, fruits and the leaves every year. The increasing trend in the incidence of primary malignant brain tumors in orchard farmers of Kashmir is alarming. Aim: To determine the relationship between the patients of primary malignant brain tumors and their occupation. Materials and Methods: Retrospectively case files along with death certificates of 432 patients of primary malignant brain tumors and 457 controls (non-tumor neurologic diseases), admitted for treatment simultaneously over a period of 4 years from January 2005 to December 2008, to the Department of Neurosurgery, Sher-I-Kashmir Institute of Medical Sciences (SKIMS), Kashmir, were studied. Follow-up and family contact was established. The serum cholinesterase activity was measured by kinetic/DGKC calorimetric method and ethylenediaminetetraacetic acid (EDTA) samples were sent to the laboratory. The results are expressed in U/l which is U/l×1000. The laboratory at SKIMS, Srinagar, and Dr Lal PathLabs at New Delhi used a reference range for serum cholinesterase as 3167–6333 U/l. Results: Analysis revealed that 90.04% (389 out of 432) patients were orchard-farm workers, orchard residents and orchard playing children exposed to the high levels of multiple types of neurotoxic and carcinogenic (chlorpyriphos, dimethoate, mancozeb and captan) chemicals for more than 10–20 years. About 31.9% (124 out of 389) of these from both sexes were younger than 40 years beginning exposure at an early age and had higher (<6334 U/l) serum cholinesterase (SCE) levels. The 9.96% (43 out of 432) patients were not exposed to pesticides. On the other hand, only 119 patients out of 457 controls had recorded history of pesticide exposure and 338 were unrelated to pesticides. Out of 389 patients, 71.7% (279 out of 389) were males and 28.3% (110 out of 389) including 7 members of three families, 6 were females and 1 male. Conclusion: All orchard-related 389 patients had high grade tumors as compared to the non-pesticide tumors. Mortality in pesticide exposed tumors was 12%. Higher levels of SCE were found in 31.9% (124 out of 389) patients and decreased levels in only 45.3% (176 out of 389) orchard-related patients. The significantcase/control odds ratio (OR) of 0.28, hospital control SCE OR of 1.1 and family control SCE OR of 1.5, points the finger of suspicion toward the link between pesticides and brain cancer. PMID:21584215

Liquid Chromatography with Post-Column Reagent Addition of Ammonia in Methanol Coupled to Negative Ion Electrospray Ionization Tandem Mass Spectrometry for Determination of Phenoxyacid Herbicides and their Degradation Products in Surface Water

PubMed Central

Raina, Renata; Etter, Michele L.

2010-01-01

A new liquid chromatography (LC)-negative ion electrospray ionization (ESI−)–tandem mass spectrometry (MS/MS) method with post-column addition of ammonia in methanol has been developed for the analysis of acid herbicides: 2,4-dichlorophenoxy acetic acid, 4-chloro-o-tolyloxyacetic acid, 2-(2-methyl-4-chlorophenoxy)butyric acid, mecoprop, dichlorprop, 4-(2,4-dichlorophenoxy) butyric acid, 2,4,5-trichlorophenoxy propionic acid, dicamba and bromoxynil, along with their degradation products: 4-chloro-2-methylphenol, 2,4-dichlorophenol, 2,4,5-trichlorophenol and 3,5-dibromo-4-hydroxybenzoic acid. The samples were extracted from the surface water matrix using solid-phase extraction (SPE) with a polymeric sorbent and analyzed with LC ESI− with selected reaction monitoring (SRM) using a three-point confirmation approach. Chromatography was performed on a Zorbax Eclipse XDB-C18 (50 × 4.6 mm i.d., 1.8 μm) with a gradient elution using water-methanol with 2 mM ammonium acetate mobile phase at a flow rate of 0.15 mL/min. Ammonia in methanol (0.8 M) was added post-column at a flow rate of 0.05 mL/min to enhance ionization of the degradation products in the MS source. One SRM transition was used for quantitative analysis while the second SRM along with the ratio of SRM1/SRM2 within the relative standard deviation determined by standards for each individual pesticide and retention time match were used for confirmation. The standard deviation of ratio of SRM1/SRM2 obtained from standards run on the day of analysis for different phenoxyacid herbicides ranged from 3.9 to 18.5%. Limits of detection (LOD) were between 1 and 15 ng L−1 and method detection limits (MDL) with strict criteria requiring <25% deviation of peak area from best-fit line for both SRM1 and SRM2 ranged from 5 to 10 ng L−1 for acid ingredients (except dicamba at 30 ng L−1) and from 2 to 30 ng L−1 for degradation products. The SPE-LC-ESI− MS/MS method permitted low nanogram-per-liter determination of pesticides and degradation products for surface water samples. PMID:20212919

Human health risk from arsenical pesticide contaminated soils: a long-term greenhouse study.

PubMed

Quazi, Shahida; Sarkar, Dibyendu; Datta, Rupali

2013-11-15

Arsenic (As) bioaccessibility is an important factor in estimating human health risk. Bioaccessibility of As in soils is primarily dependent on As adsorption, which varies with residence time. This study evaluated the effect of soil aging on potential lifetime cancer risk associated with chronic exposure to As contaminated soils. Four soils, chosen based on their differences in As reactivity, were amended with two arsenical pesticides--sodium arsenate, and dimethylarsinic acid (DMA) at two rates (675 and 1500 mg kg(-1)). Rice was used as the test crop. Soil was sampled immediately after spiking, after 6 months, 1 year, and 3 years. Bioaccessible and total soil As concentrations were used to calculate lifetime excess cancer risk (ECR), which decreased significantly with soil-pesticide equilibration time. Immokalee soil, with the least As adsorption capacity, showed the highest decrease in ECR after 6 months resulting in values lower than the USEPA's cancer risk range of 1 × 10(-4) to 1 × 10(-6). For all other soils, the ECR was much higher than the target range even after 3 years. In the absence of significant changes in As bioaccessibility with time, the total soil As concentration more directly influenced the changes in ECR values with soil aging. Copyright © 2012 Elsevier B.V. All rights reserved.

Cloning and characterization of a pyrethroid pesticide decomposing esterase gene, Est3385, from Rhodopseudomonas palustris PSB-S.

PubMed

Luo, Xiangwen; Zhang, Deyong; Zhou, Xuguo; Du, Jiao; Zhang, Songbai; Liu, Yong

2018-05-09

Full length open reading frame of pyrethroid detoxification gene, Est3385, contains 963 nucleotides. This gene was identified and cloned based on the genome sequence of Rhodopseudomonas palustris PSB-S available at the GneBank. The predicted amino acid sequence of Est3385 shared moderate identities (30-46%) with the known homologous esterases. Phylogenetic analysis revealed that Est3385 was a member in the esterase family I. Recombinant Est3385 was heterologous expressed in E. coli, purified and characterized for its substrate specificity, kinetics and stability under various conditions. The optimal temperature and pH for Est3385 were 35 °C and 6.0, respectively. This enzyme could detoxify various pyrethroid pesticides and degrade the optimal substrate fenpropathrin with a Km and Vmax value of 0.734 ± 0.013 mmol·l -1 and 0.918 ± 0.025 U·µg -1 , respectively. No cofactor was found to affect Est3385 activity but substantial reduction of enzymatic activity was observed when metal ions were applied. Taken together, a new pyrethroid degradation esterase was identified and characterized. Modification of Est3385 with protein engineering toolsets should enhance its potential for field application to reduce the pesticide residue from agroecosystems.

Selective solid-phase extraction based on molecularly imprinted technology for the simultaneous determination of 20 triazole pesticides in cucumber samples using high-performance liquid chromatography-tandem mass spectrometry.

PubMed

Zhao, Fengnian; She, Yongxin; Zhang, Chao; Cao, Xiaolin; Wang, Shanshan; Zheng, Lufei; Jin, Maojun; Shao, Hua; Jin, Fen; Wang, Jing

2017-10-01

A selective analytical method for the simultaneous determination of 20 triazole fungicides and plant growth regulators in cucumber samples was developed using solid-phase extraction with specific molecularly imprinted polymers (MIPs) as adsorbents. The MIPs were successfully prepared by precipitation polymerization using triadimefon as the template molecule, methacrylic acid as the functional monomer, trimethylolpropane trimethacrylate as the crosslinker, and acetonitrile as the porogen. The performance and recognition mechanism for both the MIPs and non-molecularly imprinted polymers were evaluated using adsorption isotherms and adsorption kinetics. Liquid chromatography-tandem quadrupole mass spectrometry was used to identify and quantify the target analytes. The solid-phase extraction using the MIPs was rapid, convenient, and efficient for extraction and enrichment of the 20 triazole pesticides from cucumber samples. The recoveries obtained at three concentration levels (1, 2, and 10μgL -1 ) ranged from 82.3% to 117.6% with relative standard deviations of less than 11.8% (n=5) for all analytes. The limits of detection for the 20 triazole pesticides were all less than 0.4μgL -1 , and were sufficient to meet international standards. Copyright © 2017 Elsevier B.V. All rights reserved.

