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Sample records for organophosphorus organohalogen organonitrogen

  1. An update on organohalogen metabolites produced by basidiomycetes

    Field, J.A.; Wijnberg, J.B.P.A.

    2003-01-01

    Basidiomycetes are an ecologically important group of higher fungi known for their widespread capacity to produce organohalogen metabolites. To date, 100 different organohalogen metabolites (mostly chlorinated) have been identified from strains in 70 genera of Basidiomycetes. This manuscript

  2. Neutron activation analysis of organohalogens in Chinese human hair

    Zhang, H.; Chai, Z.F.; Chinese Academy of Sciences, Beijing; Sun, H.B.; Xu, H.F.

    2007-01-01

    To effectively extract organohalogens from human hair, two factors, the extracting time and hair length on the extraction efficiency of organohalogens were studied by neutron activation analysis (NAA) and gas chromatograph-electron capture detector (GC-ECD), respectively. Furthermore, the concentrations of extractable organohalogens (EOX) and extractable persistent organohalogens (EPOX) in hair samples from angioma and control babies were also measured by the established method. The results indicated that the optimal Soxhlet-extraction time for EOX and EPOX in hair was from 8 to 11 hours, and the extraction efficiencies for organochlorine pesticides in hair were in the order of powder >2 mm>5 mm. Also, the mean levels of EOCl and EPOCl in hair of the angioma babies were significantly higher than those in the control babies (P EOCl EPOCl <0.05), which implied the possible relationship between the environmental pollution and angioma. (author)

  3. Molecular activation analysis for organo-halogen contaminants in yogurt

    Zhang Hong; Chai Zhifang

    2004-01-01

    The concentrations of total halogen (TX), extractable organo-halogen (EOX), extractable persistent organo-halogen (EPOX), organo-chlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in 18 different yogurt specimens of 14 brands from Beijing, Tianjin, Shanghai, Guangzhou and Shijiazhuang were determined by epithermal neutron activation analysis (ENAA), molecular activation analysis (MAA) and GC-Mass Spectrometry (GC-MS), respectively. The results indicated that the halogen in yogurt mainly existed as inorganic species and non-extractable organo-halogen compounds. About 1/3 to 1/4 of EOX was EPOX. Further, EOCl and EPOCl were the main organo-halogen species in yogurt. The average concentration of the unknown organo-chlorine was 96% of the EPOCl. HCHs and DDTs were still the main contaminants of OCPs in the yogurt of interest. Also, PCB202, PCB103 and PCB208 were the main contaminants of PCBs. (authors)

  4. Identification of organosulfurs and organonitrogens in the extracts of Pocahontas No. 3 Coal

    Jing-Pei Cao; Zhi-Min Zong; Xiao-Yan Zhao; Chang-Cheng Liu; Guang-Feng Liu; Hong Zhang; Chul Wee Lee; Xian-Yong Wei [China University of Mining and Technology, Xuzhou (China). School of Chemical Engineering

    2007-07-01

    Pocahontas No. 3 coal was extracted with CS{sub 2}, n-hexane, benzene, methanol, acetone and acetone/CS{sub 2} (1:1 vol/vol) mixed solvent sequentially. The resulting six extracts were analyzed with GC and GC/MS. Hexathiane, octathiane, twenty-one organosulfurs (OSs) and twenty-one organonitrogens (ONs) were detected in the extracts. OSs detected in the extracts include ethylmethylsulfane, 1,2-dimethyldisulfane, S-ethyl dipropylcarbamothioate, dimexano and its derivatives, dibenzothiophene, mono- and dimethyldibenzothiophenes, benzonaphthothiophene, mono- and dimethyl benzonaphthothiophenes, among which dimexano and dixanthogen were seldom reported in any sediments. Benzene is effective for extracting aromatic-ring-containing OSs, while OSs without aromatic ring tend to dissolve in methanol. Most of ONs detected in the extracts are acridinone, methylacridinones, carbazole, methylcarbazoles, benzocarbazoles, amines, phenanthridinone and piperidinone. Species and amounts of ONs detected in the extracts were increased along with the increasing of solvent polarity. N and O atoms often coexist in the same compounds. 2 figs., 3 tabs.

  5. The organophosphorus extractants

    Zaoul, B.; Attou, M.; Azzouz, A.

    1989-07-01

    This work consists in a bibliographic review dealing with phosphorus and organophosphorus compounds chemistry and especially with the main extracting agents used in uranium ore treatment. In this context, a special interest is devoted to TBP, D 2 EHPA and TOPO. The content of this work is based on a large bibliography including cca. One hundred references related to many aspects concerning as well the nomenclature, the classification and the chemical structures of the organophosphorus compounds as synthesis methods, purification and analysis of the main extracting agents used in uranium extraction

  6. NAA of organohalogens in air particles and precipitation in Shanghai

    Li Xinnian; Yu Tailiu; Guo Junpeng; Xiong Youyou; Luo Wenyun

    2006-01-01

    Organohalogens are ubiquitous pollutants which are especially controlled in many countries and their behaviors in environment become the hot topic in environment science. By the method of neutron activation analysis (NAA) combined with chemical separation, the extractable organohalogens (EOX) in environmental samples were determined. NAA is a nuclear analysis method, which has high sensibility and high precision. The detection limits were 50ng, 8ng, 3.5ng for Cl, Br, I, respectively. The principle is that when the sample was irradiated by thermal neutron, the energies and the intensities of γ ray of halogen nuclides ( 38 Cl, E γ =1642keV, t 1/2 =37.24min; 80 Br,E γ =617keV, t 1/2 =17.68min; 128 I, E γ =443keV, t 1/2 =24.99min)produced by nuclear reaction can be measured. Total content of halogens were analyzed and the organochlorines, organobromines and organoiodines in the samples were detected. In this paper, NAA and gas chromatography (GC) were used to determine organohalogens in air particles and precipitation samples in Jiading District, Shanghai, collected between December 2004 and August 2005. Extractable organohalogens (EOX), extractable persistent organohalogens (EPOX), organochlorine pesticides (OCPs) and polychlorinated diphenyls (PCBs) in atmosphere were analyzed. The effect of preference for absorbance of organohalogens in fine air particles has been found. The sources for organochlorines in atmospheres are miscellaneous, while organobromine unitary and its possible souce is PBDEs. The contamination levels of HCH and DDT that are forbidden from 1983 in our country are coming down every year, but still being affected by transfusing of pesticides. The migration of lower chloro-diphenyls and HCH in ecosphere is larger than higher chloro-diphenyls, DDT and its metabolites. This work is supported by Foundation of Key Laboratory of Nuclear Analytical Techniques, Institute of High Energy Physics, Chinese Academy of Sciences (Grant No. K117). (authors)

  7. New procedure for the examination of the degradation of volatile organonitrogen compounds during the treatment of industrial effluents.

    Boczkaj, Grzegorz; Makoś, Patrycja; Fernandes, Andre; Przyjazny, Andrzej

    2017-03-01

    We present a new procedure for the determination of 32 volatile organonitrogen compounds in samples of industrial effluents with a complex matrix. The procedure, based on dispersive liquid-liquid microextraction followed by gas chromatography with nitrogen-phosphorus and mass spectrometric detection, was optimized and validated. Optimization of the extraction included the type of extraction and disperser solvent, disperser solvent volume, pH, salting out effect, extraction, and centrifugation time. The procedure based on nitrogen-phosphorus detection was found to be superior, having lower limits of detection (0.0067-2.29 μg/mL) and quantitation as well as a wider linear range. The developed procedure was applied to the determination of content of volatile organonitrogen compounds in samples of raw effluents from the production of bitumens in which 13 compounds were identified at concentrations ranging from 0.15 to 10.86 μg/mL and in samples of effluents treated by various chemical methods. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Organophosphorus poisoning (acute).

    Blain, Peter G

    2011-05-17

    Acetylcholinesterase inhibition by organophosphorus pesticides or organophosphate nerve agents can cause acute parasympathetic system dysfunction, muscle weakness, seizures, coma, and respiratory failure. Prognosis depends on the dose and relative toxicity of the specific compound, as well as pharmacokinetic factors. We conducted a systematic review and aimed to answer the following clinical question: What are the effects of treatments for acute organophosphorus poisoning? We searched: Medline, Embase, The Cochrane Library, and other important databases up to April 2010 (Clinical Evidence reviews are updated periodically; please check our website for the most up-to-date version of this review). We included harms alerts from relevant organisations such as the US Food and Drug Administration (FDA) and the UK Medicines and Healthcare products Regulatory Agency (MHRA). We found 62 systematic reviews, RCTs, or observational studies that met our inclusion criteria. We performed a GRADE evaluation of the quality of evidence for interventions. In this systematic review we present information relating to the effectiveness and safety of the following interventions: activated charcoal (single or multiple doses), alpha(2) adrenergic receptor agonists, atropine, benzodiazepines, butyrylcholinesterase replacement therapy, cathartics, extracorporeal clearance, gastric lavage, glycopyrronium bromide (glycopyrrolate), ipecacuanha (ipecac), magnesium sulphate, milk or other home remedy immediately after ingestion, N-methyl-D-aspartate receptor antagonists, organophosphorus hydrolases, oximes, removing contaminated clothes and washing the poisoned person, and sodium bicarbonate.

  9. Study of organohalogen contaminants in yogurt by NAA and GC-ECD

    Zhang, H.; Chai, Z.F.; Shenzen Univ.; Sun, H.B.; Zhang, J.L.; Ouyang, H.; Xin, L.; Chuai, Y.D.

    2007-01-01

    The concentrations and distributions of total halogen (TX), extractable organohalogen (EOX) and extractable persistent organohalogen (EPOX) were determined in 20 kinds of yogurt specimens collected from Chinese supermarkets using neutron activation analysis (NAA) and gas chromatography equipped with a 63 Ni electron capture detector (GC-ECD). The results indicated that the halogens in yogurt mainly existed as non-extractable organohalogen compounds. About 25-30% of EOX was EPOX. EOCl and EPOCl were the main organohalogen species in yogurt. The average concentration of the identified organochlorine, such as organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs), was below 4% of EPOCl. (author)

  10. An interlaboratory comparison exercise for organohalogens in marine mammal blubber

    Kucklick, J.; Becker, P.; Pugh, R. [NIST, Hollings Marine Lab., Charleston (United States); Schantz, M.; Porter, B.; Wise, S. [NIST, Gaithersburg (United States); Rowles, T. [NOAA, Silversprings (United States)

    2004-09-15

    For analytical data generated on marine mammal tissues, such as blubber, harmonizing measurements of organohalogen compounds is very important. Often organohalogen data on marine mammal samples from different laboratories are combined to provide an indication of geographical trends or to help ascertain toxicological significance. In at least one study that combined data on organohalogen concentrations from marine mammal blubber to examine geographical trends, it was found that among laboratory variability contributed significantly to the observed data variability (Schwacke, personal communication). To help resolve such problems, NIST and the National Oceanic and Atmospheric Administration (NOAA) initiated an interlaboratory comparison exercise program patterned after the exercise described above but using marine mammal blubber as the exercise materials. The objective of this paper is to describe the exercises, summarize selected results, and discuss the value of these interterlaboratory comparison exercises. The exercises have been held on a small scale (<10 laboratories) starting in 1991 and on a larger scale (10 or more laboratories) starting in 1999. Twenty-four laboratories participated in the 2003 exercise.

  11. NAA for study of organohalogen levels in placenta, umbilical cord and hair of mothers with disabled newborns

    Zhang, H.; Chai, Z.F.; Chinese Academy of Sciences, Beijing; Wang, J.B.

    2008-01-01

    The concentrations of extractable organohalogens (EOX) and extractable persistent organohalogens (EPOX) in placenta, umbilical cord and hair of mothers delivering disabled or normal newborns as well as the compositions of EPOCl in three analyzed matrices were determined by a combination of NAA, gas chromatography and chemical separation. The results indicated that both EOX and EPOX decreased in the order: hair > umbilical cord > placenta. Organochlorines were the major fraction of organohalogens. More than 77% of EPOCl were unidentified. High organohalogens exposure may induce adverse health effects, and hair, as a biomonitor for organohalogens assessment, is more recommendable. (author)

  12. Occurrence of organohalogens at the Dead Sea Basin

    Tubbesing, Christoph; Kotte, Karsten; Keppler, Frank; Krause, Torsten; Bahlmann, Enno; Schöler, Heinfried

    2013-04-01

    Most arid and semi-arid regions are characterized by evaporites, which are assured sources for volatile organohalogens (VOX) [1]. These compounds play an important role in tropospheric and stratospheric chemistry. The Dead Sea between Israel and Jordan is the world's most famous and biggest all-season water covered salt lake. In both countries chemical plants like the Dead Sea Works and the Arab Potash Company are located at the southern part of the Dead Sea and mine various elements such as bromine and magnesium. Conveying sea water through constructed evaporation pans multifarious salts are enriched and precipitated. In contrast, the Northern basin and main part of the Dead Sea has remained almost untouched by industrial salt production. Its fresh water supply from the Jordan River is constantly decreasing, leading to further increased salinity. During a HALOPROC campaign (Natural Halogenation Processes in the Environment) we collected various samples including air, soils, sediments, halophytic plants, ground- and seawater from the Northern and Southern basin of the Israeli side of the Dead Sea. These samples were investigated for the occurrence of halocarbons using different analytical techniques. Most samples were analyzed for volatile organohalogens such as haloalkanes using gas chromatography- mass spectrometry (GC-MS). Interestingly, there is a strong enrichment of trihalomethanes (THM), especially all chlorinated and brominated ones and also the iodinated compound dichloroiodomethane were found in the Southern basin. In addition, volatile organic carbons (VOC) such as ethene and some other alkenes were analyzed by a gas chromatography-flame ionisation detector (GC-FID) to obtain further information about potential precursors of halogenated compounds. Halophytic plants were investigated for their potential to release chloromethane and bromomethane but also for their stable carbon and hydrogen isotope composition. For this purpose, a plant chamber was

  13. Group separation of organohalogenated contaminants by GCxGC

    Korytar, P.; Leonards, P.; Boer, J. de [Netherlands Institute for Fisheries Research, IJmuiden (Netherlands); Parera, J. [Barcelona Univ. (Spain); Brinkman, U. [Vrije Univ., Amsterdam (Netherlands)

    2004-09-15

    The congener specific analysis of organohalogenated compounds is challenging, because of a large number of possibly interfering compounds not only within the compound class but also from congeners of other compound classes. Therefore, analytical procedures usually include complicated and time-consuming multi-step sample pre-treatment and/or selective detection (e.g. HRMS, MS/MS) in the consequent gas chromatographic analysis, what makes the procedures laborious and expensive. One way how to improve the situation would be to considerably increase the separation efficiency of the gas chromatographic analysis by replacing conventional GC by so-called comprehensive two-dimensional gas chromatography (GC x GC). In GC x GC two independent separations are applied to an entire sample which effects a considerably enhanced overall resolution and also, because of the analyte refocusing during modulation, an improved analyte detectability. One further aspect which makes GC x GC especially attractive is the ordered structure of the two-dimensional chromatograms, which is observed when mixtures of related compounds, homologues or congeners are analysed. One good example are the bands of alkanes, naphthenes and aromatics present in 2D chromatogram when petrochemical samples are analysed. The ordered structure was reported also within the compound class of some organohalogenated contaminants, more precisely, of polychlorinated biphenyls and toxaphenes (ordering to number of chlorine atoms on the skeleton). However, to date, no study of separation among the different compound classes has been reported. In the present paper, this topic will be studied for the most common contaminants. While the principle aim is the group type separation, some attention will be devoted also to within the class separation (e.g., for polychlorinated diphenylethers and polychlorinated alkanes).

  14. Androgen receptor gene CAG repeat length as modifier of the association between Persistent Organohalogen Pollutant exposure markers and semen characteristics

    Giwercman, Aleksander; Rylander, Lars; Rignell-Hydbom, Anna

    2007-01-01

    OBJECTIVES: Exposure to persistent organohalogen pollutants was suggested to impair male reproductive function. A gene-environment interaction has been proposed. No genes modifying the effect of persistent organohalogen pollutants on reproductive organs have yet been identified. We aimed to inves...

  15. Organophosphorus pesticide poisoning : cases and developments

    Aardema, H.; Ligtenberg, J. J. M.; Peters-Polman, O. M.; Tulleken, J. E.; Zijlstra, J. G.; Meertens, John H. J. M.

    Self-poisoning with organophosphate pesticides is a major health problem world-wide. Through the inhibition of acetylcholinesterase, organophosphorus poisoning is characterised by the clinical picture of acute cholinergic crisis. Other manifestations are the intermediate neurotoxic syndrome and

  16. Method for purifying bidentate organophosphorus compounds

    Schulz, W.W.

    1977-01-01

    Bidentate organophosphorus compounds useful for extracting actinide elements from acidic nuclear waste solutions are purified of undesirable acidic impurities by contacting the compounds with ethylene glycol which preferentially extracts the impurities found in technical grade bidentate compounds

  17. Management of acute organophosphorus pesticide poisoning

    Eddleston, Michael; Buckley, Nick A; Eyer, Peter; Dawson, Andrew H

    2008-01-01

    Summary Organophosphorus pesticide self-poisoning is an important clinical problem in rural regions of the developing world, and kills an estimated 200?000 people every year. Unintentional poisoning kills far fewer people but is a problem in places where highly toxic organophosphorus pesticides are available. Medical management is difficult, with case fatality generally more than 15%. We describe the limited evidence that can guide therapy and the factors that should be considered when design...

  18. Is the fact of parenting couples cohabitation affecting the serum levels of persistent organohalogen pollutants?

    Góralczyk, Katarzyna; Struciński, Paweł; Wojtyniak, Bogdan

    2015-01-01

    Organohalogen compounds constitute one of the important groups of persistent organic pollutants (POPs). Among them, due to their long-term health effects, one should pay attention on organochlorine pesticides, polychlorinated biphenyls (PCBs) and perfluoroalkylated substances (PFASs). This paper...... is an attempt to answer the question about relation between the fact of cohabitation by couples expecting a child and the level of the organohalogen compounds in the blood serum of both parents. The study was done on a population of parent couples from Greenland, Poland and Ukraine, from whom blood samples were...

  19. Neutron activation analysis for study of distribution patterns of organo-halogen pollutants in apple

    Zhang Hong; Luo Jialing; Sun Huibin; Chai Zhifang; Chinese Academy of Sciences, Beijing

    2007-01-01

    The distribution characteristics of organo-halogens in apple and their sources were studied by neutron activation analysis combined with statistical analysis. The results indicated that concentrations of organo-halogens in apple were in the order of organo-chlorine >> organo-bromine > organo-iodine, and concentrations of the organo-chlorine in four parts of apple were in the order of seed >> peel >> endocarp ≥ pulp. Also, the organo-chlorine, -bromine and-iodine in apple were found to have different sources. The latter two were mainly from naturally synthetic products by plant itself, while the former was mainly from anthropogenic pollutants. (authors)

  20. Reproductive failure and endocrine disruption by organohalogens in fish-eating birds

    Bosveld, A.T.C.; Berg, van den M.

    2002-01-01

    Effects of organohalogens in fish-eating birds in the field have been monitored largely by studying reproductive outcome in contaminated populations or, at the individual level, by studying the sexual behaviour, egg production, or embryonal and postnatal development and survival. Endocrine

  1. Neutron activation analysis for the optimal sampling and extraction of extractable organohalogens in human hari

    Zhang, H.; Chai, Z.F.; Sun, H.B.; Xu, H.F.

    2005-01-01

    Many persistent organohalogen compounds such as DDTs and polychlorinated biphenyls have caused seriously environmental pollution problem that now involves all life. It is know that neutron activation analysis (NAA) is a very convenient method for halogen analysis and is also the only method currently available for simultaneously determining organic chlorine, bromine and iodine in one extract. Human hair is a convenient material to evaluate the burden of such compounds in human body and dan be easily collected from people over wide ranges of age, sex, residential areas, eating habits and working environments. To effectively extract organohalogen compounds from human hair, in present work the optimal Soxhelt-extraction time of extractable organohalogen (EOX) and extractable persistent organohalogen (EPOX) from hair of different lengths were studied by NAA. The results indicated that the optimal Soxhelt-extraction time of EOX and EPOX from human hair was 8-11 h, and the highest EOX and EPOX contents were observed in hair powder extract. The concentrations of both EOX and EPOX in different hair sections were in the order of hair powder ≥ 2 mm > 5 mm, which stated that hair samples milled into hair powder or cut into very short sections were not only for homogeneous. hair sample but for the best hair extraction efficiency.

  2. Prenatal Exposure to Organohalogens, Including Brominated Flame Retardants, Influences Motor, Cognitive, and Behavioral Performance at School Age

    Roze, Elise; Meijer, Lisethe; Bakker, Attie; Van Braeckel, Koenraad N. J. A.; Sauer, Pieter J. J.; Bos, Arend F.

    2009-01-01

    BACKGROUND: Organohalogen compounds (OHCs) are known to have neurotoxic effects on the developing brain. OBJECTIVE: We investigated the influence of prenatal exposure to OHCs, including brominated flame retardants, on motor, cognitive, and behavioral outcome in healthy children of school age.

  3. of Several Organophosphorus Insecticide Metabolites

    Russell L. Carr

    2015-01-01

    Full Text Available Paraoxonase (PON1 is a calcium dependent enzyme that is capable of hydrolyzing organophosphate anticholinesterases. PON1 activity is present in most mammals and previous research established that PON1 activity differs depending on the species. These studies mainly used the organophosphate substrate paraoxon, the active metabolite of the insecticide parathion. Using serum PON1 from different mammalian species, we compared the hydrolysis of paraoxon with the hydrolysis of the active metabolites (oxons of two additional organophosphorus insecticides, methyl parathion and chlorpyrifos. Paraoxon hydrolysis was greater than that of methyl paraoxon, but the level of activity between species displayed a similar pattern. Regardless of the species tested, the hydrolysis of chlorpyrifos-oxon was significantly greater than that of paraoxon or methyl paraoxon. These data indicate that chlorpyrifos-oxon is a better substrate for PON1 regardless of the species. The pattern of species differences in PON1 activity varied with the change in substrate to chlorpyrifos-oxon from paraoxon or methyl paraoxon. For example, the sex difference observed here and reported elsewhere in the literature for rat PON1 hydrolysis of paraoxon was not present when chlorpyrifos-oxon was the substrate.

  4. Lysophospholipase inhibition by organophosphorus toxicants

    Quistad, Gary B.; Casida, John E.

    2004-01-01

    Lysophospholipases (LysoPLAs) are a large family of enzymes for removing lysophospholipids from cell membranes. Potent inhibitors are needed to define the importance of LysoPLAs as targets for toxicants and potential therapeutics. This study considers organophosphorus (OP) inhibitors with emphasis on mouse brain total LysoPLA activity relative to the mipafox-sensitive neuropathy target esterase (NTE)-LysoPLA recently established as 17% of the total activity and important in the action of OP delayed toxicants. The most potent inhibitors of total LysoPLA in mouse brain are isopropyl dodecylphosphonofluoridate (also for LysoPLA of Vibrio bacteria), ethyl octylphosphonofluoridate (EOPF), and two alkyl-benzodioxaphosphorin 2-oxides (BDPOs)[(S)-octyl and dodecyl] (IC50 2-8 nM). OP inhibitors acting in vitro and in vivo differentiate a more sensitive portion but not a distinct NTE-LysoPLA compared with total LysoPLA activity. For 10 active inhibitors, NTE-LysoPLA is 17-fold more sensitive than total LysoPLA, but structure-activity comparisons give a good correlation (r 2 = 0.94) of IC50 values, suggesting active site structural similarity or identity. In mice 4 h after intraperitoneal treatment with discriminating doses, EOPF, tribufos (a plant defoliant), and dodecanesulfonyl fluoride inhibit 41-57% of the total brain LysoPLA and 85-99% of the NTE-LysoPLA activity. Total LysoPLA as well as NTE-LysoPLA is decreased in activity in Nte +/- -haploinsufficient mice compared to their Nte +/+ littermates. The lysolecithin level of spinal cord but not brain is elevated significantly following EOPF treatment (3 mg/kg), thereby focusing attention on localized rather than general alterations in lysophospholipid metabolism in OP-induced hyperactivity and toxicity

  5. Efficacious Oxime for Organophosphorus Poisoning: A Minireview

    Erah

    Abstract. Oximes are well known as acetylcholinesterase reactivators and are used in ... activity against structurally different kinds of organophosphorus ... serious threat with regard to occupational .... choose an oxime for unknown OPC exposure. Secondly, there is a lack of .... oximes, and hence cannot pass the blood.

  6. A retrospective analysis of acute organophosphorus poisoning ...

    A retrospective analysis of acute organophosphorus poisoning cases admitted to the tertiary care teaching hospital in South India. ... Young adult males were more commonly involved than females (M:F 2.5:1). The mean age of the patients was 28 years (range 2-72 years, SD ± 14.3 years). Mean time to receive treatment ...

  7. A retrospective analysis of acute organophosphorus poisoning ...

    organophosphorus (OP) poisoning cases in a tertiary care hospital. Materials and ... In a pre-structured proforma, data regarding age, sex, time elapsed after intake, circumstances of poisoning, duration of hospitalization ... responsible for majority of self-attempted deaths ... cleansed with water at the time of admission.

  8. Determination of selected organophosphorus pesticides using GC ...

    A reproducible analytical method utilising GC-MS is presented for the analysis of thirteen organophosphorus insecticides (OPs) often found in environmental aqueous samples. Extraction of filtered river and canal water (100 mL), fortified with the OPs, was conducted using solid-phase extraction and eluted with a variety of ...

  9. Efficacious Oxime for Organophosphorus Poisoning: A Minireview ...

    Oximes are well known as acetylcholinesterase reactivators and are used in organophosphorus poisoning to reactivate inhibited acetylcholinesterase. Therapeutically available oximes, namely, pralidoxime (2-PAM), obidoxime, trimedoxime and Hagedorn oxime (HI-6), have no broad-spectrum activity against structurally ...

  10. A review on current knowledge and future prospects of organohalogen contaminants (OHCs) in Asian birds.

    Abbasi, Naeem Akhtar; Malik, Riffat Naseem; Frantz, Adrien; Jaspers, Veerle Leontina Bernard

    2016-01-15

    The release of harmful chemicals in the Asian environment has recently increased dramatically due to rising industrial and agricultural activities. About 60% of the global human population is currently living on the Asian continent and may thus be exposed to a large range of different chemicals. Different classes of organohalogen chemicals have indeed been reported in various environmental compartments from Asia including humans and wildlife, but this issue has received less attention in birds. In this article, we reviewed the available literature on levels of legacy persistent organic pollutants (POPs) and various flame retardants (FRs) in Asian avifauna to analyze the existing pool of knowledge as well as to identify the gaps that should be addressed in future research. Furthermore, we discussed the variation in levels of organohalogens based on differences in regions, trophic level, dietary sources and migratory behaviors of species including distribution patterns in different tissues of birds. Although the mass of published literature is very low and even absent in many important regions of Asia, we deduced from the reported studies that levels of almost all classes of organohalogens (OHCs) including FRs were highest in East Asian countries such as Japan, China and South Korea, except for HCHs that were found at maximum levels in birds of South India. Concentrations (ng/g LW) of different OHCs in Asian birds ranged between birds, vicinity to sources and trans-boundary movement of pollutants were identified as key exposure routes and subsequent OHCs contamination in Asian birds. There is extreme scarcity of literature on organohalogen contamination in birds from Northern, South-eastern and west Asian countries where an industrial boom has been witnessed in the past few decades. Current scenarios suggest that levels of OHCs, particularly the FRs, are rising in birds of Asia and it would be wise to develop baseline information and to regulate the OHCs emission

  11. Study of organohalogens in foodstuffs and environmental samples by neutron activation analysis and related techniques

    Xu, D. D.; Mao, X.Y.; Ouyang, H.; Chai, Z. F.; Zhang, H.; Sun, H. B.

    2004-01-01

    Pine needles and foodstuffs collected from Beijing, China, were analyzed by instrumental neutron activation analysis (INAA) combined with organic solvent extraction for total halogens, extractable organohalogens (EOX) and extractable persistent organohalogens (EPOX). The INAA detection limits are 50 ng, 8 ng and 3.5 ng for Cl, Br and I, respectively. The contents and distribution patterns of organohalogens in these samples are reported. EOCl accounted for 0.013-0.016% and 1.6-2.7% of the total chlorine in yogurt and apples, respectively, which suggested that chlorine in foodstuffs mainly existed as inorganic species and non-extractable organochlorines. EOCl contents in pine needles and foodstuffs were noticeably higher than those of EOBr and EOI. For pine needles, yogurt and apples, 1.6-34%, 23-58% and 29-35% of EOCl remained as extractable persistent organochlorine (EPOCl), respectively. Pine needle containing higher EOCl contents in chemical industrial and traffic hub areas indicated that chemical industries and exhaust emission from vehicle were the main sources of organochlorines in the Beijing's air. The relative proportions of the known organochlorines (such as HCHs, DDTs, chlordanes, heptachlor, HCB and PCBs) to the total EOCl and EPOCl were 0.04-1.6% and 0.7-21.5%, respectively, which implied that the identity of species of a major portion of the EOCl and EPOCl measured in pine needles was unknown. (author)

  12. Organohalogen products from chlorination of cooling water at nuclear power stations

    Bean, R.M.