Application of the Prunus spp. Cyanide Seed Defense System onto Wheat: Reduced Insect Feeding and Field Growth Tests.

PubMed

Mora, Carlos A; Halter, Jonas G; Adler, Cornel; Hund, Andreas; Anders, Heidrun; Yu, Kang; Stark, Wendelin J

2016-05-11

Many crops are ill-protected against insect pests during storage. To protect cereal grains from herbivores during storage, pesticides are often applied. While pesticides have an undoubtable functionality, increasing concerns are arising about their application. In the present study, we investigated a bioinspired cyanogenic grain coating with amygdalin as cyanogenic precursor mimicking the feeding-triggered release of hydrogen cyanide (HCN) found for example in bitter almonds. The multilayer coating consisted of biodegradable polylactic acid with individual layers containing amygdalin or β-glucosidase which is capable of degrading amygdalin to HCN. This reaction occurred only when the layers were ruptured, e.g., by a herbivore attack. Upon feeding coated cyanogenic wheat grains to Tenebrio molitor (mealworm beetle), Rhizopertha dominica (lesser grain borer), and Plodia interpunctella (Indianmeal moth), their reproduction as well as consumption rate were significantly reduced, whereas germination ability increased compared to noncoated grains. In field experiments, we observed an initial growth delay compared to uncoated grains which became negligible at later growth stages. The here shown strategy to artificially apply a naturally occurring defense mechanisms could be expanded to other crops than wheat and has the potential to replace certain pesticides with the benefit of complete biodegradability and increased safety during storage.

Physical, chemical, and biological data for detailed study of irrigation drainage in the Klamath Basin, California and Oregon, 1990-92

USGS Publications Warehouse

MacCoy, D.E.

1994-01-01

Physical, chemical, and biological data were collected between 1990 and 1992 as part of a detailed study by the U.S. Department of Interior of the effects of irrigation drainage on aquatic resources in the Klamath Basin of California and Oregon. Most of the sites for data collection were in and around the upper and lower sump of Tule Lake, in the Tule Lake National Wildlife Refuge, and along major drains in Lower Klamath National Wildlife Refuge. The physical and chemical data consist of particle-size determinations and concentrations of carbon, mercury, arsenic, chlorophenoxy acid, and organochlorine, organophosphate, and carbamate pesticides in bottom sediment; and concentrations of organophosphate, carbamate, and pyrethroid pesticides, major and trace inorganic constituents, nitrogen, phosphorus, and organic carbon in water. Continuous dissolved oxygen, pH, specific conduc- tance, and temperature data from selected sites in 1991 and 1992 are presented in graphical form to summarize the diel water-quality conditions. The biological data consists of concentrations of inorganic constituents and organochlorine pesticides in tissue, invertebrate and fish population surveys, fish health surveys, frog call surveys, egg shell thickness of avian eggs, and in situ and static toxicity bioassay data collected in 1991 and 1992 using aquatic bacteria, plants, invertebrates, fish, and bird species as test organisms.

Comparing atrazine and cyanuric acid electro-oxidation on mixed oxide and boron-doped diamond electrodes.

PubMed

Malpass, Geoffroy R P; Salazar-Banda, Giancarlo R; Miwa, Douglas W; Machado, Sérgio A S; Motheo, Artur J

2013-01-01

The breakdown of pesticides has been promoted by many methods for clean up of contaminated soil and wastewaters. The main goal is to decrease the toxicity of the parent compound to achieve non-toxic compounds or even, when complete mineralization occurs, carbon dioxide and water. Therefore, electrochemical degradation (potentiostatic and galvanostatic) of both the pesticide atrazine and cyanuric acid (CA) at boron-doped diamond (BDD) and Ti/Ru0.3Ti0.7O2 dimensionally stable anode (DSA) electrodes, in different supporting electrolytes (NaCl and Na2SO4), is presented with the aim of establishing the influence of the operational parameters on the process efficiency. The results demonstrate that both the electrode material and the supporting electrolyte have a strong influence on the rate of atrazine removal. In the chloride medium, the rate of atrazine removal is always greater than in sulfate under all conditions employed. Furthermore, in the sulfate medium, atrazine degradation was significant only at the BDD electrode. The total organic carbon (TOC) load decreased by 79% and 56% at the BDD and DSA electrodes, respectively, in the chloride medium. This trend was maintained in the sulfate medium but the TOC removal was lower (i.e. 33% and 13% at BDD and DSA electrodes, respectively). CA, a stable atrazine degradation intermediate, was also studied and it is efficiently removed using the BDD electrode in both media, mainly when high current densities are employed. The use of the BDD electrode in the chloride medium not only degrades atrazine but also mineralized cyanuric acid leading to the higher TOC removal.

Detection of Aryl Hydrocarbon Receptor Activation by Some Chemicals in Food Using a Reporter Gene Assay

PubMed Central

Amakura, Yoshiaki; Tsutsumi, Tomoaki; Yoshimura, Morio; Nakamura, Masafumi; Handa, Hiroshi; Matsuda, Rieko; Teshima, Reiko; Watanabe, Takahiro

2016-01-01

The purpose of this study was to examine whether a simple bioassay used for the detection of dioxins (DXNs) could be applied to detect trace amounts of harmful DXN-like substances in food products. To identify substances with possible DXN-like activity, we assessed the ability of various compounds in the environment to bind the aryl hydrocarbon receptor (AhR) that binds specifically to DXNs. The compounds tested included 19 polycyclic aromatic hydrocarbons (PAHs), 20 PAH derivatives (nitrated, halogenated, and aminated derivatives), 23 pesticides, six amino acids, and eight amino acid metabolites. The AhR binding activities (AhR activity) of these compounds were measured using the chemical activated luciferase gene expression (CALUX) reporter gene assay system. The majority of the PAHs exhibited marked AhR activity that increased in a concentration-dependent manner. Furthermore, there was a positive link between AhR activity and the number of aromatic rings in the PAH derivatives. Conversely, there appeared to be a negative correlation between AhR activity and the number of chlorine residues present on halogenated PAH derivatives. However, there was no correlation between AhR activity and the number and position of substituents among nitrated and aminated derivatives. Among the pesticides tested, the indole-type compounds carbendazim and thiabendazole showed high levels of activity. Similarly, the indole compound tryptamine was the only amino acid metabolite to induce AhR activity. The results are useful in understanding the identification and characterization of AhR ligands in the CALUX assay. PMID:28231110

Multi-residue determination of pesticides in tropical fruits using liquid chromatography/tandem mass spectrometry.

PubMed

Botero-Coy, A M; Marín, J M; Ibáñez, M; Sancho, J V; Hernández, F

2012-03-01

Monitoring pesticide residues in tropical fruits is of great interest for many countries, e.g., from South America, that base an important part of their economy on the exportation of these products. In this work, a LC-MS/MS multi-residue method using a triple quadrupole analyzer has been developed for around 30 pesticides in seven Colombian tropical fruits of high commercial value for domestic and international markets (uchuva, tamarillo, granadilla, gulupa, maracuya, papaya, and pithaya). After sample extraction with acetonitrile, an aliquot of the extract was diluted with water and directly injected into the HPLC-MS/MS system (electrospray interface) without any cleanup step. The formation of sodium adducts-of poor fragmentation-was minimized using 0.1% formic acid in the mobile phase, which favored the formation of the protonated molecule. However, the addition of ammonium acetate made the formation of the ammonium adducts in some particular cases possible, avoiding the presence of the sodium adducts. The highest sensitivity was observed in positive electrospray ionization for the wide majority of pesticides, with a few exceptions for acidic compounds that gave better response in the negative mode (e.g., 2,4-D, fluazinan). Thus, simultaneous acquisition on the positive/negative mode was applied. Two MS/MS transitions were acquired for each compound to ensure a reliable quantification and identification of the compounds detected in samples, although for malathion a third transition was acquired due to the presence of interfering isobaric compounds in the sample extracts. A detailed study of matrix effects was made by a comparison of standards in solvent and in matrix. Both ionization suppression and ionization enhancement were observed depending on the analyte/matrix combination tested. Correction of matrix effects was made by the application of calibration in matrix. Three matrices were selected (uchuva, maracuya, gulupa) to perform matrix calibration in the analysis of all seven fruit varieties studied. The method was validated by recovery experiments in samples spiked at two levels (0.05 and 0.5 mg/kg). The data were satisfactory for the wide majority of analyte/matrix combinations, with most recoveries between 70% and 110% and the RSD below 15%. Several samples collected from the market were finally analyzed. Positive findings were confirmed by evaluating the experimental Q/q ratios and retention times, and comparing them with those of reference standards.

75 FR 34448 - Pesticides; Draft Guidance for Pesticide Registrants on False or Misleading Pesticide Product...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-06-17

... Pesticide Registrants on False or Misleading Pesticide Product Brand Names; Extension of Comment Period... Pesticide Product Brand Names.'' This document extends the comment period for 60 days, from June 18, 2010... draft Pesticide Registration Notice (PR Notice) entitled ``False or Misleading Pesticide Product Brand...

Hydrogeology and water quality of the Pepacton Reservoir Watershed in southeastern New York. Part 1. Concentrations of pesticides and their degradates in stream baseflow, 2000-2001

USGS Publications Warehouse

Phillips, Patrick J.; Heisig, Paul M.

2004-01-01

Baseflow samples were collected from 20 small streams in the Pepacton Reservoir watershed in Delaware County, N.Y., from December 2000 through November 2001 as part of an investigation to define the occurrence of pesticides in shallow ground water in watersheds containing either a recent (2001) corn crop, a previous (1993-94) corn crop, or no history of row-crop cultivation. Baseflow water quality was assumed to represent the chemical quality of shallow ground water within the drainage area above each sampling site.Baseflow samples were analyzed for 57 pesticides and pesticide degradates. Three herbicides (atrazine, metolachlor and simazine) and three herbicide degradates (alachlor ESA [ethanesulfonic acid], deethylatrazine, and metolachlor ESA) were detected, but no concentrations exceeded any Federal or State water-quality criteria, and the maximum concentrations of all compounds except metolachlor ESA were less than 0.10 microgram per liter. The most frequently detected compounds (atrazine, metolachlor, deethylatrazine and metolachlor ESA) are either those typically used on corn crops, or those whose parent compounds are commonly used on corn crops and have been detected in streams that drain row-crop settings elsewhere in New York State. The pesticide and pesticide-degradate concentrations in baseflow samples collected in December 2000 and July 2001 samples generally corresponded to the amount of cornfield acreage in each watershed in 2001.The types of pesticides detected, and their median concentrations, were similar to those noted in two previous ground-water studies in row-crop areas elsewhere in upstate New York. Also the SAM ratios (ratio of metolachlor ESA concentration to metolachlor concentration) for the Pepacton samples were similar to those for ground-water samples from other agricultural settings in upstate New York, but were significantly higher than that for stormflow and baseflow samples collected in 1997-98 from Canajoharie Creek, an upstate stream that drains row-crop farmland. These comparisons confirm that the baseflow samples were derived from, and were representative of, ground water in their respective watersheds. Late-summer decreases in atrazine and deethylatrazine concentrations at a site where corn was grown in 2001 may have resulted from the seasonally dry conditions and the accompanying decrease in ground-water discharge from the upper-most part of the surficial aquifer system to streams. The lack of a similar decrease in metolachlor ESA concentrations during this period may reflect the transport of metolachlor ESA to deeper parts of the surficial aquifer that continued to discharge to streams during the dry period.

Production of 3-Oxo-2-(2'-pentenyl)-cyclopentane-1-octanoic Acid in the Fungus Aspergillus oryzae: A Step Towards Heterologous Production of Pyrethrins in Fungi.

PubMed

Mohamed, Maged E; Pahirulzaman, Khomaizon A K; Lazarus, Colin M

2016-03-01

Pyrethrins are natural insecticides, which accumulate to high concentrations in pyrethrum (Chrysanthemum cinerariaefolium) flowers. Synthetic pyrethroids are more stable, more efficacious and cheaper, but contemporary requirements for safe and environmentally friendly pesticides encourage a return to the use of natural pyrethrins, and this would be favoured by development of an efficient route to their production by microbial fermentation. The biosynthesis of pyrethrins involves ester linkage between an acid moiety (chrysanthemoyl or pyrethroyl, synthesised via the mevalonic acid pathway from glucose), and an alcohol (pyrethrolone). Pyrethrolone is generated from 3-oxo-2-(2'-pentenyl)-cyclopentane-1-octanoic acid, which originates from α-linolenic acid via the jasmonic acid biosynthetic cascade. The first four genes in this cascade, encoding lipoxygenase 2, allene-oxide synthase, allene-oxide cyclase 2 and 12-oxophytodienoic acid reductase 3, were amplified from an Arabidopsis thaliana cDNA library, cloned in a purpose-built fungal multigene expression vector and expressed in Aspergillus oryzae. HPLC-MS analysis of the transgenic fungus homogenate gave good evidence for the presence of 3-oxo-2-(2'-pentenyl)-cyclopentane-1-octanoic acid.

75 FR 28012 - Pesticides; Draft Guidance for Pesticide Registrants on False or Misleading Pesticide Product...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-05-19

... Pesticide Registrants on False or Misleading Pesticide Product Brand Names AGENCY: Environmental Protection... Pesticide Product Brand Names.'' PR Notices are issued by the Office of Pesticide Programs (OPP) to inform... concerning pesticide product brand names that may be false or misleading, either by themselves or in...

Acetylcholinesterase of the Sand Fly, Phlebotomus papatasi (Scopoli): cDNA Sequence, Baculovirus Expression, and Biochemical Properties

DTIC Science & Technology

2013-01-01

identity to acetylcholinesterase mRNA sequences of Culex tritaeniorhynchus and Lutzomyia longipalpis, respectively. The P. papatasi cDNA ORF encoded a...tritaeniorhynchus and Lutzomyia longipalpis, respectively. The P. papatasi cDNA ORF encoded a 710-amino acid protein [GenBank: AFP20868] exhibiting 85...improve effectiveness of pesticide application for control of the new world sand fly Lutzomyia longipalpis in chicken sheds [13]. Attempts to control

U.S. EPA, Pesticide Product Label, TRIPLE ACTION 10-6-4 LITE WGT PLNT FD CRABGRSS PREVNTR INSECT CTRL, 04/02/1968

EPA Pesticide Factsheets

2011-04-19

li!"~:'i • 1l1t.

US Army Biomedical Laboratory Annual Progress Report, 1 October 1986-30 September 1987. Volume 1

DTIC Science & Technology

1987-12-07

support of casualties during evacuation within the theater of operations . To fulfill this requirement USABRDL has initiated a project to identify and...Tests of its operational capabilities will be conducted. Aerial application of granular pesticide was done to control ticks at Fort A.P. Hill, Virginia...with limited amounts of hypochlorous acid ; and the testing of several polymeric and monomeric diacetylene compounds as potential indicators to be used

Extraction and GC determination of volatile aroma compounds from extracts of three plant species of the Apiaceae family

NASA Astrophysics Data System (ADS)

Stan, M.; Soran, M. L.; Varodi, C.; Lung, I.; Copolovici, L.; MǎruÅ£oiu, C.

2013-11-01

Parsley (Petroselinum crispum), dill (Anethum graveolens) and celery (Apium graveolens), three aromatic plants belonging to the Apiaceae (Umbelliferae) botanical family, were selected as sources of essential or volatile oils. Essential oils are composed of a large diversity of volatile aroma compounds. Plant-derived essential oils and extracts have long been used as natural agents in food preservation, pharmaceuticals and medicinal therapies. In the present study, the plant extracts from leaves of parsley, dill and celery, were obtained by maceration, ultrasound-assisted extraction and microwave-assisted extraction. All extractions were performed at 30°C, using different solvents (ethanol, diethyl ether, n-hexane) and solvent mixtures (1:1, v/v). The most effective solvent system for the extraction of volatile aroma compounds was diethyl ether - n-hexane (1:1, v/v). Extraction efficiency and determination of aroma volatiles were performed by GC-FID and GC-MS, respectively. The major volatile compounds present in plant extracts were myristicin, α-phellandrene, β-phellandrene, 1,3,8-p-menthatriene, apiol, dill ether and allyl phenoxyacetate.

[Pidemiological analysis of pesticide poisoning in hangzhou during 2006-2013].