    1983-10-01

    Eight nuclear power units at seven locations in the US were studied to determine the effects of chlorine, added as a biocide, on the composition of cooling water discharge. Water, sediment and biota samples from the sites were analyzed for total organic halogen and for a variety of organohalogen compounds. Haloforms were discharged from all plants studied, at concentrations of a few μg/L (parts-per-billion). Evidence was obtained that power plants with cooling towers discharge a significant portion of the haloforms formed during chlorination to the atmosphere. A complex mixture of halogenated phenols was found in the cooling water discharges of the power units. Cooling towers can act to concentrate halogenated phenols to levels approaching those of the haloforms. Examination of samples by capillary gas chromatography/mass spectrometry did not result in identification of any significant concentrations of lipophilic base-neutral compounds that could be shown to be formed by the chlorination process. Total concentrations of lipophilic (Bioabsorbable) and volatile organohalogen material discharged ranged from about 2 to 4 μg/L. Analysis of sediment samples for organohalogen material suggests that certain chlorination products may accumulate in sediments, although no tissue bioaccumulation could be demonstrated from analysis of a limited number of samples. 58 references, 25 figures, 31 tables

  13. Maternal transfer of organohalogen contaminants and metabolites to eggs of Arctic-breeding glaucous gulls

    Verreault, Jonathan; Villa, Rosa A.; Gabrielsen, Geir W.; Skaare, Janneche U.; Letcher, Robert J.

    2006-01-01

    Eggs of seabirds have routinely been used as indicators of environmental pollution in the Arctic. However, the variability in organohalogen concentration and composition associated with the laying sequence, have not been defined. We examined a suite of PCBs, organochlorine (OC) pesticides and by-products, polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs) and methylsulfonyl- (MeSO 2 ) PCBs in complete 3-egg clutches of glaucous gulls (Larus hyperboreus), and plasma samples of the laying females collected from the Norwegian Arctic. ΣPCB, ΣOC and ΣPBDE, but not ΣMeSO 2 -PCB, concentrations in eggs were positively associated, with increasing magnitude and significance from the first through the last-laid egg, with concentrations in female plasma. However, the concentrations of these organohalogen classes fluctuated irrespective of the laying order in the clutch. In general, maternal transfer favored low K ow and/or less persistent compounds, whereas the recalcitrant and/or higher-halogenated compounds were less readily transferred, and consequently more selectively retained in the mother. - Concentrations of organohalogen contaminants and metabolites in eggs of glaucous gulls do not fluctuate with the laying order in a three-egg clutch

  14. Biochemical Markers for Exposure to Low Doses of Organophosphorus Insecticides

    Lockridge, Oksana

    2003-01-01

    Though acetylcholinesterase is the primary target of organophosphorus toxicants, our finding that acetylcholinesterase knockout mice are supersensitive to the lethal effects of VX, DFP, chlorpyrifos...

  15. Biochemical Markers for Exposure to Low Doses of Organophosphorus Insecticides

    Lockridge, Oksana

    2004-01-01

    Though acetylcholinesterase is the primary target of organophosphorus toxicants, our finding that acetylcholinesterase knockout mice are supersensitive to the lethal effects of VX, DFP, chlorpyrifos...

  16. Biochemical Markers for Exposure to Low Doses of Organophosphorus Insecticides

    Lockridge, Oksana

    2002-01-01

    Though acetyicholinesterase is the primary target of organophosphorus toxicants, our finding that acetyicholinesterase knockout mice are supersensitive to the lethal effects of VX, DFP, chlorpyrifos...

  17. Technical Note: Reactivity of C1 and C2 organohalogens formation – from plant litter to bacteria

    J. J. Wang

    2012-10-01

    Full Text Available C1/C2 organohalogens (organohalogens with one or two carbon atoms can have significant environmental toxicity and ecological impact, such as carcinogenesis, ozone depletion and global warming. Natural halogenation processes have been identified for a wide range of natural organic matter, including soils, plant and animal debris, algae, and fungi. Yet, few have considered these organohalogens generated from the ubiquitous bacteria, one of the largest biomass pools on earth. Here, we report and confirm the formation of chloroform (CHCl3 dichloro-acetonitrile (CHCl2CN, chloral hydrate (CCl3CH(OH2 and their brominated analogues by direct halogenation of seven strains of common bacteria and nine cellular monomers. Comparing different major C stocks during litter decomposition stages in terrestrial ecosystems, from plant litter, decomposed litter, to bacteria, we found increasing reactivity for nitrogenous organohalogen yield with decreasing C/N ratio. Our results raise the possibility that natural halogenation of bacteria represents a significant and overlooked contribution to global organohalogen burdens. As bacteria are decomposers that alter the C quality by transforming organic matter pools from high to low C/N ratio and constitute a large organic N pool, the bacterial activity is expected to affect the C, N, and halogen cycling through natural halogenation reactions.

  18. Different approaches to acute organophosphorus poison treatment.

    Nurulain, Syed Muhammad

    2012-07-01

    Organophosphorus compounds (OPCs) have a wide variety of applications and are a serious threat for self-poisoning, unintentional misuse, terrorist attack, occupational hazard and warfare attack. The present standard treatment has been reported to be unsatisfactory. Many novel approaches are being used and tested for acute organophosphorus (OP) poison treatment. The bioscavenger concept captured high attention among the scientific community during the last few decades. Other approaches like alkalinisation of blood plasma/serum and use of weak inhibitors against strong inhibitors, though it showed promising results, did not get such wide attention. The introduction of a novel broad-spectrum oxime has also been in focus. In this mini-review, an update of the overview of four different approaches has been discussed. The standard therapy that is atropine+oxime+benzodiazepine along with supportive measures will continue to be the best option with only the replacement of a single oxime to improve its broad-spectrum efficacy.

  19. Management of acute organophosphorus pesticide poisoning.

    Eddleston, Michael; Buckley, Nick A; Eyer, Peter; Dawson, Andrew H

    2008-02-16

    Organophosphorus pesticide self-poisoning is an important clinical problem in rural regions of the developing world, and kills an estimated 200,000 people every year. Unintentional poisoning kills far fewer people but is a problem in places where highly toxic organophosphorus pesticides are available. Medical management is difficult, with case fatality generally more than 15%. We describe the limited evidence that can guide therapy and the factors that should be considered when designing further clinical studies. 50 years after first use, we still do not know how the core treatments--atropine, oximes, and diazepam--should best be given. Important constraints in the collection of useful data have included the late recognition of great variability in activity and action of the individual pesticides, and the care needed cholinesterase assays for results to be comparable between studies. However, consensus suggests that early resuscitation with atropine, oxygen, respiratory support, and fluids is needed to improve oxygen delivery to tissues. The role of oximes is not completely clear; they might benefit only patients poisoned by specific pesticides or patients with moderate poisoning. Small studies suggest benefit from new treatments such as magnesium sulphate, but much larger trials are needed. Gastric lavage could have a role but should only be undertaken once the patient is stable. Randomised controlled trials are underway in rural Asia to assess the effectiveness of these therapies. However, some organophosphorus pesticides might prove very difficult to treat with current therapies, such that bans on particular pesticides could be the only method to substantially reduce the case fatality after poisoning. Improved medical management of organophosphorus poisoning should result in a reduction in worldwide deaths from suicide.

  20. Organohalogen concentrations and a gross and histologic assessment of multiple organ systems in East Greenland polar bears (Ursus maritimus)

    Sonne, C.

    To investigate the relation between biological parameters, not earlier investigated in the polar bear, and organohalogen pollution in East Greenland polar bears, we initiated a sampling of adipose tissue, internal organs and skulls from more than 100 free-ranging polar bears killed by local...... in the adipose tissue and pathological changes in skulls and internal organs. Our results suggested a decrease in adipose tissue concentrations of organohalogens in East Greenland polar bears from 1990 to 1999-2001. Two of the biological effect parameters (FA and enlarged clitoris) did not indicate a link......, infectious agents, season and meaby chronic exposure to organohalogens. These result fill out an existing knowledge gap in potential effects of environmental, organic contaminants on fluctuating asymmetry, bone mineral density and functional anatomy (histology) in the polar bear. In addition, the results may...

  1. A review on current knowledge and future prospects of organohalogen contaminants (OHCs) in Asian birds

    Abbasi, Naeem Akhtar [Environmental Biology and Ecotoxicology Laboratory, Department of Environmental Sciences, Faculty of Biological Sciences, Quaid-i-Azam University, Islamabad 45320 (Pakistan); Malik, Riffat Naseem, E-mail: r_n_malik2000@yahoo.co.uk [Environmental Biology and Ecotoxicology Laboratory, Department of Environmental Sciences, Faculty of Biological Sciences, Quaid-i-Azam University, Islamabad 45320 (Pakistan); Frantz, Adrien [Sorbonne Universités, UPMC Univ Paris 06, UPEC, Paris 7, CNRS, INRA, IRD, Institut d' Ecologie et des Sciences de l' Environnement de Paris, F-75005, Paris (France); Jaspers, Veerle Leontina Bernard [Environmental Toxicology, Department of Biology, Norwegian University of Science and Technology (NTNU), Trondheim (Norway)

    2016-01-15

    The release of harmful chemicals in the Asian environment has recently increased dramatically due to rising industrial and agricultural activities. About 60% of the global human population is currently living on the Asian continent and may thus be exposed to a large range of different chemicals. Different classes of organohalogen chemicals have indeed been reported in various environmental compartments from Asia including humans and wildlife, but this issue has received less attention in birds. In this article, we reviewed the available literature on levels of legacy persistent organic pollutants (POPs) and various flame retardants (FRs) in Asian avifauna to analyze the existing pool of knowledge as well as to identify the gaps that should be addressed in future research. Furthermore, we discussed the variation in levels of organohalogens based on differences in regions, trophic level, dietary sources and migratory behaviors of species including distribution patterns in different tissues of birds. Although the mass of published literature is very low and even absent in many important regions of Asia, we deduced from the reported studies that levels of almost all classes of organohalogens (OHCs) including FRs were highest in East Asian countries such as Japan, China and South Korea, except for HCHs that were found at maximum levels in birds of South India. Concentrations (ng/g LW) of different OHCs in Asian birds ranged between < LOD (limit of detection) to 14,000,000 for polychlorinated biphenyls (PCBs), < LOD to 790,000 for dichlorodiphenyltrichloroethane (DDTs), < LOD to 12,000 for hexachlorobenzene (HCB), < LOD to 29,000 for hexachlorocyclohexanes (HCHs), < LOD to 47,000 for chlordanes (CHLs) and < LOD to 4600 for total cyclodienes. Further, ranges (ng/g LW) of 1.1 to 150,000 for Co-PCBs; < LOD to 27 for polychlorinated dibenzo-p-dioxins (PCDDs); < LOD to 45 for polychlorinated dibenzofurans (PCDFs) and 0.02 to 73 for PCDD/DFs have been reported in Asian aves

  2. A review on current knowledge and future prospects of organohalogen contaminants (OHCs) in Asian birds

    Abbasi, Naeem Akhtar; Malik, Riffat Naseem; Frantz, Adrien; Jaspers, Veerle Leontina Bernard

    2016-01-01

    The release of harmful chemicals in the Asian environment has recently increased dramatically due to rising industrial and agricultural activities. About 60% of the global human population is currently living on the Asian continent and may thus be exposed to a large range of different chemicals. Different classes of organohalogen chemicals have indeed been reported in various environmental compartments from Asia including humans and wildlife, but this issue has received less attention in birds. In this article, we reviewed the available literature on levels of legacy persistent organic pollutants (POPs) and various flame retardants (FRs) in Asian avifauna to analyze the existing pool of knowledge as well as to identify the gaps that should be addressed in future research. Furthermore, we discussed the variation in levels of organohalogens based on differences in regions, trophic level, dietary sources and migratory behaviors of species including distribution patterns in different tissues of birds. Although the mass of published literature is very low and even absent in many important regions of Asia, we deduced from the reported studies that levels of almost all classes of organohalogens (OHCs) including FRs were highest in East Asian countries such as Japan, China and South Korea, except for HCHs that were found at maximum levels in birds of South India. Concentrations (ng/g LW) of different OHCs in Asian birds ranged between < LOD (limit of detection) to 14,000,000 for polychlorinated biphenyls (PCBs), < LOD to 790,000 for dichlorodiphenyltrichloroethane (DDTs), < LOD to 12,000 for hexachlorobenzene (HCB), < LOD to 29,000 for hexachlorocyclohexanes (HCHs), < LOD to 47,000 for chlordanes (CHLs) and < LOD to 4600 for total cyclodienes. Further, ranges (ng/g LW) of 1.1 to 150,000 for Co-PCBs; < LOD to 27 for polychlorinated dibenzo-p-dioxins (PCDDs); < LOD to 45 for polychlorinated dibenzofurans (PCDFs) and 0.02 to 73 for PCDD/DFs have been reported in Asian aves

  3. Analysis of organophosphorus pesticides using FT-NMR

    Miyata, Yoshihiko; Takahashi, Yoshikazu; Ando, Hiroaki

    1988-01-01

    A rapid and highly selective method of the identification of 23 kinds of organophosphorus pesticides was develop by using 31 P FT-NMR with 1 H complete decoupling method. Chemical shifts referenced by 85 % H 3 PO 4 were within -4 to 100 ppm, and there was no overlapping among the organophosphorus pesticides used in this experiment. (author)

  4. Concentrations, distribution, sources and risk assessment of organohalogenated contaminants in soils from Kenya, Eastern Africa

    Sun, Hongwei; Qi, Yueling; Zhang, Di; Li, Qing X.; Wang, Jun

    2016-01-01

    The organohalogenated contaminants (OCs) including 12 organochlorine pesticides (OCPs), 7 indicator polychlorinated biphenyls (PCBs) and 7 polybrominated diphenyl ethers (PBDEs) were determined in soils collected from Kenya, Eastern Africa. The total OCPs fell in the range of n.d–49.74 μg kg"−"1 dry weight (dw), which was dominated by DDTs and endosulfan. Identification of pollution sources indicated new input of DDTs for malaria control in Kenya. The total PCBs ranged from n.d. to 55.49 μg kg"−"1 dw, dominated by penta- and hexa-PCBs, probably associated with the leakage of obsolete transformer oil. The soils were less contaminated by PBDEs, ranging from 0.19 to 35.64 μg kg"−"1 dw. The predominant PBDE congeners were penta-, tri- or tetra-BDEs, varying among different sampling sites. Risk assessment indicated potential human health risks posed by OCs in soils from Kenya, with PCBs as the most contributing pollutants. The local authorities are recommended to make best efforts on management of OC pollution, particularly from DDTs and PCBs to meet the requirement of Stockholm Convention. - Highlights: • The first report on organohalogen contaminants (OCs) in soils from Kenya. • OCs including OCPs, PCBs and PBDEs were determined simultaneously. • Sources of OCPs, PCBs and PBDEs emission were identified. • Human health risk posed by OCs in soil from Kenya were assessed. • Measures for OCs management were suggested for local authority. - The soils from Kenya were heavily polluted by organohalogenated contaminants (OCs). New input of DDTs probably occurred. Among all OCs, PCBs were predominant.