PubMed

Zhang, Lei; Hao, Li; Zhang, Xuhui; Chen, Jianchun; Wang, Qiang; Yu, Long

2015-01-01

The purpose of this current investigation was to describe the distribution characteristics of pesticides poisoning in Hangzhou during 2006-2013. The registration data of pesticide poisoning in Hangzhou during 2006-2013 were collected from health disserve surveillance information system which was part of China information system for disease control and prevention. The statistical analysis method included Pearson Chi-square test and Cochran-Armitage trend test. There were totally 6232 cases with pesticide poisoning during 2006-2013, of which 414 cases died. The fatality rate of poisoning patients was 6.64%. The pesticides, especially organophosphorus pesticides, were the main poison that caused poisoning, and patients with pesticide poisoning accounted for 80.60% of all the poisoning patient. There was more female patients than male patients among non-productive pesticide poisoning, but on the contrary among productive pesticide poisoning. The incidence of pesticides poisoning had significant increase in the third season. Occupational pesticide poisoning and non-occupational pesticide poisoning had the different distribution character. Non-occupational pesticide poisoning was the chief reason of pesticide poisoning. The pesticides, especially organophosphorus pesticides, were the main poisons threatening the health of people in Hangzhou, and the effective prevention and control measures should be taken immediately.

40 CFR 165.81 - Scope of stationary pesticide containers included.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Scope of stationary pesticide... (CONTINUED) PESTICIDE PROGRAMS PESTICIDE MANAGEMENT AND DISPOSAL Standards for Pesticide Containment Structures § 165.81 Scope of stationary pesticide containers included. (a) What is a stationary pesticide...

40 CFR 165.81 - Scope of stationary pesticide containers included.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 24 2011-07-01 2011-07-01 false Scope of stationary pesticide... (CONTINUED) PESTICIDE PROGRAMS PESTICIDE MANAGEMENT AND DISPOSAL Standards for Pesticide Containment Structures § 165.81 Scope of stationary pesticide containers included. (a) What is a stationary pesticide...

40 CFR 165.81 - Scope of stationary pesticide containers included.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Scope of stationary pesticide... (CONTINUED) PESTICIDE PROGRAMS PESTICIDE MANAGEMENT AND DISPOSAL Standards for Pesticide Containment Structures § 165.81 Scope of stationary pesticide containers included. (a) What is a stationary pesticide...

40 CFR 165.81 - Scope of stationary pesticide containers included.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 25 2012-07-01 2012-07-01 false Scope of stationary pesticide... (CONTINUED) PESTICIDE PROGRAMS PESTICIDE MANAGEMENT AND DISPOSAL Standards for Pesticide Containment Structures § 165.81 Scope of stationary pesticide containers included. (a) What is a stationary pesticide...

40 CFR 165.81 - Scope of stationary pesticide containers included.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Scope of stationary pesticide... (CONTINUED) PESTICIDE PROGRAMS PESTICIDE MANAGEMENT AND DISPOSAL Standards for Pesticide Containment Structures § 165.81 Scope of stationary pesticide containers included. (a) What is a stationary pesticide...

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. Published by Elsevier Ltd.

Nanoparticle-Based Electrochemical Immunosensor for the Detection of Phosphorylated Acetylcholinesterase: An Exposure Biomarker of Organophosphate Pesticides and Nerve AgentsOrganophosphate Pesticides and Nerve Agents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Guodong; Wang, Jun; Barry, Richard C.

A nanoparticle-based electrochemical immunosensor has been developed for the detection of phosphorylated acetylcholinesterase (AChE) adducts, which is a potential exposure biomarker for organophosphate pesticides (OP) and chemical warfare nerve agent exposures. Zirconia nanoparticles (ZrO2 NPs) were used as selective sorbents to capture the phosphorylated AChE adduct, and quantum dots (ZnS@CdS, QDs) were used as tags to label monoclonal anti-AChE antibody to track the immunorecognition events. The sandwich-like immunoreactions were performed among the ZrO2 NPs, which were pre-coated on a screen printed electrode (SPE) by electrodeposition, phosphorylated AChE and QD-anti-AChE. The captured QD tags were determined on the SPE by electrochemicalmore » stripping analysis of its metallic component (cadmium) after an acid-dissolution step. Paraoxon was used as a model OP insecticide to prepare the phosphorylated AChE adduct to demonstrate the proof of principle for this sensor technology. The paraoxon-AChE adduct was characterized by Fourier Transform Infrared Spectrum, and the binding affinity of anti-AChE to the paraoxon-AChE was validated with an enzyme-linked immunosorbent assay. The parameters (e.g., amount of ZrO2 NP, QD-anti-AChE concentration,) that govern the electrochemical response of immunosensors were optimized. The voltammetric response of the immunosensor is highly linear over the range of 10 pM to 4 nM paraoxon-AChE, and the limit of detection is estimated to be 8 pM. This new nanoparticle-based electrochemical immunosensor thus provides a sensitive and quantitative tool for biomonitoring exposure to OP pesticides and nerve agents.« less

A toolbox for microbore liquid chromatography tandem-high-resolution mass spectrometry analysis of albumin-adducts as novel biomarkers of organophosphorus pesticide poisoning.

PubMed

von der Wellen, Jens; Winterhalter, Peter; Siegert, Markus; Eyer, Florian; Thiermann, Horst; John, Harald

2018-08-01

Exposure to toxic organophosphorus pesticides (OPP) represents a serious problem in the public healthcare sector and might be forced in terroristic attacks. Therefore, reliable verification procedures for OPP-intoxications are required for forensic, toxicological and clinical reasons. We developed and optimized a toolbox of methods to detect adducts of human serum albumin (HSA) with OPP considered as long-term biomarkers. Human serum was incubated with diethyl-oxono and diethyl-thiono pesticides for adduct formation used as reference. Afterwards serum was subjected to proteolysis using three proteases separately thus yielding phosphorylated tyrosine residues (Y*) detected as single amino acid (pronase), as hexadecapeptide LVRY* 411 TKKVPQVSTPTL (pepsin) and as the tripeptide Y* 411 TK (trypsin), respectively. Adducts were analyzed via microbore liquid chromatography coupled to electrospray ionization (μLC-ESI) and tandem-high-resolution mass spectrometry (MS/HR MS). Using paraoxon-ethyl as model OPP for adduct formation, methods were optimized with respect to MS/HR MS-parameters, protease concentrations and incubation time for proteolysis. HSA-adducts were found to be stable in serum in vitro at +37 °C and -30 °C for at least 27 days and resulting biomarkers were stable in the autosampler at 15 °C for at least 24 h. Limits of identification of adducts varied between 0.25 μM and 4.0 μM with respect to the corresponding pesticide concentrations in serum. Applicability of the methods was proven by successful detection of the adducts in samples of OPP-poisoned patients thus demonstrating the methods as a reliable toolbox for forensic and toxicological analysis. Copyright © 2018 Elsevier B.V. All rights reserved.

Markers of genotoxicity and oxidative stress in farmers exposed to pesticides.

PubMed

Hilgert Jacobsen-Pereira, Carolina; Dos Santos, Claudia Regina; Troina Maraslis, Flora; Pimentel, Luisi; Feijó, Ana Júlia Lobo; Iomara Silva, Clarice; de Medeiros, Guilherme da Silva; Costa Zeferino, Rodrigo; Curi Pedrosa, Rozangela; Weidner Maluf, Sharbel

2018-02-01

The effects of chronic exposure to pesticides can lead to the development of several diseases, including different types of cancer, since the genotoxic and mutagenic capacity of these substances can be observed. The objective of this study is to investigate the relation between the occupational exposure to various pesticides and the presence of DNA damage and oxidative stress. Blood samples from 50 rural workers (41 men and 9 women) exposed to pesticides, 46 controls (20 men and 26 women) from the same city (Antônio Carlos, Santa Catarina state, Brazil) and 29 controls (15 men and 14 women) from another city (Florianópolis, Santa Catarina state, Brazil), were evaluated using the comet assay and the cytokinesis-block micronucleus (CBMN) technique for genetic damage, and the test of thiobarbituric acid reactive substances (TBARS) and catalase (CAT) activity for the oxidative stress. Cholinesterase activities were also determined, but there was no statistical difference among exposed workers and controls. Significant differences were found in DNA damage among groups. The comet assay performed on peripheral blood lymphocytes of these individuals had a significantly higher DNA damage index in the exposed group comparing to controls (p < 0.0001). MNi (p < 0.001), NBUDs (p < 0.005) and NPBs (p < 0.0001) were also found to be significantly higher in the exposed group. The TBARS values were significantly higher comparing to the Florianopolis control group (p < 0.0001). Even though CAT values were higher than controls, there was no statistical difference. Thus, it is concluded that the exposed individuals, participants of this study, are more subject to suffer genetic damage and, consequently, more susceptible to diseases resulting from such damages. Copyright © 2017 Elsevier Inc. All rights reserved.

Human health implications of organic food and organic agriculture: a comprehensive review.

PubMed

Mie, Axel; Andersen, Helle Raun; Gunnarsson, Stefan; Kahl, Johannes; Kesse-Guyot, Emmanuelle; Rembiałkowska, Ewa; Quaglio, Gianluca; Grandjean, Philippe

2017-10-27

This review summarises existing evidence on the impact of organic food on human health. It compares organic vs. conventional food production with respect to parameters important to human health and discusses the potential impact of organic management practices with an emphasis on EU conditions. Organic food consumption may reduce the risk of allergic disease and of overweight and obesity, but the evidence is not conclusive due to likely residual confounding, as consumers of organic food tend to have healthier lifestyles overall. However, animal experiments suggest that identically composed feed from organic or conventional production impacts in different ways on growth and development. In organic agriculture, the use of pesticides is restricted, while residues in conventional fruits and vegetables constitute the main source of human pesticide exposures. Epidemiological studies have reported adverse effects of certain pesticides on children's cognitive development at current levels of exposure, but these data have so far not been applied in formal risk assessments of individual pesticides. Differences in the composition between organic and conventional crops are limited, such as a modestly higher content of phenolic compounds in organic fruit and vegetables, and likely also a lower content of cadmium in organic cereal crops. Organic dairy products, and perhaps also meats, have a higher content of omega-3 fatty acids compared to conventional products. However, these differences are likely of marginal nutritional significance. Of greater concern is the prevalent use of antibiotics in conventional animal production as a key driver of antibiotic resistance in society; antibiotic use is less intensive in organic production. Overall, this review emphasises several documented and likely human health benefits associated with organic food production, and application of such production methods is likely to be beneficial within conventional agriculture, e.g., in integrated pest management.

Occupation and risk of parkinsonism: a multicenter case-control study.

PubMed

Tanner, Caroline M; Ross, G Webster; Jewell, Sarah A; Hauser, Robert A; Jankovic, Joseph; Factor, Stewart A; Bressman, Susan; Deligtisch, Amanda; Marras, Connie; Lyons, Kelly E; Bhudhikanok, Grace S; Roucoux, Diana F; Meng, Cheryl; Abbott, Robert D; Langston, J William

2009-09-01

We examined risk of parkinsonism in occupations (agriculture, education, health care, welding, and mining) and toxicant exposures (solvents and pesticides) putatively associated with parkinsonism. To investigate occupations, specific job tasks, or exposures and risk of parkinsonism and clinical subtypes. Case-control. Eight movement disorders centers in North America. Inclusion criteria were parkinsonism (>or=2 cardinal signs), diagnosis within 8 years of recruitment (to minimize survival bias), and ability to participate in detailed telephone interviews. Control subjects were primarily nonblood relatives or acquaintances of patients. This multicenter case-control study compared lifelong occupational and job task histories to determine associations with parkinsonism and certain clinical subtypes (postural instability and gait difficulty and age at diagnosis

Regulation of pesticide degradation in the detritusphere

NASA Astrophysics Data System (ADS)

Pagel, Holger; Poll, Christian; Ingwersen, Joachim; Ditterich, Franziska; Gebala, Aurelia; Kandeler, Ellen; Streck, Thilo

2015-04-01

The detritusphere is a microbial hot spot of C turnover and degradation of pesticides in soils. We aimed at an improved understanding of the regulation mechanisms, which are responsible for stimulated degradation of the herbicide MCPA (2-Methyl-4-chlorophenoxyacetic acid) in response to increased C availability in the detritusphere. We combined a microcosm experiment with biogeochemical modeling and linked genetic information on abundances of total bacteria, fungi and specific pesticide degraders in soil to the coupled biogeochemical dynamics of C and MCPA. As a result of diffusive and convective C transport from litter into the adjacent soil we found increased dissolved organic C (DOC) in soil up to a 6 mm distance to litter (detritusphere). In the detritusphere, we observed increased microbial C and accelerated MCPA degradation. These dynamics were accurately reproduced by the model. Whereas the observed increase of bacteria and pesticide degrader populations in the detritusphere was simulated satisfactorily, the model could not reproduce the steep increase of fungi indicated by the fungal marker gene. Our simulations suggest that bacterial MCPA degraders mostly benefited from high-quality DOC, whereas fungal activity and growth were specifically stimulated by low-quality DOC. According to the simulations, MCPA was predominantly degraded via fungal co-metabolism. Our study demonstrates that biogeochemical processes in soil hotspots are regulated by the interaction of transport processes and microbial dynamics. It further reveals that mathematical modelling is as powerful tool to gain comprehensive insight into the microbial regulation of matter cycling in soil. Genetic information has a high potential to parameterize and evaluate complex mechanistic models, but model approaches must be improved based on extended information on gene dynamics at the cellular level.

78 FR 9688 - Pesticides; Draft Guidance for Pesticide Registrants on Antimicrobial Pesticide Products With...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-02-11

... Pesticide Registrants on Antimicrobial Pesticide Products With Mold-Related Label Claims; Notice of... Register issue of December 12, 2012, requesting comments on Guidance for Antimicrobial Pesticide Products... CONTACT: Melba S. Morrow, Antimicrobials Division (7510P), Office of Pesticide Programs, Environmental...

40 CFR 158.2110 - Microbial pesticides data requirements.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Microbial pesticides data requirements...) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Microbial Pesticides § 158.2110 Microbial pesticides data requirements. (a) For all microbial pesticides. (1) The following § 158.2120 through § 158.2150...

78 FR 3418 - Pesticides; Draft Guidance for Pesticide Registrants on Web-Distributed Labeling for Pesticide...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-01-16

... with pesticide labeling requirements and thereby protecting human health and the environment from... ENVIRONMENTAL PROTECTION AGENCY [EPA-HQ-OPP-2012-0906; FRL-9374-4] Pesticides; Draft Guidance for Pesticide Registrants on Web- Distributed Labeling for Pesticide Products AGENCY: Environmental Protection...

40 CFR 165.82 - Scope of pesticide dispensing areas included.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 24 2011-07-01 2011-07-01 false Scope of pesticide dispensing areas...) PESTICIDE PROGRAMS PESTICIDE MANAGEMENT AND DISPOSAL Standards for Pesticide Containment Structures § 165.82 Scope of pesticide dispensing areas included. (a) What pesticide dispensing areas are subject to the...

40 CFR 165.82 - Scope of pesticide dispensing areas included.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Scope of pesticide dispensing areas...) PESTICIDE PROGRAMS PESTICIDE MANAGEMENT AND DISPOSAL Standards for Pesticide Containment Structures § 165.82 Scope of pesticide dispensing areas included. (a) What pesticide dispensing areas are subject to the...

40 CFR 165.82 - Scope of pesticide dispensing areas included.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 25 2012-07-01 2012-07-01 false Scope of pesticide dispensing areas...) PESTICIDE PROGRAMS PESTICIDE MANAGEMENT AND DISPOSAL Standards for Pesticide Containment Structures § 165.82 Scope of pesticide dispensing areas included. (a) What pesticide dispensing areas are subject to the...

40 CFR 165.82 - Scope of pesticide dispensing areas included.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Scope of pesticide dispensing areas...) PESTICIDE PROGRAMS PESTICIDE MANAGEMENT AND DISPOSAL Standards for Pesticide Containment Structures § 165.82 Scope of pesticide dispensing areas included. (a) What pesticide dispensing areas are subject to the...

40 CFR 165.82 - Scope of pesticide dispensing areas included.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Scope of pesticide dispensing areas...) PESTICIDE PROGRAMS PESTICIDE MANAGEMENT AND DISPOSAL Standards for Pesticide Containment Structures § 165.82 Scope of pesticide dispensing areas included. (a) What pesticide dispensing areas are subject to the...

Pesticides and Human Health

Science.gov Websites

. People come into contact with pesticides in many ways, including: When pesticides are used in and around Disponible en español Pesticides and Human Health Pesticides have a specific purpose in society. Pesticides . Because people use pesticides to kill, prevent, repel, or in some way adversely affect some living

Pesticide Information for Veterinarians

Science.gov Websites

; Environment Human Health Animal Health Safe Use Practices Food Safety Environment Air Water Soil Wildlife Ingredients Low-Risk Pesticides Organic Pesticide Ingredients Pesticide Incidents Human Exposure Pet Exposure Home Page Pesticide Health and Safety Information Pesticides and Animal Health Pesticide Information

Development of a QuEChERS-Based Stable-Isotope Dilution LC-MS/MS Method To Quantitate Ferulic Acid and Its Main Microbial and Hepatic Metabolites in Milk.