  5. Detection of dehalogenation impurities in organohalogenated pharmaceuticals by UHPLC-DAD-HRESIMS.

    Regalado, Erik L; Dermenjian, Renee K; Joyce, Leo A; Welch, Christopher J

    2014-04-01

    The presence of dehalogenated impurities is often observed in halogen-containing pharmaceuticals, and can present a difficult analytical challenge, as the chromatographic behavior of the halogenated drug and the hydrogen-containing analog can be quite similar. In this study we describe the chromatographic separation and unambiguous identification of dehalogenation impurities or associated isomers in organohalogenated pharmaceuticals using UHPLC with a pentafluorophenyl column coupled with diode-array and high resolution electrospray ionization mass spectrometry detection (UHPLC-DAD-HRESIMS). Copyright © 2014 Elsevier B.V. All rights reserved.

  6. Levels and distribution of organohalogenated contaminants in 5 fish species from Sir Dam Lake, Kahramanmaras, Turkey

    Erdogrul, Oe [Faculty of Agriculture, Kahramanmaras (Turkey). Dept. of Food Engineering; Covaci, A; Schepens, P [Antwerp Univ. (Belgium). Toxicological Center

    2004-09-15

    In Turkey, OCPs have been used since 1945, with large quantities of these chemicals being used during the 1960s and 1970s. Since 1983, the usage of OCPs has been severely restricted or banned. Only few studies have investigated the presence of OCPs in Turkish aquatic environment, where they have been evidenced in relatively high concentrations. The aim of this study was to investigate the levels and distribution of organohalogenated contaminants in several fish species from Syr Dam Lake (Kahramanmarab, Turkey), an artificial lake with great economical importance for the region.

  7. Reproductive hormone levels in men exposed to persistent organohalogen pollutants: a study of inuit and three European cohorts

    Giwercman, Aleksander; Rignell-Hydbom, Anna; Toft, Gunnar

    2006-01-01

    OBJECTIVE: Persistent organohalogen pollutant (POP) exposure may have a negative impact on reproductive function. The objective of this study was to assess the impact of POP exposure on the male hypothalamo-pituitary-gonadal axis. PARTICIPANTS: Participants included 184 Swedish fishermen and spou...

  8. Determination of extractable organohalogens in apple by neutron activation analysis and gas chromatography

    Zhang, H.; Chai, Z.F.; Sun, H.B.; Zhang, J.L.; Sun, J.Q.

    2005-01-01

    In addition to compounds such as dichlorodiphenyl trichloroethanes (DDTs) and polychlorinated biphenyls (PCBs), which originate from by now well-known anthropogenic sources, there is increasing awareness of other halogenated compounds coming from a number of different processes, and probably also from natural source. To provide the reliable results and data for evaluation of hazard of extractable persistent organohalogen (EPOX) to food safety and to further characterize halogenated compounds in fruits, the concentrations of extractable organohalogen (EOX), EPOX, and identified organochlorine compounds including DDTs, hexachlorinated cyclohexanes (HCHs), chlordanes and PCBs in apple samples from Chinese homegrown and imports were determined by neutron activation analysis (NAA) and gas chromatography. The results indicated that the levels of EPOX in apples was in the order of EPOCl >> EPOBr > EPOI, which showed that EPOCl was the major fraction of the EPOX pollutions. Also, most chlorinated compounds in apple samples existed as inorganic species and water-soluble polar compounds, and about 1/10-4/5 of EOX was sulfuric acid-resistant EPOX contaminants. Meanwhile, about more than 94 % of EPOCl in detected specimens cannot be accounted for by DDTs, HCHs, chlordanes and PCBs. Furthermore, the T-test result indicated that the EPOCl levels in apple were significantly higher than those in peeled apple , which stated that people consuming peeled apple will get lesser intakes of EPOCl pollutants than they consume unpeeled apple.

  9. Emission of Volatile OrganoHalogens by Southern African Solar Salt Works

    Kotte, Karsten; Weissflog, Ludwig; Lange, Christian Albert; Huber, Stefan; Pienaar, Jacobus J.

    2010-05-01

    Volatile organic compounds containing halogens - especially chlorine - have been considered for a long time of industrial origin only, and it was assumed that the production and emission of these compounds can easily be controlled by humans in case they will cause a threat for life on Earth. Since the middle of the 80ies of the last century it became clear that the biologically active organohalogens isolated by chemists are purposefully produced by nature as antibiotics or as antifeedant etc. To date more than 3800 organohalogens are known to be naturally produced by bio-geochemical processes. The global budgets of many such species are poorly understood and only now with the emergence of better analytical techniques being discovered. For example the compound chloromethane nature's production (5 GT) outdates the anthropogenic production (50 KT) by a factor of 100. Thus organohalogens are an interesting recent case in point since they can influence the ozone budget of the boundary layer, play a role in the production of aerosols and the climate change discussion. An intriguing observation is that most of the atmospheric CH3Cl and CH3Br are of terrestrial rather than of marine origin and that a number of halogenated small organic molecules are produced in soils. The high concentrations of halides in salt soils point to a possibly higher importance of natural halogenation processes as a source of volatile organohalogens. Terrestrial biota, such as fungi, plants, animals and insects, as well as marine algea, bacteria and archaea are known or suspected to be de-novo producers of volatile organohalogens. In recent years we revealed the possibility for VOX to form actively in water and bottom sediments of hyper-saline environments in the course of studying aridization processes during climatic warming. Due to the nature of their production process solar salt works, as to be found along-side the Southern African coast line but also upcountry, combine a variety of semi- and

  10. Chlorination of organophosphorus pesticides in natural waters

    Acero, Juan L. [Departamento de Ingenieria Quimica y Energetica, Universidad de Extremadura, 06071 Badajoz (Spain)], E-mail: jlacero@unex.es; Benitez, F. Javier; Real, Francisco J.; Gonzalez, Manuel [Departamento de Ingenieria Quimica y Energetica, Universidad de Extremadura, 06071 Badajoz (Spain)

    2008-05-01

    Unknown second-order rate constants for the reactions of three organophosphorus pesticides (chlorpyrifos, chlorfenvinfos and diazinon) with chlorine were determined in the present study, and the influence of pH and temperature was established. It was found that an increase in the pH provides a negative effect on the pesticides degradation rates. Apparent second-order rate constants at 20 {sup o}C and pH 7 were determined to be 110.9, 0.004 and 191.6 M{sup -1} s{sup -1} for chlorpyrifos, chlorfenvinfos and diazinon, respectively. A higher reactivity of chlorine with the phosphorothioate group (chlorpyrifos and diazinon) than with the phosphate moiety (chlorfenvinfos) could explain these results. Intrinsic rate constant for the elementary reactions of chlorine species with chlorpyrifos and diazinon were also calculated, leading to the conclusion that the reaction between hypochlorous acid and the pesticide is predominant at neutral pH. The elimination of these pesticides in surface waters was also investigated. A chlorine dose of 2.5 mg L{sup -1} was enough to oxidize chlorpyrifos and diazinon almost completely, with a formation of trihalomethanes below the EU standard for drinking water. However, the removal of chlorfenvinfos was not appreciable. Therefore, chlorination is a feasible option for the removal of organophosphorus pesticides with phosphorothioate group during oxidation and disinfection processes, but not for the elimination of pesticides with phosphate moiety.

  11. Chlorination of organophosphorus pesticides in natural waters

    Acero, Juan L.; Benitez, F. Javier; Real, Francisco J.; Gonzalez, Manuel

    2008-01-01

    Unknown second-order rate constants for the reactions of three organophosphorus pesticides (chlorpyrifos, chlorfenvinfos and diazinon) with chlorine were determined in the present study, and the influence of pH and temperature was established. It was found that an increase in the pH provides a negative effect on the pesticides degradation rates. Apparent second-order rate constants at 20 o C and pH 7 were determined to be 110.9, 0.004 and 191.6 M -1 s -1 for chlorpyrifos, chlorfenvinfos and diazinon, respectively. A higher reactivity of chlorine with the phosphorothioate group (chlorpyrifos and diazinon) than with the phosphate moiety (chlorfenvinfos) could explain these results. Intrinsic rate constant for the elementary reactions of chlorine species with chlorpyrifos and diazinon were also calculated, leading to the conclusion that the reaction between hypochlorous acid and the pesticide is predominant at neutral pH. The elimination of these pesticides in surface waters was also investigated. A chlorine dose of 2.5 mg L -1 was enough to oxidize chlorpyrifos and diazinon almost completely, with a formation of trihalomethanes below the EU standard for drinking water. However, the removal of chlorfenvinfos was not appreciable. Therefore, chlorination is a feasible option for the removal of organophosphorus pesticides with phosphorothioate group during oxidation and disinfection processes, but not for the elimination of pesticides with phosphate moiety

  12. QSAR for cholinesterase inhibition by organophosphorus esters and CNDO/2 calculations for organophosphorus ester hydrolysis

    Johnson, H.; Kenley, R. A.; Rynard, C.; Golub, M. A.

    1985-01-01

    Quantitative structure-activity relationships were derived for acetyl- and butyrylcholinesterase inhibition by various organophosphorus esters. Bimolecular inhibition rate constants correlate well with hydrophobic substituent constants, and with the presence or absence of catonic groups on the inhibitor, but not with steric substituent constants. CNDO/2 calculations were performed on a separate set of organophosphorus esters, RR'P(O)X, where R and R' are alkyl and/or alkoxy groups and X is fluorine, chlorine or a phenoxy group. For each subset with the same X, the CNDO-derived net atomic charge at the central phosphorus atom in the ester correlates well with the alkaline hydrolysis rate constant. For the whole set of esters with different X, two equations were derived that relate either charge and leaving group steric bulk, or orbital energy and bond order to the hydrogen hydrolysis rate constant.

  13. Treatment Strategies for the NMDA Component of Organophosphorus Convulsions

    Peterson, Steven

    2003-01-01

    ...) induced status epilepticus (SE) used here as a model of organophosphorus nerve agents. The nonbarbiturate anesthetic propofol was found to induce significant anticonvulsant and neuroprotectant effects in Li-pilo SE...

  14. Levels and trends of organohalogen compounds in mussels from the Seine estuary in 1981 - 2003

    Johansson, I.; Moisan, K.; Guiot, N.; Truquet, I.; Munschy, C.; Tronczynski, J. [IFREMER, Nantes (France)

    2004-09-15

    Even though the use of many organohalogen compounds have decreased or even ceased during the recent years, the release of these contaminants to the environment from different sources continues. The research efforts of the last two decades provided evidence of the spread throughout the global environment of certain persistent organic compounds and quantitative understanding of the mechanisms of the distribution of these and other compounds in the environmental reservoirs, including living organisms and human population. It appears that these compounds are now embedded in the natural biogeochemical cycles. The recent data reveal also pulses of banned POPs in air concentrations in U.S. and Canada. Furthermore, the inventory of a global cumulative usage of PCBs shows also that usage of theses chemicals were highest in western central Europe (ex. France, Benelux, UK and Germany), in eastern U.S. and in Japan, and that in these countries significant amounts are still deposited on various sites. Finally, it has been found, that certain of the ''novel'' contaminants are organohalogens (brominated, fluorinated chemicals) and might be indeed of environmental concern, because they have been shown to be mobile, persistent and toxic and some are bioaccumulative. The long term environmental monitoring enables to reveal temporal trends of concentration levels in the marine environment. These data is also necessary to verify if the international measures undertaken to phaseout, reduce losses and emissions of POPs, are effective. There are different ways of performing observation programs but marine mussels, as filtering organisms, have proven to be useful for biomonitoring and assessment of the current state of a site. In our study, we have undertaken the retrospective analysis of ''classic'' and ''novel'' persistent organic contaminants in the archived samples of marine mussels (Mytilus edulis) collected over the past 22

  15. [Decontamination of organophosphorus compounds: Towards new alternatives].

    Poirier, L; Jacquet, P; Elias, M; Daudé, D; Chabrière, E

    2017-05-01

    Organophosphorus coumpounds (OP) are toxic chemicals mainly used for agricultural purpose such as insecticides and were also developed and used as warfare nerve agents. OP are inhibitors of acetylcholinesterase, a key enzyme involved in the regulation of the central nervous system. Chemical, physical and biological approaches have been considered to decontaminate OP. This review summarizes the current and emerging strategies that are investigated to tackle this issue with a special emphasis on enzymatic remediation methods. During the last decade, many studies have been dedicated to the development of biocatalysts for OP removal. Among these, recent reports have pointed out the promising enzyme SsoPox isolated from the archaea Sulfolobus solfataricus. Considering both its intrinsic stability and activity, this hyperthermostable enzyme is highly appealing for the decontamination of OP. Copyright © 2017 Académie Nationale de Pharmacie. All rights reserved.

  16. Seasonal variation in the levels of organohalogen compounds in herring (Clupea harengus) from the Norwegian Sea.

    Frantzen, Sylvia; Måge, Amund; Iversen, Svein Arnholt; Julshamn, Kåre

    2011-09-01

    The Norwegian spring spawning (NSS) herring is an ecologically important fish stock in the Norwegian Sea, and with a catch volume exceeding one million tons a year it is also economically important and a valuable food source. In order to provide a baseline of the levels of contaminants in this fish stock, the levels of organohalogen compounds were determined in 800 individual herring sampled at 29 positions in the Norwegian Sea and off the coast of Norway. Due to seasonal migration, the herring were sampled where they were located during the different seasons. Concentrations of dioxins and dioxin-like PCBs, non-dioxin-like PCBs (PCB(7)) and PBDEs were determined in fillet samples of individual herring, and found to be relatively low, with means (min-max) of 0.77 (0.24-3.5) ng TEQ kg(-1) wet weight (ww), 5.0 (1.4-24) μg kg(-1) ww and 0.47 (0.091-3.1) μg kg(-1) ww, respectively. The concentrations varied throughout the year due to the feeding- and spawning cycle: Starved, pre-spawning herring caught off the Norwegian coast in January-February had the highest levels and those caught in the Norwegian Sea in April-June, after further starvation and spawning, had the lowest levels. These results show that the concentrations of organohalogen compounds in NSS herring are relatively low and closely tied to their physiological condition, and that in the future regular monitoring of NSS herring should be made in the spawning areas off the Norwegian coast in late winter. Copyright © 2011 Elsevier Ltd. All rights reserved.