PubMed

Waterstraat, Martin; Hildebrand, Andreas; Rosler, Margit; Bunzel, Mirko

2016-11-16

Forage plants of the Poaceae family are grown as pasturage or used for the production of hay, straw, corn stover, etc. Although ferulic acid contents of grasses are generally high, the amount of ingested ferulic acid differs depending on the type of forage, resulting in varying contents of ferulic acid and its microbial and hepatic metabolites in milk. Concentrations and patterns of these metabolites may be used as markers to track different forages in livestock feeding. Therefore, we developed a stable isotope dilution assay to quantitate ferulic acid, 12 ferulic acid-based metabolites, p-coumaric acid, and cinnamic acid in milk. Because most analytes were not commercially available as stable isotope labeled standard compounds, they were synthesized as 13 C- or deuterium-labeled standard compounds. A modification of the QuEChERS method, a Quick, Easy, Cheap, Effective, Rugged, and Safe approach usually applied to analyze pesticides in plant-based products, was used to extract the phenolic acids from milk. Determination was carried out by LC-ESI-MS/MS in scheduled multiple reaction monitoring modus. By using three different milk samples, the applicability of the validated approach was demonstrated.

Susceptibility of nine organophosphorus pesticides in skimmed milk towards inoculated lactic acid bacteria and yogurt starters.

PubMed

Zhou, Xin-Wei; Zhao, Xin-Huai

2015-01-01

Previous research has shown that fresh milk might be polluted by some organophosphorus pesticides (OPPs). In this study the dissipation of nine OPPs, namely chlorpyrifos, chlorpyrifos-methyl, diazinon, dichlorvos, fenthion, malathion, phorate, pirimiphos-methyl and trichlorphon, in skimmed milk was investigated to clarify their susceptibility towards lactic acid bacteria (LAB) and yogurt starters. Skimmed milk was spiked with nine OPPs, inoculated with five strains of LAB and two commercial yogurt starters at 42 °C for 24 and 5 h respectively and subjected to quantitative OPP analysis by gas chromatography. Degradation kinetic constants of these OPPs were calculated based on a first-order reaction model. OPP dissipation in the milk was enhanced by the inoculated strains and starters, resulting in OPP concentrations decreasing by 7.0-64.6 and 7.4-19.2% respectively. Totally, the nine OPPs were more susceptible to Lactobacillus bulgaricus, as it enhanced their degradation rate constants by 18.3-133.3%. Higher phosphatase production of the assayed stains was observed to bring about greater OPP degradation in the milk. Both LAB and yogurt starters could enhance OPP dissipation in skimmed milk, with the nine OPPs studied having different susceptibilities towards them. Phosphatase was a key factor governing OPP dissipation. The LAB of higher phosphatase production have more potential to decrease OPPs in fermented foods. © 2014 Society of Chemical Industry.

Acylamino acid chiral fungicides on toxiciepigenetics in lambda DNA methylation.

PubMed

Yin, Jing; Zhu, Feilong; Hao, Weiyu; Xu, Qi; Chang, Jin; Wang, Huili; Guo, Baoyuan

2017-11-01

Acylamino acid chiral fungicides (AACFs) are low-toxicity pesticides and considered as non-carcinogenic chemicals to laboratory animals. Though AACFs have potential toxicological effects on mammals by non-genotoxic mechanisms, the toxicoepigenomics of AACFs has not been documented. In this article, we explored toxiciepigenetics of metalaxyl, benalaxyl and furalaxyl through epigenetics research on lambda DNA under different concentration exposure. The toxicoepigenomic difference of stereoisomers was examined also. Our results showed that AACFs would affect methyltransferase activity resulting in modulating DNA methylation levels and pattern. The LOAEL of R-metalaxyl and S-metalaxyl were 30 mM and 0.3 mM, respectively. The LOAEL of (R, S)-benalaxyl and (R, S)-furalaxyl were 0.3 Mm and 30 mM, respectively. A significant dose-response effect between (R, S)-benalaxyl and global methylation level was observed. Global methylation level was more susceptible to S-enantiomer compared to R-enantiomer, which indicated enantiomers of AACFs have the enantioselectivity in toxiciepigenetics. Moreover, the dependence of the methylation inhibition on the chiral center of metalaxyl may suggest a considerable specificity of the compound of AACFs for DNA methyltransferases. The inhibition effect between R-enantiomer and S-enantiomer of AACFs on DNA methylation levels generated in this study is important for low-toxicity pesticides toxicoepigenomics evaluation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Assessing the transport potential of polymeric nanocapsules developed for crop protection.

PubMed

Petosa, Adamo Riccardo; Rajput, Faraz; Selvam, Olivia; Öhl, Carolin; Tufenkji, Nathalie

2017-03-15

Nanotechnology is increasingly important in the agricultural sector, with novel products being developed to heighten crop yields and increase pesticide efficacy. Herein, the transport potential of different polymeric nanocapsules (nCAPs) developed as pesticide delivery vehicles was assessed in model soil systems. The nCAPs examined are (i) poly(acrylic acid)-based (nCAP1), (ii) poly(methacrylic acid)-ran-poly(ethyl acrylate) copolymer-based (nCAP2), (iii) poly(methacrylic acid-ran-styrene) copolymer-based (nCAP3), and (iv) poly(methacrylic acid-ran-butylmethacrylate)-based (nCAP4). nCAP mobility was examined in columns packed with agricultural loamy sand saturated with artificial porewater containing Ca 2+ and Mg 2+ cations (10 mM ionic strength, pH 6 and 8). Furthermore, the impact of (i) cation species, (ii) sand type, and (iii) ammonium polyphosphate fertilizer on the transport potential of a nanoformulation combining nCAP4 capsules and the pyrethroid bifenthrin (nCAP4-BIF) was examined and compared to a commercial bifenthrin formulation (Capture ® LFR). Although nCAP4-BIF and Capture ® LFR formulations were highly mobile in quartz sand saturated with 10 mM NaNO 3 (≥95% elution), they were virtually immobile in the presence of 10% ammonium polyphosphate fertilizer. The presence of Ca 2+ and Mg 2+ did not hinder nCAP4-BIF elution in quartz sand saturated with 10 mM standard CIPAC D synthetic porewater; however, limited Capture ® LFR transport (<10% elution) was observed under the same conditions. Capture ® LFR also exhibited limited mobility in the presence or absence of fertilizer in loamy sand saturated with divalent salt solutions, whereas nCAP4-BIF exhibited increased elution with time and enhanced transport upon the addition of fertilizer. Overall, nCAP4 is a promising delivery vehicle in pyrethroid nanoformulations such as nCAP4-BIF. Copyright © 2016 Elsevier Ltd. All rights reserved.

Risk assessment of pesticide transport with water erosion: A conceptual model

NASA Astrophysics Data System (ADS)

Yang, Xiaomei; Van Der Zee, Sjoerd E. A. T. M.; Gai, Lingtong; Wesseling, Jan G.; Ritsema, Coen J.; Geissen, Violette

2017-04-01

Pesticides are widely used in agriculture, horticulture, and forestry, and pesticide pollution has become an important issue worldwide. Entraining in runoff and being attached to eroded soil particles, posing a risk to water and soil quality and human health. In order to assess the risk of pesticide during water erosion processes, a simple integrative model of pesticide transport by runoff and erosion was developed. Taking soil hydrological and pesticide behaviour into account, such as water infiltration, erosion, runoff, and pesticide transport and degradation in soil, the conceptual framework was based on the known assumptions such as the convection-dispersion equation and lognormal distributions of soil properties associated with transport, sorption, degradation, and erosion. A sensitivity analysis was conducted and the results indicated that the total amount of pesticide related to soil eroded by water washing increased with slope gradient, rainfall intensity, and water field capacity of the soil. The mass of transported pesticide decreased as the micro-topography of the soil surface became obviously and the time from pesticide sprayed to erosion occurring associated with pesticide degradation negatively influenced the total amount of transported pesticide. The mechanisms involved in pesticide transport, such as runoff, infiltration, soil erosion, and pesticide transport and decay in the topsoil, thus can be well accounted for pesticide risk assessment especially in the region with intensive pesticide use and soil water erosion events.

Pesticide risk behaviors and factors influencing pesticide use among farmers in Kuwait.

PubMed

Jallow, Mustapha F A; Awadh, Dawood G; Albaho, Mohammed S; Devi, Vimala Y; Thomas, Binson M

2017-01-01

The widespread overuse of pesticides in agriculture has generated increasing concerns about the negative effects of pesticides on human health and the environment. Understanding farmers' perceptions of risk of pesticides and the determinants of pesticide overuse is important to modifying their behavior towards reducing pesticide use. A survey of 250 randomly selected smallholder vegetable farmers in Kuwait was conducted to quantify the extent of pesticide use, their pesticide risk perceptions and factors influencing their pesticide use behaviors. The majority of the farmers perceived pesticides pose some risk to the environment (65%) and human health (70.5%), while younger farmers were more likely to perceive this risk than older farmers. When asked to rate how risky pesticides were regarding several aspects of human health and the environment on a scale of 1(not risky) to 5 (extremely risky), concern was highest for the health of applicators (x̅=4.28) and lowest for air quality (x̅=2.32). The risk perceptions of the farmers did not have a positive influence on their pesticide use practices. A total of 76 pesticide active ingredients were found in use, and 9% of these belong to the WHO toxicity class II (moderately hazardous). On average, farmers applied 12.8kg of active ingredients per hectare per year, and 58% of the farmers were found to have overused pesticides, with an average overuse rate of 2.5kg. Pesticide application frequency ranged from two times a month up to once a week, depending on the crop. A binary probit model reveals that farmers' inadequate knowledge of pesticides, the influence of pesticide retailers and lack of access to non-synthetic methods of pest control are positively associated with pesticide overuse, while the propensity to overuse decreases with higher levels of education, training in Integrated Pest Management (IPM) and the safe use and handling of pesticides, and access to extension support. Comprehensive intervention measures for reducing pesticide overuse and limit the health and environmental hazards caused by pesticides are provided in this paper. Copyright © 2016 Elsevier B.V. All rights reserved.

Effects of Short-Term Biosolarization Using Mature Compost and Industrial Tomato Waste Amendments on the Generation and Persistence of Biocidal Soil Conditions and Subsequent Tomato Growth.

PubMed

Achmon, Yigal; Sade, Nir; Wilhelmi, María Del Mar Rubio; Fernández-Bayo, Jesus D; Harrold, Duff R; Stapleton, James J; VanderGheynst, Jean S; Blumwald, Eduardo; Simmons, Christopher W

2018-06-06

Conventional solarization and biosolarization with mature compost and tomato processing residue amendments were compared with respect to generation of pesticidal conditions and tomato ( Solanum lycopersicum L.) plant growth in treated soils. Soil oxygen depletion was examined as a response that has previously not been measured across multiple depths during biosolarization. For biosolarized soil, volatile fatty acids were found to accumulate concurrent with oxygen depletion, and the magnitude of these changes varied by soil depth. Two consecutive years of experimentation showed varying dissipation of volatile fatty acids from biosolarized soils post-treatment. When residual volatile fatty acids were detected in the biosolarized soil, fruit yield did not significantly differ from plants grown in solarized soil. However, when there was no residual volatile fatty acids in the soil at the time of planting, plants grown in biosolarized soil showed a significantly greater vegetation amount, fruit quantity, and fruit ripening than those of plants grown in solarized soil.

An overview of the recent developments in polylactide (PLA) research.

PubMed

Madhavan Nampoothiri, K; Nair, Nimisha Rajendran; John, Rojan Pappy

2010-11-01

The concept of biodegradable plastics is of considerable interest with respect to solid waste accumulation. Greater efforts have been made in developing degradable biological materials without any environmental pollution to replace oil-based traditional plastics. Among numerous kinds of degradable polymers, polylactic acid sometimes called polylactide, an aliphatic polyester and biocompatible thermoplastic, is currently a most promising and popular material with the brightest development prospect and was considered as the 'green' eco friendly material. Biodegradable plastics like polyglycolic acid, polylactic acid, polycaprolactone, polyhydroxybutyrate, etc. are commercially available for controlled drug releases, implantable composites, bone fixation parts, packaging and paper coatings, sustained release systems for pesticides and fertilizers and compost bags etc. This review will provide information on current PLA market, brief account on recent developments in the synthesis of lactic acid (monomer of PLA) through biological route, PLA synthesis, unique material properties of PLA and modification of those by making copolymers and composites, PLA degradation and its wide spectrum applications.

40 CFR 158.2080 - Experimental use permit data requirements-biochemical pesticides.

Code of Federal Regulations, 2011 CFR

2011-07-01

... requirements-biochemical pesticides. 158.2080 Section 158.2080 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Biochemical Pesticides § 158.2080 Experimental use permit data requirements—biochemical pesticides. (a) Sections 158.2081...

40 CFR 158.2080 - Experimental use permit data requirements-biochemical pesticides.

Code of Federal Regulations, 2012 CFR

2012-07-01

... requirements-biochemical pesticides. 158.2080 Section 158.2080 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Biochemical Pesticides § 158.2080 Experimental use permit data requirements—biochemical pesticides. (a) Sections 158.2081...

40 CFR 158.2080 - Experimental use permit data requirements-biochemical pesticides.

Code of Federal Regulations, 2014 CFR

2014-07-01

... requirements-biochemical pesticides. 158.2080 Section 158.2080 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Biochemical Pesticides § 158.2080 Experimental use permit data requirements—biochemical pesticides. (a) Sections 158.2081...

40 CFR 158.2080 - Experimental use permit data requirements-biochemical pesticides.

Code of Federal Regulations, 2010 CFR

2010-07-01

... requirements-biochemical pesticides. 158.2080 Section 158.2080 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Biochemical Pesticides § 158.2080 Experimental use permit data requirements—biochemical pesticides. (a) Sections 158.2081...

40 CFR 158.2080 - Experimental use permit data requirements-biochemical pesticides.

Code of Federal Regulations, 2013 CFR

2013-07-01

... requirements-biochemical pesticides. 158.2080 Section 158.2080 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Biochemical Pesticides § 158.2080 Experimental use permit data requirements—biochemical pesticides. (a) Sections 158.2081...

Water pollution: Pesticides in Aquatic environments. (Latest citations from Pollution abstracts). Published Search

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1993-01-01

The bibliography contains citations concerning the physicochemical and biochemical dynamics of pesticides in aquatic environments. The effects of organophosphorus, organochlorine, and arsenical pesticides on marine, surface, and groundwater ecosystems are discussed. Topics include biological fate and transformation of pesticides in waters, sources of release and transport of pesticides, bioaccumulation and metabolism of pesticides by aquatic organisms, ecological concentration and degradability of pesticides in model ecosystems, and marine ecology. Guidelines for pesticide registration and pesticide effluents are also referenced. (Contains a minimum of 205 citations and includes a subject term index and title list.)

Simulating pesticide transport in urbanized catchments: a new spatially-distributed dynamic pesticide runoff model

NASA Astrophysics Data System (ADS)

Tang, Ting; Seuntjens, Piet; van Griensven, Ann; Bronders, Jan

2016-04-01

Urban areas can significantly contribute to pesticide contamination in surface water. However, pesticide behaviours in urban areas, particularly on hard surfaces, are far less studied than those in agricultural areas. Pesticide application on hard surfaces (e.g. roadsides and walkways) is of particular concern due to the high imperviousness and therefore high pesticide runoff potential. Experimental studies have shown that pesticide behaviours on and interactions with hard surfaces are important factors controlling the pesticide runoff potential, and therefore the magnitude and timing of peak concentrations in surface water. We conceptualized pesticide behaviours on hard surfaces and incorporated the conceptualization into a new pesticide runoff model. The pesticide runoff model was implemented in a catchment hydrological model WetSpa-Python (Water and Energy Transfer between Soil, Plants and Atmosphere, Python version). The conceptualization for pesticide processes on hard surfaces accounts for the differences in pesticide behaviour on different hard surfaces. Four parameters are used to describe the partitioning and wash-off of each pesticide on hard surfaces. We tested the conceptualization using experimental dataset for five pesticides on two types of hard surfaces, namely concrete and asphalt. The conceptualization gave good performance in accounting for the wash-off pattern for the modelled pesticides and surfaces, according to quantitative evaluations using the Nash-Sutcliffe efficiency and percent bias. The resulting pesticide runoff model WetSpa-PST (WetSpa for PeSTicides) can simulate pesticides and their metabolites at the catchment scale. Overall, it includes four groups of pesticide processes, namely pesticide application, pesticide interception by plant foliage, pesticide processes on land surfaces (including partitioning, degradation and wash-off on hard surface; partitioning, dissipation, infiltration and runoff in soil) and pesticide processes in depression storage (including degradation, infiltration and runoff). Processes on hard surfaces employs the conceptualization described in the paragraph above. The WetSpa-PST model can account for various spatial details of the urban features in a catchment, such as asphalt, concrete and roof areas. The distributed feature also allows users to input detailed pesticide application data of both non-point and point origins. Thanks to the Python modelling framework prototype used in the WetSpa-Python model, processes in the WetSpa-PST model can be simulated at different time steps depending on data availability and the characteristic temporal scale of each process. This helps to increase the computational accuracy during heavy rainfall events, especially for the associated fast transport of pesticides into surface water. Overall, the WetSpa-PST model has good potential in predicting effects of management options on pesticide releases from heavily urbanized catchments.

Air and Pesticides

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Pesticides in Mississippi air and rain: A comparison between 1995 and 2007

USGS Publications Warehouse

Majewski, Michael S; Coupe, Richard H.; Foreman, William T.; Capel, Paul D.