  17. A New Approach on Estimation of Solubility and n-Octanol/ Water Partition Coefficient for Organohalogen Compounds

    Chenzhong Cao

    2008-06-01

    Full Text Available The aqueous solubility (logW and n-octanol/water partition coefficient (logPOW are important properties for pharmacology, toxicology and medicinal chemistry. Based on an understanding of the dissolution process, the frontier orbital interaction model was suggested in the present paper to describe the solvent-solute interactions of organohalogen compounds and a general three-parameter model was proposed to predict the aqueous solubility and n-octanol/water partition coefficient for the organohalogen compounds containing nonhydrogen-binding interactions. The model has satisfactory prediction accuracy. Furthermore, every item in the model has a very explicit meaning, which should be helpful to understand the structure-solubility relationship and may be provide a new view on estimation of solubility.

  18. Blood plasma clinical-chemical parameters as biomarker endpoints for organohalogen contaminant exposure in Norwegian raptor nestlings

    Sonne, Christian; Bustnes, Jan O.; Herzke, Dorte

    2012-01-01

    Raptors are exposed to biomagnifying and toxic organohalogenated compounds (OHCs) such as organochlorines, brominated flame retardants and perfluorinated compounds. To investigate how OHC exposure may affect biochemical pathways we collected blood plasma from Norwegian northern goshawk (n=56...... it is uncertain if such changes have any health effects. The OHC concentrations were below concentrations causing reproductive toxicity in adults of other raptor species but similar to those of concern for endocrine disruption of thyroid hormones in e.g., bald eagles....

  19. Biodegradation of organophosphorus pesticides by soil bacteria

    de Pasquale, C.; Fodale, R.; Lo Piccolo, L.; Palazzolo, E.; Alonzo, G.; Quatrini, P.

    2009-04-01

    A number of studies in the 1980s and 1990s showed that crop-protection products, applied to drained fields, could move downwards through the soil profile and to the groundwater. Organophosphorus insecticides (OPs) are used all over the world for crop protection, for other agricultural practices such as sheep dipping and, in aquaculture, for the control of sea lice. Ops besides showing a specific neurotoxicity and have also been related to various modern diseases, including Creutzfeldt-Jakob (CJD) and the Gulf War syndrome. Although OPs are less persistent than Organoclorine pesticides (OCs), they still constitute an environmental risks thus increasing the social concern about their levels in soils, surface waters, and ground waters. Degradation of OPs by microorganisms has been assessed for a few bacterial strains. In the present study the OPs degrading potential of indigenous soil microorganisms was investigated. Using enrichment cultures in which parathion was the only C and energy sources many bacterial strains were isolated from OPs contaminated and pristine agricultural soils characterized by different physico-chemical properties. More than 40 potential OPs degraders were isolated and grouped in operational taxonomic units (OTU) using analysis of polymorphism showed by the ribosomal internal transcribed spacer (ITS). Partial sequencing of 16S rRNA gene of representative isolates of each OTU revealed that most of them belong to Proteobacteria and Actinobacteria. All the analyzed soils showed the presence of putative OPs degraders: the highest diversity was found in organic cultivated soils, the lowest in chemically cultivated soils. Degradation of different OPs, characterized by different physical and chemical properties, was obtained by different selected representative strains using SPME GC-MS analysis on water and soil microcosms. The results showed that, after the incubation period, the amount of pesticide residues were in the range 20-80%. Some of the

  20. Organohalogen pollutants in herring from the northern Baltic Sea: Concentrations, congener profiles and explanatory factors

    Koistinen, Jaana; Kiviranta, Hannu; Ruokojaervi, Paeivi; Parmanne, Raimo; Verta, Matti; Hallikainen, Anja; Vartiainen, Terttu

    2008-01-01

    Organohalogen contaminants were investigated in Baltic herring caught from three catchment areas in the Baltic Sea, off the coasts of Finland. Pools of both small and large herring were analysed for polychlorinated biphenyls (PCB), dibenzo-p-dioxins, dibenzofurans, naphthalenes, camphenes (toxaphene), polybrominated diphenyl ethers and the pesticide DDT and its metabolites. PCB concentrations per fresh weight in small herring were at the same level in all catchment areas, i.e. the Bothnian Bay, the Bothnian Sea and the Gulf of Finland, revealing no hot spots and reflecting most likely long term emissions and atmospheric deposition. Differences in the levels and/or congener profiles of other contaminants between catchment areas may be explained by point sources. Similar concentrations in small and large herring in the Gulf of Finland were possibly due to their common nutrition. In the other areas, differences between small and large herring most likely reflected their different food sources. - Sources of pollutants are reflected in levels and congener profiles of pollutants in Baltic herring

  1. Absorption of decabromodiphenyl ether and other organohalogen chemicals by grey seals (Halichoerus grypus)

    Thomas, Gareth O.; Moss, Simon E.W.; Asplund, Lillemor; Hall, Ailsa J.

    2005-01-01

    An input-output balance study was performed for polybrominated diphenyl ethers, polychlorinated biphenyls and some organochlorine pesticides on three captive, juvenile grey seals (Halichoerus grypus). The animals were fed a diet of herring for six months, during the last three months of which this study was performed. A supplement of decabromodiphenyl ether was included in the diet during the second month of the study. Consistently high absorption (>89%) was observed for all of the chemicals studied, whereas work on other animals has generally shown high (>80%) net absorption at log K OW OW , and very low absorption of decabromodiphenyl ether. The half-life of decabromodiphenyl ether in blood was estimated to be between 8.5 and 13 days. Measurable concentrations of decabromodiphenyl ether were detected in seal blubber at the end of the study, indicating that this chemical can be stored in adipose and may bioaccumulate. Current understanding of the mechanism of absorption of organohalogen chemicals and the potential for accumulation of decabromodiphenyl ether will need reassessing in the light of these results. - Decabromodiphenyl ether is absorbed effectively from the diet by grey seals, and can be stored in the blubber even after exposure ceases

  2. Legacy and emerging organohalogenated contaminants in wild edible aquatic organisms: Implications for bioaccumulation and human exposure.

    Sun, Runxia; Luo, Xiaojun; Li, Qing X; Wang, Tao; Zheng, Xiaobo; Peng, Pingan; Mai, Bixian

    2018-03-01

    Highly industrialized and urbanized watersheds may receive various contaminants from anthropogenic activities. In this study, legacy and emerging organohalogenated contaminants (OHCs) were measured in edible wild aquatic organisms sampled from the Pearl River and Dongjiang River in a representative industrial and urban region in China. High concentrations of target contaminants were observed. The Pearl River exhibited higher concentrations of OHCs than the Dongjiang River due to high industrialization and urbanization. Agrochemical inputs remained an important source of OHCs in industrialized and urbanized watershed in China, but vigilance is needed for recent inputs of polychlorinated biphenyls (PCBs) originated from e-waste recycling activities. Bioaccumulation of dichlorodiphenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexanes (HCHs), PCBs, polybrominated diphenyl ethers (PBDEs), and Dechlorane Plus (DP) was biological species- and compound-specific, which can be largely attributed to metabolic capability for xenobiotics. No health risk was related to the daily intake of DDTs, HCHs, and PBDEs via consumption of wild edible species investigated for local residents. However, the current exposure to PCBs through consuming fish is of potential health concern. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Organohalogen body burdens in a breast cancer case-control study

    Petreas, M.; She, J.; Visita, P.; Winkler, J. [Hazardous Materials Lab., California Dept. of Toxic Substances Control, Berkeley, CA (United States); Hurley, S.; Smith, D.; Reynolds, P. [Environmental Health Investigations Branch, California Dept. of Health Services, Oakland, CA (United States); Jeffrey, S.; Mahoney, E. [Dept. of Surgery, Stanford Univ. School of Medicine, Stanford, CA (United States)

    2004-09-15

    Due to their lipophilic properties, dioxins (PCDD/PCDFs) and other organohalogen compounds bioaccumulate in the food chain, with diet accounting for over 90% of non-occupational exposures. To date, few epidemiologic studies have examined the relationship between dioxins and breast cancer in human populations. Most have examined risks in occupational cohorts or in populations exposed to dioxins from the Seveso accident6-8. Results from these studies have been conflicting and have largely been limited by a lack of individual-level measures of exposure, small numbers of cases, and inability to account for established breast cancer risk factors. Very little is known about the potential health effects of low-level environmental dioxin contamination. We present data on PCDD/PCDFs, organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) in adipose tissues of women participating in a breast cancer case-control study centered in the San Francisco Bay Area. In addition, we examine distributions of these chemicals in breast and abdominal adipose of women undergoing mastectomies with concurrent breast reconstruction. If concentrations were equivalent, use of abdominal adipose would greatly enhance the pool for controls for future epidemiological studies.

  4. Organohalogen compounds in human breast milk from Republic of Buryatia, Russia

    Tsydenova, Oyuna V. [Center for Marine Environmental Studies (CMES), Ehime University, Bunkyo-cho 2-5, Matsuyama 790-8577 (Japan); Sudaryanto, Agus [Center for Marine Environmental Studies (CMES), Ehime University, Bunkyo-cho 2-5, Matsuyama 790-8577 (Japan); Kajiwara, Natsuko [Center for Marine Environmental Studies (CMES), Ehime University, Bunkyo-cho 2-5, Matsuyama 790-8577 (Japan); Kunisue, Tatsuya [Center for Marine Environmental Studies (CMES), Ehime University, Bunkyo-cho 2-5, Matsuyama 790-8577 (Japan); Batoev, Valeriy B. [Baikal Institute of Nature Management, Siberian Branch of Russian Academy of Sciences, Sakhyanova st. 6, Ulan-Ude 670047 (Russian Federation); Tanabe, Shinsuke [Center for Marine Environmental Studies (CMES), Ehime University, Bunkyo-cho 2-5, Matsuyama 790-8577 (Japan)]. E-mail: shinsuke@agr.ehime-u.ac.jp

    2007-03-15

    Human breast milk samples collected during 2003/04 in Buryatia, a Russian autonomous republic, were analyzed in order to assess human exposure to organohalogen compounds including organochlorine pesticides, polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). When compared with available worldwide data, levels of HCB (23-880 ng/g lipid wt.), PCBs (69-680 ng/g lipid wt.), and HCHs (100-3700 ng/g lipid wt.) were relatively high, indicating elevated human exposure to these organochlorines (OCs) in Buryatia. In contrast to OCs, PBDE concentrations were low (0.46-1.7 ng/g lipid wt.). Out of 14 BDE congeners analyzed, BDE-28, BDE-47, BDE-100, BDE-153, BDE-197, and BDE-207 were detected. Estimated daily intakes (EDIs) of HCHs, HCB, CHLs, and PCBs by infants solely from human milk for 100%, 43%, 34%, and 17% of the samples, respectively, exceeded guideline thresholds. Although high EDIs raise concern for possible toxic effects of OCs, women in Buryatia are recommended to breastfeed due to numerous advantages of breastfeeding for mother and child. - People in the Republic of Buryatia, Russia are exposed to relatively high levels of HCHs, HCB and PCBs.

  5. Organohalogen compounds in human breast milk from Republic of Buryatia, Russia

    Tsydenova, Oyuna V.; Sudaryanto, Agus; Kajiwara, Natsuko; Kunisue, Tatsuya; Batoev, Valeriy B.; Tanabe, Shinsuke

    2007-01-01

    Human breast milk samples collected during 2003/04 in Buryatia, a Russian autonomous republic, were analyzed in order to assess human exposure to organohalogen compounds including organochlorine pesticides, polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). When compared with available worldwide data, levels of HCB (23-880 ng/g lipid wt.), PCBs (69-680 ng/g lipid wt.), and HCHs (100-3700 ng/g lipid wt.) were relatively high, indicating elevated human exposure to these organochlorines (OCs) in Buryatia. In contrast to OCs, PBDE concentrations were low (0.46-1.7 ng/g lipid wt.). Out of 14 BDE congeners analyzed, BDE-28, BDE-47, BDE-100, BDE-153, BDE-197, and BDE-207 were detected. Estimated daily intakes (EDIs) of HCHs, HCB, CHLs, and PCBs by infants solely from human milk for 100%, 43%, 34%, and 17% of the samples, respectively, exceeded guideline thresholds. Although high EDIs raise concern for possible toxic effects of OCs, women in Buryatia are recommended to breastfeed due to numerous advantages of breastfeeding for mother and child. - People in the Republic of Buryatia, Russia are exposed to relatively high levels of HCHs, HCB and PCBs

  6. Study of Serum Amylase and Serum Cholinesterase in Organophosphorus Poisoning

    Sharan Badiger

    2016-04-01

    Full Text Available Background: Poisoning due to organophosphorus compounds is most commonly seen. Earlier plasma cholinesterase level was used to assess the severity of poisoning. Presently serum amylase is being recommended as a better indicator of severity. Aims and Objectives: To study plasma cholinesterase and serum amylase levels in acute organophosphorus and to correlate serum amylase levels with clinical severity and outcome. Material and Methods: A total of 80 patients in the study admitted to a tertiary care centre within 24 hours with a history of organophosphorus poisoning were included in study. Estimation of plasma cholinesterase and serum rd amylase was done at the time of admission, and on 3 th day and on 5 day. Results: Occurrence of organophosphorus poisoning was more common among age group 21-30 years and among males (57.5%. They were 25 (31.2% farmers, 23 (28.8% st u d e n ts, a n d 2 2 ( 2 7 . 5% h o u s ewi v e s. Monocrotophos (45.0% was commonly used compound. Mean value of plasma cholinesterase and serum amylase at admission are 3693 U/L, and 185.4 U/L. There was significant inhibition of plasma cholinesterase and elevation of serum amylase at th admission with return to normal values on 5 day. Conclusion: Plasma cholinesterase inhibition 200 U/L has been associated with poor prognosis and proneness to respiratory failure.

  7. Acute organophosphorus compound poisoning in cattle: A case report

    A case of an acute organophosphorus compound, GOLDFLEECE poisoning involving 39 cattle at Abubakar Tafawa Balewa University, Bauchi is reported. The animals were overexposed to the compound following routine tick spray. Within 15 minutes after the spray of the compound, 26 animals were recumbent showing ...

  8. Acute organo-phosphorus pesticide poisoning in North Karnataka ...

    Background: Pesticide poisoning is an important cause of morbidity and mortality in India. Objectives: To assess the oxidative damage, hemoglobin level and leukocyte count in acute organophosphorus pesticide poisoning. Methods: Plasma cholinesterase was assessed as a toxicity marker. Oxidative damage was ...

  9. Altered vitamin D status in liver tissue and blood plasma from Greenland sledge dogs (Canis familiaris) dietary exposed to organohalogen contaminated minke whale (Balaenoptera acuterostrata) blubber

    Sonne, Christian; Kirkegaard, Maja; Jakobsen, Jette

    2014-01-01

    This study compared vitamin D3 (vitD3) and 25-OH vitamin D3 (25OHD3) status in Greenland sledge dogs (Canis familiaris) given either minke whale (Balaenoptera acuterostrata) blubber high in organohalogen contaminants (OHCs) or clean porcine (Suis scrofa) fat for up to 636 days. A group of six...

  10. A screening of persistent organohalogenated contaminants in hair of East Greenland polar bears.

    Jaspers, Veerle L B; Dietz, Rune; Sonne, Christian; Letcher, Robert J; Eens, Marcel; Neels, Hugo; Born, Erik W; Covaci, Adrian

    2010-10-15

    In this pilot study, we report on levels of persistent organohalogenated contaminants (OHCs) in hair of polar bears (Ursus maritimus) from East Greenland sampled between 1999 and 2001. To our knowledge, this is the first study on the validation of polar bear hair as a non-invasive matrix representative of concentrations and profiles in internal organs and blood plasma. Because of low sample weights (13-140mg), only major bioaccumulative OHCs were detected above the limit of quantification: five polychlorinated biphenyl (PCB) congeners (CB 99, 138, 153, 170 and 180), one polybrominated diphenyl ether (PBDE) congener (BDE 47), oxychlordane, trans-nonachlor and β-hexachlorocyclohexane. The PCB profile in hair was similar to that of internal tissues (i.e. adipose, liver, brain and blood), with CB 153 and 180 as the major congeners in all matrices. A gender difference was found for concentrations in hair relative to concentrations in internal tissues. Females (n=6) were found to display negative correlations, while males (n=5) showed positive correlations, although p-values were not found significant. These negative correlations in females may reflect seasonal OHC mobilisation from periphery adipose tissue due to, for example, lactation and fasting. The lack of significance in most correlations may be due to small sample sizes and seasonal variability of concentrations in soft tissues. Further research with larger sample weights and sizes is therefore necessary to draw more definitive conclusions on the usefulness of hair for biomonitoring OHCs in polar bears and other fur mammals. Copyright © 2010 Elsevier B.V. All rights reserved.

  11. Bioaccumulation of organohalogenated compounds in sharks and rays from the southeastern USA.

    Weijs, Liesbeth; Briels, Nathalie; Adams, Douglas H; Lepoint, Gilles; Das, Krishna; Blust, Ronny; Covaci, Adrian

    2015-02-01

    Organohalogenated compounds are widespread in the marine environment and can be a serious threat to organisms in all levels of aquatic food webs, including elasmobranch species. Information about the concentrations of POPs (persistent organic pollutants) and of MeO-PBDEs (methoxylated polybrominated diphenyl ethers) in elasmobranchs is scarce and potential toxic effects are poorly understood. The aims of the present study were therefore to investigate the occurrence of multiple POP classes (PCBs, PBDEs, DDXs, HCB, CHLs) and of MeO-PBDEs in various elasmobranch species from different trophic levels in estuarine and marine waters of the southeastern United States. Overall, levels and patterns of PCBs, PBDEs, DDXs, HCB, CHLs and of MeO-PBDEs varied according to the species, maturity stage, gender and habitat type. The lowest levels of POPs were found in Atlantic stingrays and the highest levels were found in bull sharks. As both species are respectively near the bottom and at top of the trophic web, with juvenile bull sharks frequently feeding on Atlantic stingrays, these findings further suggest a bioaccumulation and biomagnification process with trophic position. MeO-PBDEs were not detected in Atlantic stingrays, but were found in all shark species. HCB was not found in Atlantic stingrays, bonnetheads or lemon sharks, but was detected in the majority of bull sharks examined. Comparison with previous studies suggests that Atlantic stingrays may be experiencing toxic effects of PCBs and DDXs on their immune system. However, the effect of these compounds on the health of shark species remains unclear. Copyright © 2014 Elsevier Inc. All rights reserved.

  12. Denaturation/Renaturation of Organophosphorus Acid Anhydrolase (OPAA) Using Guanidinium Hydrochloride and Urea

    Ong, K. K; Sun, Z; Cheng, T. C; Wei, Y; Yuan, J. M; Yin, R

    2004-01-01

    .... Using organophosphorus acid anhydrolase (OPAA) as the model protein, a guanidinium hydrochloride and urea denaturation/renaturation study was conducted and measured both optically and enzymatically...

  13. Organophosphorus pentavalent compounds: history, synthetic methods of preparation and application as insecticides and antitumor agents

    Santos, Viviane Martins Rebello dos; Donnici, Claudio Luis; DaCosta, Joao Batista Neves; Caixeiro, Janaina Marques Rodrigues

    2007-01-01

    This paper is a review of the history, synthesis and application of organophosphorus compounds, especially of those of pentavalent phosphorus, such as phosphoramidates, phosphorothioates, phosphonates and phosphonic acids with insecticide and anticancer activities. The organophosphorus compounds with agrochemical applications show great structural variety, They include not only insecticides, but also fungicides, herbicides, and others. The large variety of commercially available organophosphorus pesticides is remarkable. Even more interesting is the high efficiency of some organophosphorus compounds as anticancer agents such as cyclophosphamide and its derivatives. (author)

  14. Temporal variation and biomagnification of organohalogen compounds in finless porpoises (Neophocaena phocaenoides) from the South China Sea

    Ramu, Karri; Kajiwara, Natsuko; Lam, Paul K.S.; Jefferson, Thomas A.; Zhou Kaiya; Tanabe, Shinsuke

    2006-01-01

    Polybrominated diphenyl ethers (PBDEs) and organochlorine compounds (OCs) were determined in the blubber of male finless porpoises (Neophocaena phocaenoides) collected in 1990 and 2000/01 from the South China Sea. Among the organohalogen compounds analyzed, DDTs and PCBs were the predominant contaminants in the porpoises, ranging from 26,000 to 260,000 and 1400 to 28,000 ng/g lipid wt., respectively. PBDEs ranged from a minimum of 84 ng/g lipid wt., in 1990 to a maximum of 980 ng/g lipid wt., in 2001, showing a significant increase during the time period investigated. Congener profiles in finless porpoises did not shift to higher BDE congeners during these years, implying a continuous discharge of lower BDE commercial mixtures, such as PentaBDE. For OCs, HCHs concentrations decreased significantly, while others did not exhibit any significant temporal variation. Biomagnification factors (BMFs) were found to be highest for CHLs and lowest for HCB. PBDEs and PCBs had comparable BMFs, indicating a similar potential for biomagnification through the food web. - Levels and temporal variations of organohalogen contaminants in the South China Sea

  15. Biodegradation and Utilization of Organophosphorus Pesticide Malathion by Cyanobacteria

    Wael M. Ibrahim

    2014-01-01

    Full Text Available Three strains of filamentous Cyanobacteria were used to study their growth and utilization of organophosphorus pesticide malathion. A sharp decrease in the growth of the algal strains was observed by increasing the concentration of malathion. Amongst them Nostoc muscorum tolerated different concentrations and was recorded as the highest efficient strain for biodegradation (91% of this compound. Moreover, carbohydrate and protein content of their cells overtopped the other strains especially at higher concentrations. The algal strains were further subjected to grow under P-limitation in absence and presence of malathion. Although, the algal growth under P-limitation recorded a very poor level, a massive enhanced growth and phosphorous content of cells were obtained when the P-limited medium was amended with malathion. This study clarified that N. muscorum with its capability to utilize malathion as a sole phosphorous source is considered as an inexpensive and efficient biotechnology for remediation of organophosphorus pesticide from contaminated wastewater.

  16. Acute organophosphorus poisoning complicated by acute coronary syndrome.

    Pankaj, Madhu; Krishna, Kavita

    2014-07-01

    We report a case of 30 year old alcoholic male admitted with vomiting, drowsiness, limb weakness and fasciculations after alleged history of consumption of 30 ml of chlorpyriphos insecticide. He had low serum cholinesterase levels. With standard treatment for organophosphorus poisoning (OPP), he improved gradually until day 5, when he developed neck and limb weakness and respiratory distress. This intermediate syndrome was treated with oximes, atropine and artificial ventilation. During treatment, his ECG showed fresh changes of ST elevation. High CPK & CPK-MB levels, septal hypokinesia on 2D echo suggested acute coronary syndrome. Coronary angiography was postponed due to his bedridden and obtunded status. The patient finally recovered fully by day 15 and was discharged. Acute coronary syndrome is a rare occurrence in OP poisoning. The present case thus emphasises the need for careful electrocardiographic and enzymatic monitoring of all patients of organophosphorus poisoning to prevent potential cardiac complication which can prove fatal.

  17. Novel organophosphorus compounds; synthesis, spectroscopy and X-ray crystallography

    Shariatinia, Z.; Sohrabi, M.; Yousefi, M.; Kovaľ, Tomáš; Dušek, Michal

    2012-01-01

    Roč. 11, č. 2 (2012), s. 125-133 ISSN 1024-1221 Grant - others:AV ČR(CZ) AP0701 Program:Akademická prémie - Praemium Academiae Institutional research plan: CEZ:AV0Z10100521 Keywords : organophosphorus compounds * NMR * X-ray crystallography * hydrogen bond Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.686, year: 2012

  18. The application of green chemistry methods in organophosphorus synthesis

    Odinets, Irina L; Matveeva, E V

    2012-01-01

    Data concerning the synthesis of organophosphorus compounds in ionic liquids, in water and under solvent-free conditions are considered and summarized. It is shown that this strategy, which complies with the definition of green chemistry, has advantages in terms of the rate of the process and the yields of target products as compared with syntheses in common organic solvents. The Wittig, Horner–Wadsworth–Emmons, Kabachnik–Fields, Arbuzov and Michaelis reactions are considered as examples. The bibliography includes 178 references.

  19. Rapid biodegradation of organophosphorus pesticides by Stenotrophomonas sp. G1

    Deng, Shuyan; Chen, Yao; Wang, Daosheng; Shi, Taozhong; Wu, Xiangwei; Ma, Xin; Li, Xiangqiong; Hua, Rimao; Tang, Xinyun; Li, Qing X.

    2015-01-01

    Highlights: • Stenotrophomonas sp. G1 was isolated from chlorpyrifos contaminated sludge. • Strain G1 is closest to Stenotrophomonas acidaminiphila. • Strain G1 can efficiently degrade 8 organophosphorus pesticides (OPs). • Intracellular methyl parathion hydrolase is responsible for the OP degradation. • Three factors were orthogonally optimized for degradation of methyl parathion. - Abstract: Organophosphorus insecticides have been widely used, which are highly poisonous and cause serious concerns over food safety and environmental pollution. A bacterial strain being capable of degrading O,O-dialkyl phosphorothioate and O,O-dialkyl phosphate insecticides, designated as G1, was isolated from sludge collected at the drain outlet of a chlorpyrifos manufacture plant. Physiological and biochemical characteristics and 16S rDNA gene sequence analysis suggested that strain G1 belongs to the genus Stenotrophomonas. At an initial concentration of 50 mg/L, strain G1 degraded 100% of methyl parathion, methyl paraoxon, diazinon, and phoxim, 95% of parathion, 63% of chlorpyrifos, 38% of profenofos, and 34% of triazophos in 24 h. Orthogonal experiments showed that the optimum conditions were an inoculum volume of 20% (v/v), a substrate concentration of 50 mg/L, and an incubation temperature in 40 °C. p-Nitrophenol was detected as the metabolite of methyl parathion, for which intracellular methyl parathion hydrolase was responsible. Strain G1 can efficiently degrade eight organophosphorus pesticides (OPs) and is a very excellent candidate for applications in OP pollution remediation

  20. Rapid biodegradation of organophosphorus pesticides by Stenotrophomonas sp. G1

    Deng, Shuyan; Chen, Yao [Key Laboratory of Agri-food Safety of Anhui Province, Lab of Quality & Safety and Risk Assessment for Agro-products on Storage and Preservation (Hefei), Ministry of Agriculture, School of Resource and Environment, Anhui Agricultural University, Hefei 230036 (China); Wang, Daosheng [School of Life Science, Anhui Agricultural University, Hefei 230036 (China); Shi, Taozhong; Wu, Xiangwei; Ma, Xin; Li, Xiangqiong [Key Laboratory of Agri-food Safety of Anhui Province, Lab of Quality & Safety and Risk Assessment for Agro-products on Storage and Preservation (Hefei), Ministry of Agriculture, School of Resource and Environment, Anhui Agricultural University, Hefei 230036 (China); Hua, Rimao, E-mail: rimaohua@ahau.edu.cn [Key Laboratory of Agri-food Safety of Anhui Province, Lab of Quality & Safety and Risk Assessment for Agro-products on Storage and Preservation (Hefei), Ministry of Agriculture, School of Resource and Environment, Anhui Agricultural University, Hefei 230036 (China); Tang, Xinyun [School of Life Science, Anhui Agricultural University, Hefei 230036 (China); Li, Qing X. [Department of Molecular Biosciences and Bioengineering, University of Hawaii at Manoa, 1955 East–West Road, Honolulu, HI 957822 (United States)

    2015-10-30

    Highlights: • Stenotrophomonas sp. G1 was isolated from chlorpyrifos contaminated sludge. • Strain G1 is closest to Stenotrophomonas acidaminiphila. • Strain G1 can efficiently degrade 8 organophosphorus pesticides (OPs). • Intracellular methyl parathion hydrolase is responsible for the OP degradation. • Three factors were orthogonally optimized for degradation of methyl parathion. - Abstract: Organophosphorus insecticides have been widely used, which are highly poisonous and cause serious concerns over food safety and environmental pollution. A bacterial strain being capable of degrading O,O-dialkyl phosphorothioate and O,O-dialkyl phosphate insecticides, designated as G1, was isolated from sludge collected at the drain outlet of a chlorpyrifos manufacture plant. Physiological and biochemical characteristics and 16S rDNA gene sequence analysis suggested that strain G1 belongs to the genus Stenotrophomonas. At an initial concentration of 50 mg/L, strain G1 degraded 100% of methyl parathion, methyl paraoxon, diazinon, and phoxim, 95% of parathion, 63% of chlorpyrifos, 38% of profenofos, and 34% of triazophos in 24 h. Orthogonal experiments showed that the optimum conditions were an inoculum volume of 20% (v/v), a substrate concentration of 50 mg/L, and an incubation temperature in 40 °C. p-Nitrophenol was detected as the metabolite of methyl parathion, for which intracellular methyl parathion hydrolase was responsible. Strain G1 can efficiently degrade eight organophosphorus pesticides (OPs) and is a very excellent candidate for applications in OP pollution remediation.