2014-01-01

A variety of current-use pesticides were determined in weekly composite air and rain samples collected during the 1995 and 2007 growing seasons in the Mississippi Delta (MS, USA) agricultural region. Similar sampling and analytical methods allowed for direct comparison of results. Decreased overall pesticide use in 2007 relative to 1995 generally resulted in decreased detection frequencies in air and rain; observed concentration ranges were similar between years, however, even though the 1995 sampling site was 500 m from active fields whereas the 2007 sampling site was within 3 m of a field. Mean concentrations of detections were sometimes greater in 2007 than in 1995, but the median values were often lower. Seven compounds in 1995 and 5 in 2007 were detected in ≥50% of both air and rain samples. Atrazine, metolachlor, and propanil were detected in ≥50% of the air and rain samples in both years. Glyphosate and its degradation product, aminomethyl-phosphonic acid (AMPA), were detected in ≥75% of air and rain samples in 2007 but were not measured in 1995. The 1995 seasonal wet depositional flux was dominated by methyl parathion (88%) and was >4.5 times the 2007 flux. Total herbicide flux in 2007 was slightly greater than in 1995 and was dominated by glyphosate. Malathion, methyl parathion, and degradation products made up most of the 2007 nonherbicide flux.

Pesticides in Mississippi air and rain: a comparison between 1995 and 2007.

PubMed

Majewski, Michael S; Coupe, Richard H; Foreman, William T; Capel, Paul D

2014-06-01

A variety of current-use pesticides were determined in weekly composite air and rain samples collected during the 1995 and 2007 growing seasons in the Mississippi Delta (MS, USA) agricultural region. Similar sampling and analytical methods allowed for direct comparison of results. Decreased overall pesticide use in 2007 relative to 1995 generally resulted in decreased detection frequencies in air and rain; observed concentration ranges were similar between years, however, even though the 1995 sampling site was 500 m from active fields whereas the 2007 sampling site was within 3 m of a field. Mean concentrations of detections were sometimes greater in 2007 than in 1995, but the median values were often lower. Seven compounds in 1995 and 5 in 2007 were detected in ≥50% of both air and rain samples. Atrazine, metolachlor, and propanil were detected in ≥50% of the air and rain samples in both years. Glyphosate and its degradation product, aminomethyl-phosphonic acid (AMPA), were detected in ≥75% of air and rain samples in 2007 but were not measured in 1995. The 1995 seasonal wet depositional flux was dominated by methyl parathion (88%) and was >4.5 times the 2007 flux. Total herbicide flux in 2007 was slightly greater than in 1995 and was dominated by glyphosate. Malathion, methyl parathion, and degradation products made up most of the 2007 nonherbicide flux. © 2014 SETAC.

Occurrence of organochlorines in the green sea turtle (Chelonia mydas) on the northern coast of the state of São Paulo, Brazil.

PubMed

da Silva, Josilene; Taniguchi, Satie; Becker, José Henrique; Werneck, Max Rondon; Montone, Rosalinda Carmela

2016-11-15

Organochlorines (OCs), such as pesticides and polychlorinated biphenyls (PCBs), are persistent, toxic and widely distributed through atmospheric transport and ocean currents. Few studies have been conducted on OCs in sea turtles, especially on the coast of Brazil. Chelonia mydas is the largest hard-shell sea turtle and is found tropical and subtropical regions in all oceans. The aim of the present study was to determine the occurrence of OCs in the green sea turtle (C. mydas). Fat, liver, kidney and muscle samples were collected from 27 juveniles found on the beach of the city of Ubatuba on the northern coast of the state of São Paulo, Brazil. OCs were extracted with organic solvents and the extract was purified with concentrated acid. Gas chromatography-mass spectrometry and electron capture detection were used for the identification and quantification of PCBs and pesticides, respectively. No organochlorine pesticides were detected in any of the samples. Concentrations of total PCBs in wet weight were <1.6 to 48.9ng/g in fat tissue, <1.6 to 17.4ng/g in liver tissue and <1.6 to 37.7ng/g in kidney tissue. The low levels found are mainly related to diet, as the green sea turtle is basically herbivorous and lower PCB contamination compared to other regions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Biodegradability of HCH in agricultural soils from Guadeloupe (French West Indies): identification of the lin genes involved in the HCH degradation pathway.

PubMed

Laquitaine, L; Durimel, A; de Alencastro, L F; Jean-Marius, C; Gros, O; Gaspard, S

2016-01-01

Banana has been a main agricultural product in the French West Indies (Guadeloupe and Martinique) since the 1960s. This crop requires the intensive use of pesticides to prevent attacks by insect pests. Chlorinated pesticides, such as hexachlorocyclohexane (HCH), chlordecone and dieldrin, were used until the beginning of the 1990s, resulting in a generalized diffuse contamination of the soil and water in the areas of banana production, hence the need to develop solutions for cleanup of the polluted sites. The aims of this work were (i) to assess lindane degradation in soil slurry microcosms treated with lindane at 10 mg/L and (ii) to detect the catabolic genes involved in the HCH degradation pathway. The soil slurry microcosm system showed a 40% lindane degradation efficiency at the end of a 30-day experiment. Lower lindane removal was also detected in the abiotic controls, probably caused by pesticide adsorption to soil particles. Indeed, the lindane concentration decreased from 6000 to 1330 ng/mL and from 800 to 340 ng/mL for the biotic and abiotic soils, respectively. Nevertheless, some of the genes involved in the HCH degradation pathway were amplified by polymerase chain reaction (PCR) from crude deoxyribonucleic acid (DNA) extracted from the Guadeloupe agricultural soil, suggesting that HCH degradation is probably mediated by bacteria closely related to the family Sphingomonadaceae.

Viral-toxin interactions and Parkinson’s disease: poly(I:C) priming enhanced the neurodegenerative effects of paraquat

PubMed Central

2012-01-01

Background Parkinson’s disease (PD) has been linked with exposure to a variety of environmental and immunological insults (for example, infectious pathogens) in which inflammatory and oxidative processes seem to be involved. In particular, epidemiological studies have found that pesticide exposure and infections may be linked with the incidence of PD. The present study sought to determine whether exposure to a viral mimic prior to exposure to pesticides would exacerbate PD-like pathology. Methods Mice received a supra-nigral infusion of 5 μg of the double-stranded RNA viral analog, polyinosinic: polycytidylic acid (poly(I:C)), followed 2, 7 or 14 days later by administration of the pesticide, paraquat (nine 10 mg/kg injections over three weeks). Results As hypothesized, poly(I:C) pre-treatment enhanced dopamine (DA) neuron loss in the substantia nigra pars compacta elicited by subsequent paraquat treatment. The augmented neuronal loss was accompanied by robust signs of microglial activation, and by increased expression of the catalytic subunit (gp91) of the NADPH oxidase oxidative stress enzyme. However, the paraquat and poly(I:C) treatments did not appreciably affect home-cage activity, striatal DA terminals, or subventricular neurogenesis. Conclusions These findings suggest that viral agents can sensitize microglial-dependent inflammatory responses, thereby rendering nigral DA neurons vulnerable to further environmental toxin exposure. PMID:22559812

COMMUNICATING THE RISKS OF PESTICIDE EXPOSURE TO AGRICULTURAL WORKERS

EPA Science Inventory

The goals of the USEPA pesticide worker safety program are to protect human health and the environment by ensuring the competency of pesticide applicators to minimize pesticide exposure to occupational pesticide users and agricultural field workers, to assure use of pesticides, a...

40 CFR 158.2010 - Biochemical pesticides data requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... conditions are identified within the test notes. Definitions that apply to all biochemical data requirements... 40 Protection of Environment 25 2012-07-01 2012-07-01 false Biochemical pesticides data...) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Biochemical Pesticides § 158.2010 Biochemical pesticides...

40 CFR 158.2010 - Biochemical pesticides data requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... conditions are identified within the test notes. Definitions that apply to all biochemical data requirements... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Biochemical pesticides data...) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Biochemical Pesticides § 158.2010 Biochemical pesticides...

40 CFR 158.2010 - Biochemical pesticides data requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... conditions are identified within the test notes. Definitions that apply to all biochemical data requirements... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Biochemical pesticides data...) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Biochemical Pesticides § 158.2010 Biochemical pesticides...

40 CFR 158.2010 - Biochemical pesticides data requirements.

Code of Federal Regulations, 2010 CFR

2010-07-01

... conditions are identified within the test notes. Definitions that apply to all biochemical data requirements... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Biochemical pesticides data...) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Biochemical Pesticides § 158.2010 Biochemical pesticides...