  1. Alterations in thyroid hormone status in Greenland sledge dogs exposed to whale blubber contaminated with organohalogen compounds

    Kirkegaard, Maja; Sonne, Christian; Dietz, Rune

    2011-01-01

    As a model of high trophic level carnivores, sledge dogs were fed from 2 to 18 months of age with minke whale blubber containing organohalogen compounds (OHC) corresponding to 128µg PCB/day. Controls were fed uncontaminated porcine fat. Thyroid hormone levels were assessed in 7 exposed and 7...... control sister bitches (sampled at age 6-18 months) and 4 exposed and 4 control pups, fed the same diet as their mothers (sampled age 3-12 months). Lower free and total T3 and T4 were seen in exposed vs. control bitches beyond 10 months of age, and total T3 was lower through 3-12 months of age in exposed...

  2. The brain imaging study of the organophosphorus pesticides poisoning

    Yang Yanmei; Liu Huaijun; Li Shuling; Wang Yongsheng; Huang Boyuan; Chi Cen; Shi Zhenyang; Cui Caixia; Zhou Lixia; Liu Runtian

    2004-01-01

    Objective: To summarize the CT and MR imaging findings in acute organophosphorus pesticides poisoning patients, and to improve the early diagnostic ability. Methods: The imaging of 34 patients of organophosphorus pesticides poisoning was analyzed, the poisons were all taken orally. The pesticides included methamidophos (12 cases), omethoate (15 cases), DDV (3 cases), and methylparathion (4 cases). According to the diagnosis and classification diagnosis criterion of acute organophosphorus pesticides poisoning, the patients were divided into two groups: mild or moderate grade group (24 cases) and severe grade group (10 cases). The relationship between the clinic grade and CT and MRI findings was studied. Results: in the severe grade group, 4 patients showed brain edema, presenting as sulcus and fissure flattened or disappeared, and ventricles and cisterns narrowed or closed 2-3 days after poisoning. In 3 patients 3 days to 3 months after poisoning, bilateral basal ganglion and cerebral cortex showed prolonged T 1 and T 2 signals, and high signal intensity was detected on FLAIR, and bilateral basal ganglion low density was revealed on CT. T 1 relaxation was shortened, T 2 WI and FLAIR imaging showed high signal intensity in 1 patient. The imaging of 1 patient 6 months after poisoning showed the cerebral sulcus, fissure and ventricle were enlarged. CT and MRI in the mild or moderate group were normal. By the Fisher's exact probabilities test, the imaging exhibition difference between the severe grade and mild or moderate grade patients was significant. Conclusion: The CT and MRI can reflect the brain injury after poisoning, and the imaging exhibitions were various. The imaging information can provide credible foundation for the therapy for lightening the brain edema and nourishing the brain cell

  3. Multifunctional organophosphorus extractants: a status report on development and applications

    Schulz, W.W.; Horwitz, E.P.

    1988-01-01

    Up-to-date state of the development of science and technology of multifunctional organophosphorus extractants is considered. The detailed classification of these extractants is presented. They attracted pasticular interest because of affinity of some bifunctional phosphonates, phosphine oxides, carbamoylalkylphosphonates to trivalent Am, tetravalent and hexavalent actinides, trivalent lanthanides in strong mineral acids, and because of ability of some alkylpyrophosphoric acids to extract effectively U(4) from concentrated solutions of phosphoric acid. Application of these extractants for analytic purposes and in the field of nuclear technology is considered

  4. [Meta-analysis of association between organophosphorus pesticides and aplastic anemia].

    Zhang, Ji; Yang, Tubao

    2015-09-01

    To evaluate the association between organophosphorus pesticides and aplastic anemia, and provide scientific evidence for the primary prevention of aplastic anemia. The published papers of case control studies on the association between organophosphorus pesticides and aplastic anemia from January 1990 to August 2014 were collected from Chinese BioMedical Literature Base (CBM), Chinese National Knowledge Infrastructure (CNKI), PubMed and EMBASE. The papers which met the inclusion criteria were evaluated. The pooled odds ratios (OR) and 95% confidence interval (CI) of organophosphorus pesticides were calculated with software Review Manager 5.0. Subgroup analysis were conducted for different population and different usage of organophosphorus pesticides. A total of 9 papers were selected, involving 5 833 subjects (1 404 cases and 4 429 controls). The results showed that organophosphorus pesticides could increase the risk of aplastic anemia (OR=1.97, 95% CI: 1.60-2.44) . Subgroup analysis showed that Asian (OR=2.01, 95% CI: 1.52-2.66) had higher risk of aplastic anemia than American or European (OR=1.93, 95% CI: 1.39-2.67) . Using pure organophosphorus pesticides (OR=2.15, 95% CI: 1.60-2.88) was more prone to cause aplastic anemia than using the mixture of organophosphorus pesticides (OR=1.82, 95% CI: 1.34-2.47). The analysis indicated that organophosphorus pesticides might be a risk factor for aplastic anemia. Reducing organophosphorus pesticides exposure in daily life and industrial or agricultural production could prevent the incidence of aplastic anemia.

  5. Acute myocardial infarction: Can it be a complication of acute organophosphorus compound poisoning?

    P Joshi

    2013-01-01

    Full Text Available Organophosphorus compounds are used as pesticides and represent a common cause of poisoning in developing countries including India due to their widespread availability and use. Toxicity due to these agents can affect many organs including heart. Here, we report a case of acute organophosphorus poisoning (parathion, followed by acute myocardial infarction; documented by clinical features, electrocardiographic changes, and elevated cardiac enzymes. Myocardial infarction has been rarely reported with organophosphorus compounds exposure, thus awareness of this complication can reduce morbidity and mortality.

  6. Levels of organophosphorus pesticides in medicinal plants commonly consumed in Iran

    Sarkhail Parisa

    2012-08-01

    Full Text Available Abstract The frequent occurrence of pesticide residues in herbal materials was indicated by previous studies. In this study, the concentration of some of the organophosphorus pesticides including parathion, malathion, diazinon and pirimiphos methyl in different kinds of medicinal plants were determined. The samples were collected randomly from ten local markets of different areas of Iran. At the detection limit of 0.5 ng g-1, parathion and pirimiphos methyl were not detected in any of the samples. Some amounts of malathion and diazinon were found in Zataria, Matricaria chamomile, Spearmint and Cumin Seed samples while, the concentrations of target organophosphorus pesticides in Borage samples were below the detection limits of the methods which could be a result of intensive transformation of organophosphorus pesticides by Borage. In addition the organophosphorus pesticides were detected in all of the samples below the maximum residue levels (MRLs proposed by the international organizations.

  7. UPTAKE AND PHYTOTRANSFORMATION OF ORGANOPHOSPHORUS PESTICIDES BY AXENICALLY CULTIVATED AQUATIC PLANTS

    The uptake and phytotransformation of organophosphorus (OP) pesticides (malathion, demeton-S-methyl, and crufomate) was investigated in vitro using the axenically aquatic cultivated plants parrot feather (Myriophyllum aquaticum), duckweed (Spirodela oligorrhiza L.), and elodea (E...

  8. Surface Chemistry of Enzymes for Detection and Decontamination of Organophosphorus Compounds

    Leblanc, Roger

    2003-01-01

    ...), organophosphorus acid hydrolase (OPH), and covalent bonding of the enzyme onto the substrate. Results are encouraging and the studied enzymes form stable monolayers at the interface and can be transferred on to the solid substrate...

  9. Modulation of Immune Response by Organophosphorus Pesticides: Fishes as a Potential Model in Immunotoxicology

    Díaz-Resendiz, K. J. G.; Toledo-Ibarra, G. A.; Girón-Pérez, M. I.

    2015-01-01

    Immune response is modulated by different substances that are present in the environment. Nevertheless, some of these may cause an immunotoxic effect. In this paper, the effect of organophosphorus pesticides (frequent substances spilled in aquatic ecosystems) on the immune system of fishes and in immunotoxicology is reviewed. Furthermore, some cellular and molecular mechanisms that might be involved in immunoregulation mechanisms of organophosphorus pesticides are discussed. PMID:25973431

  10. Modulation of Immune Response by Organophosphorus Pesticides: Fishes as a Potential Model in Immunotoxicology

    K. J. G. Díaz-Resendiz

    2015-01-01

    Full Text Available Immune response is modulated by different substances that are present in the environment. Nevertheless, some of these may cause an immunotoxic effect. In this paper, the effect of organophosphorus pesticides (frequent substances spilled in aquatic ecosystems on the immune system of fishes and in immunotoxicology is reviewed. Furthermore, some cellular and molecular mechanisms that might be involved in immunoregulation mechanisms of organophosphorus pesticides are discussed.

  11. Exposure and effects assessment of persistent organohalogen contaminants in arctic wildlife and fish.

    Letcher, Robert J; Bustnes, Jan Ove; Dietz, Rune; Jenssen, Bjørn M; Jørgensen, Even H; Sonne, Christian; Verreault, Jonathan; Vijayan, Mathilakath M; Gabrielsen, Geir W

    2010-07-01

    Persistent organic pollutants (POPs) encompass an array of anthropogenic organic and elemental substances and their degradation and metabolic byproducts that have been found in the tissues of exposed animals, especially POPs categorized as organohalogen contaminants (OHCs). OHCs have been of concern in the circumpolar arctic for decades. For example, as a consequence of bioaccumulation and in some cases biomagnification of legacy (e.g., chlorinated PCBs, DDTs and CHLs) and emerging (e.g., brominated flame retardants (BFRs) and in particular polybrominated diphenyl ethers (PBDEs) and perfluorinated compounds (PFCs) including perfluorooctane sulfonate (PFOS) and perfluorooctanic acid (PFOA) found in Arctic biota and humans. Of high concern are the potential biological effects of these contaminants in exposed Arctic wildlife and fish. As concluded in the last review in 2004 for the Arctic Monitoring and Assessment Program (AMAP) on the effects of POPs in Arctic wildlife, prior to 1997, biological effects data were minimal and insufficient at any level of biological organization. The present review summarizes recent studies on biological effects in relation to OHC exposure, and attempts to assess known tissue/body compartment concentration data in the context of possible threshold levels of effects to evaluate the risks. This review concentrates mainly on post-2002, new OHC effects data in Arctic wildlife and fish, and is largely based on recently available effects data for populations of several top trophic level species, including seabirds (e.g., glaucous gull (Larus hyperboreus)), polar bears (Ursus maritimus), polar (Arctic) fox (Vulpes lagopus), and Arctic charr (Salvelinus alpinus), as well as semi-captive studies on sled dogs (Canis familiaris). Regardless, there remains a dearth of data on true contaminant exposure, cause-effect relationships with respect to these contaminant exposures in Arctic wildlife and fish. Indications of exposure effects are largely

  12. Persistent organohalogen contaminant burdens in Antarctic krill (Euphausia superba) from the eastern Antarctic sector: A baseline study

    Bengtson Nash, S.M.; Poulsen, A.H.; Kawaguchi, S.; Vetter, W.; Schlabach, M.

    2008-01-01

    A baseline for persistent organohalogen compound (POC) accumulation in the Antarctic keystone species, Antarctic krill (Euphausia superba) has been established for a 50 deg. longitudinal range of the eastern Antarctic sector. Samples of adult krill, caught from 12 sites distributed between 30 deg. and 80 deg. E (60-70 deg. S), were analysed for > 100 organohalogen compounds including chlorinated pesticides, polychlorinated biphenyls (PCBs), polybrominated organic compounds and polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs). Organochlorine pesticides dominated measured krill contaminant burdens with hexachlorobenzene (HCB) as the single most abundant compound quantified. Krill HCB concentrations were comparable to those detected at this trophic level in both the Arctic and temperate northwest Atlantic, lending support for the hypothesis that HCB will approach global equilibrium at a faster rate than other POCs. Para, para'-dichlorodiphenylethene (p,p'-DDE) was detected at notable concentrations. Measurements of DDT and its degradation products provide an important baseline for monitoring the temporal and geographical influence of renewed, DDT usage for malaria-control in affected southern hemisphere countries. In contrast to the Arctic, PCBs did not feature prominently in contaminant burdens of Antarctic krill. The major commercial polybrominated diphenyl ether (PBDE) congeners -99 and -47 were quantified at low background levels with clear concentration spikes observed at around 70 deg. E , in the vicinity of modern, active research stations. The likelihood that local anthropogenic activities are supplementing low PBDE levels, delivered otherwise primarily via long range environmental transport, is discussed. The suspected naturally occurring brominated organic compound, 2,4,6-tribromoanisole (TBA), was a ubiquitous contaminant in all samples whereas the only PCDD/Fs quantifiable were trace levels of octachlorodibenzo-p-dioxin (OCDD) and 1,2,3

  13. Organophosphorus flame retardants and plasticizers in the atmosphere of the North Sea

    Moeller, Axel; Xie Zhiyong; Caba, Armando; Sturm, Renate; Ebinghaus, Ralf

    2011-01-01

    Air samples collected in the German part of the North Sea from March to July 2010 were investigated for organophosphorus compounds (OPs) being applied as flame retardants and plasticizers. The Σ 8 OPs concentration ranged from 110 to 1400 pg m -3 while tris(2-chloroisopropyl) phosphate (TCPP) dominated all samples with individual concentrations up to 1200 pg m -3 . The highest concentrations were observed in continental air masses showing the high influence of industrialized regions including production sites on atmospheric emissions and concentrations. The occurrence of OPs even in oceanic/Arctic air masses shows that OPs can undergo long-range atmospheric transport. Dry particle-bound deposition fluxes from 9 to 240 ng m -2 d -1 for Σ 8 OPs were estimated leading to a minimum annual flux of 710 ± 580 kg y -1 OPs into the German North Sea. This study presents the first occurrence of OPs in the marine atmosphere together with important information on their long-range transport potential. - Highlights: → Organophosphorus flame retardants are detected for the first time in the marine atmosphere. → Organophosphorus compounds can undergo medium to long-range atmospheric transport. → Western Europe emits organophosphorus compounds to the marine atmosphere. → Marine air levels of organophosphorus flame retardants range up to 1 ng/m 3 . - Organophosphorus flame retardants, in particular tris(2-chloroisopropyl) phosphate, are emitted into the North Sea atmosphere by Western European countries.

  14. Determination of organophosphorus pesticide residues in tomatoes by gas chromatography

    Souissi, Sihem

    2010-01-01

    Chloropyriphos and malathion are two organophosphorus pesticides from many others pesticides widely used by famers in agriculture .Because of their bad effect on human health, officials standards are set by the international organisations and communities to ensure safer food for consumer .In the same way, scientists over the world are working hard to develop new detection techniques responding to the international requirements. In this study, an ' IAEA-ethylacetate method ', an adaptation of the popular QuEChERS multi residue method, was optimized to analyse chloropyriphos and Malathion residues in tomatoes .Ethyl-Acetate was used as an extraction solvent the PSA was kept for the clean up procedure. GC-NPD is used for samples analysis .The method optimized is specifique, selective with a recovery averaged more than 70 pour cent. A complete validation of the method is necessary to be used for routine analysis.

  15. Fluorescent Chemosensors for Toxic Organophosphorus Pesticides: A Review

    Kenneth Fletcher

    2010-07-01

    Full Text Available Many organophosphorus (OP based compounds are highly toxic and powerful inhibitors of cholinesterases that generate serious environmental and human health concerns. Organothiophosphates with a thiophosphoryl (P=S functional group constitute a broad class of these widely used pesticides. They are related to the more reactive phosphoryl (P=O organophosphates, which include very lethal nerve agents and chemical warfare agents, such as, VX, Soman and Sarin. Unfortunately, widespread and frequent commercial use of OP-based compounds in agricultural lands has resulted in their presence as residues in crops, livestock, and poultry products and also led to their migration into aquifers. Thus, the design of new sensors with improved analyte selectivity and sensitivity is of paramount importance in this area. Herein, we review recent advances in the development of fluorescent chemosensors for toxic OP pesticides and related compounds. We also discuss challenges and progress towards the design of future chemosensors with dual modes for signal transduction.

  16. Tissue-specific congener composition of organohalogen and metabolite contaminants in East Greenland polar bears (Ursus maritimus)

    Gebbink, Wouter A.; Sonne, Christian; Dietz, Rune; Kirkegaard, Maja; Riget, Frank F.; Born, Erik W.; Muir, Derek C.G.; Letcher, Robert J.

    2008-01-01

    Congener patterns of the major organohalogen contaminant classes of PCBs, PBDEs and their metabolites and/or by-products (OH-PCBs, MeSO 2 -PCBs, OH-PBDEs and MeO-PBDEs) were examined in adipose tissue, liver, brain and blood of East Greenland polar bears (Ursus maritimus). PCB, OH-PCB, MeSO 2 -PCB and PBDE congener patterns showed significant differences (p ≤ 0.05) mainly in the liver and the brain relative to the adipose tissue and the blood. OH-PBDEs and MeO-PBDEs were not detected in the brain and liver, but had different patterns in blood versus the adipose tissue. Novel OH-polybrominated biphenyls (OH-PBBs), one tri- and two tetra-brominated OH-PBBs were detected in all tissues and blood. Congener pattern differences among tissues and blood are likely due to a combination of factors, e.g., biotransformation and retention in the liver, retention in the blood and blood-brain barrier transport. Our findings suggest that different congener pattern exposures to these classes of contaminants should be considered with respect to potential target tissue-specific effects in East Greenland polar bears. - Tissues-specific (adipose tissue, liver, brain and blood) differences exist for the congener patterns of PCBs, PBDEs and their metabolites/degradation products in East Greenland polar bears

  17. Organohalogen contamination in breeding glaucous gulls from the Norwegian Arctic: Associations with basal metabolism and circulating thyroid hormones

    Verreault, Jonathan; Bech, Claus; Letcher, Robert J.; Ropstad, Erik; Dahl, Ellen; Gabrielsen, Geir W.

    2007-01-01

    Exposure to organohalogens in endotherms has been suggested to impose chemically induced stress by affecting functions related to maintenance energy requirements. Effects on basal metabolic rate (BMR) have been suggested to be, in part, mediated through interactions with the thyroid hormones (THs). We investigated the relationships between plasma concentrations of major organochlorines, PBDEs, hydroxylated (OH)- and methoxylated (MeO)-PBDEs and OH-PCBs, circulating TH levels and BMR in breeding glaucous gulls (Larus hyperboreus) from the Norwegian Arctic. Negative associations were found between BMR and concentrations of ΣPCB, ΣDDT and particularly Σchlordane, which combined made up 91% of the total contaminant burden. Levels of THs (thyroxine and triiodothyronine) were not associated significantly with variation of BMR or concentrations of any of the compounds determined. The present study suggests that BMR may be altered in glaucous gulls exposed to high loadings of persistent contaminants in the Norwegian Arctic environment. - Basal metabolic rate in glaucous gulls was negatively associated with plasma organochlorine concentrations, but not with circulating thyroid hormone levels

  18. Organohalogen compounds in blubber of Indo-Pacific bottlenose dolphin (Tursiops aduncus) and spinner dolphin (Stenella longirostris) from Zanzibar, Tanzania

    Mwevura, Haji, E-mail: mwevura@yahoo.co [Department of Chemistry, University of Dar es Salaam, Dar es Salaam (Tanzania, United Republic of); Amir, Omar A., E-mail: omar.amir@zoologi.su.s [Institute of Marine Sciences, University of Dar es Salaam, P O Box 668, Zanzibar (Tanzania, United Republic of); Department of Zoology, Stockholm University, SE-106 91 Stockholm (Sweden); Kishimba, Michael, E-mail: kishimba@chem.udsm.ac.t [Department of Chemistry, University of Dar es Salaam, Dar es Salaam (Tanzania, United Republic of); Berggren, Per, E-mail: per.berggren@zoologi.su.s [Department of Zoology, Stockholm University, SE-106 91 Stockholm (Sweden); School of Marine Science and Technology, University of Newcastle upon Tyne, NE1 7RU (United Kingdom); Kylin, Henrik, E-mail: henrik.kylin@vatten.slu.s [Department of Aquatic Sciences and Assessment, Swedish University of Agricultural Sciences, P O Box 7050, SE-750 07 Uppsala (Sweden); Norwegian Institute of Air Research, Polar Environmental Centre, NO-9296 Tromso (Norway)

    2010-06-15

    Blubber samples of Indo-Pacific bottlenose (Tursiops aduncus) and spinner (Stenella longirostris) dolphins from Zanzibar, East Africa, were analyzed for a wide range of organohalogen compounds. Methoxylated polybrominated diphenyl ethers (MeO-BDEs), presumably biogenic, were found at higher concentrations than anthropogenic organochlorine pesticides (OCPs). Only traces of industrial pollutants, such as polychlorinated biphenyls, were detected. The OCP levels found off Zanzibar were lower than those reported from other regions while MeO-BDE levels were higher. The relative composition of the OCPs indicated recent use of lindane (gamma-hexachlorocyclohexane) and aged residues of DDT and technical HCH. Placental transfer was estimated to 2.5% and 0.5% of the total burden of OCPs and MeO-BDEs, respectively. Overall transfer from mother to calf in Indo-Pacific bottlenose dolphins was estimated to 72% and 85% for the OCPs and MeO-BDEs burdens, respectively. Health effects of MeO-BDEs are not known, but structural similarities with well-known environmental toxins are cause for concern. - Biogenic brominated organic compounds were found at higher concentrations than anthropogenic organochlorine pesticides in dolphins off Zanzibar.

  19. Organohalogen compounds in blubber of Indo-Pacific bottlenose dolphin (Tursiops aduncus) and spinner dolphin (Stenella longirostris) from Zanzibar, Tanzania

    Mwevura, Haji; Amir, Omar A.; Kishimba, Michael; Berggren, Per; Kylin, Henrik

    2010-01-01

    Blubber samples of Indo-Pacific bottlenose (Tursiops aduncus) and spinner (Stenella longirostris) dolphins from Zanzibar, East Africa, were analyzed for a wide range of organohalogen compounds. Methoxylated polybrominated diphenyl ethers (MeO-BDEs), presumably biogenic, were found at higher concentrations than anthropogenic organochlorine pesticides (OCPs). Only traces of industrial pollutants, such as polychlorinated biphenyls, were detected. The OCP levels found off Zanzibar were lower than those reported from other regions while MeO-BDE levels were higher. The relative composition of the OCPs indicated recent use of lindane (γ-hexachlorocyclohexane) and aged residues of DDT and technical HCH. Placental transfer was estimated to 2.5% and 0.5% of the total burden of OCPs and MeO-BDEs, respectively. Overall transfer from mother to calf in Indo-Pacific bottlenose dolphins was estimated to 72% and 85% for the OCPs and MeO-BDEs burdens, respectively. Health effects of MeO-BDEs are not known, but structural similarities with well-known environmental toxins are cause for concern. - Biogenic brominated organic compounds were found at higher concentrations than anthropogenic organochlorine pesticides in dolphins off Zanzibar.

  20. Organohalogen contamination in breeding glaucous gulls from the Norwegian Arctic: Associations with basal metabolism and circulating thyroid hormones

    Verreault, Jonathan [Norwegian Polar Institute, Polar Environmental Centre, NO-9296 Tromso (Norway) and Department of Aquatic BioSciences, University of Tromso, NO-9037 Tromso (Norway)]. E-mail: jonathan@npolar.no; Bech, Claus [Department of Biology, Norwegian University of Science and Technology, NO-7491 Trondheim (Norway); Letcher, Robert J. [Environment Canada, Canadian Wildlife Service, National Wildlife Research Centre, Carleton University, Ottawa, ON K1A 0H3 (Canada); Ropstad, Erik [Department of Reproduction and Forensic Medicine, Norwegian School of Veterinary Science, P.O. Box 8146 Dep., NO-0033 Oslo (Norway); Dahl, Ellen [Department of Reproduction and Forensic Medicine, Norwegian School of Veterinary Science, P.O. Box 8146 Dep., NO-0033 Oslo (Norway); Gabrielsen, Geir W. [Norwegian Polar Institute, Polar Environmental Centre, NO-9296 Tromso (Norway)

    2007-01-15

    Exposure to organohalogens in endotherms has been suggested to impose chemically induced stress by affecting functions related to maintenance energy requirements. Effects on basal metabolic rate (BMR) have been suggested to be, in part, mediated through interactions with the thyroid hormones (THs). We investigated the relationships between plasma concentrations of major organochlorines, PBDEs, hydroxylated (OH)- and methoxylated (MeO)-PBDEs and OH-PCBs, circulating TH levels and BMR in breeding glaucous gulls (Larus hyperboreus) from the Norwegian Arctic. Negative associations were found between BMR and concentrations of {sigma}PCB, {sigma}DDT and particularly {sigma}chlordane, which combined made up 91% of the total contaminant burden. Levels of THs (thyroxine and triiodothyronine) were not associated significantly with variation of BMR or concentrations of any of the compounds determined. The present study suggests that BMR may be altered in glaucous gulls exposed to high loadings of persistent contaminants in the Norwegian Arctic environment. - Basal metabolic rate in glaucous gulls was negatively associated with plasma organochlorine concentrations, but not with circulating thyroid hormone levels.

  1. Organohalogen compounds in deep-sea fishes from the western North Pacific, off-Tohoku, Japan: Contamination status and bioaccumulation profiles

    Takahashi, Shin; Oshihoi, Tomoko; Ramu, Karri; Isobe, Tomohiko; Ohmori, Koji; Kubodera, Tsunemi; Tanabe, Shinsuke

    2010-01-01

    Twelve species of deep-sea fishes collected in 2005 from the western North Pacific, off-Tohoku, Japan were analyzed for organohalogen compounds. Among the compounds analyzed, concentrations of DDTs and PCBs (up to 23,000 and 12,400 ng/g lipid wt, respectively) were the highest. The present study is the foremost to report the occurrence of brominated flame retardants such as PBDEs and HBCDs in deep-sea organisms from the North Pacific region. Significant positive correlations found between δ 15 N ( per mille ) and PCBs, DDTs and PBDEs suggest the high biomagnification potential of these contaminants in food web. The large variation in δ 13 C ( per mille ) values observed between the species indicate multiple sources of carbon in the food web and specific accumulation of hydrophobic organohalogen compounds in benthic dwelling carnivore species like snubnosed eel. The results obtained in this study highlight the usefulness of deep-sea fishes as sentinel species to monitor the deep-sea environment.

  2. Altitudinal and thermal gradients of hepatic Cyp1A gene expression in natural populations of Salmo trutta from high mountain lakes and their correlation with organohalogen loads

    Jarque, Sergio; Gallego, Eva [Institute of Environmental Assessment and Water Research (IDAEA-CSIC), Jordi Girona 18, 08034-Barcelona, Catalonia (Spain); Bartrons, Mireia; Catalan, Jordi [Center for Advanced Studies of Blanes (CEAB-CSIC), Acces Cala St. Francesc 14, 17300-Blanes, Catalonia (Spain); Grimalt, Joan O. [Institute of Environmental Assessment and Water Research (IDAEA-CSIC), Jordi Girona 18, 08034-Barcelona, Catalonia (Spain); Pina, Benjamin, E-mail: bpcbmc@cid.csic.e [Institute of Environmental Assessment and Water Research (IDAEA-CSIC), Jordi Girona 18, 08034-Barcelona, Catalonia (Spain)

    2010-05-15

    The biomarker of xenobiotic exposure cytochrome p450A1 (Cyp1A) was used to analyze the biological response to chemical pollution in Salmo trutta (brown trout) from nine high mountain European lakes in Norway, Tatras, Tyrol, and central Pyrenees. Hepatic Cyp1A mRNA levels correlated both with the reciprocal of absolute annual average air temperatures of the sampled lakes and with muscle concentrations of several hydrophobic organohalogen compounds (OC), including chlorinated polychlorobiphenyls (PCB), DDE, and DDT. The correlation between Cyp1A expression and OC content was observed across the whole temperature range (between -0.7 deg. C and +6.2 deg. C), but also in the absence of any thermal gradient. We concluded that airborne pollutants accumulate in high mountain lake fish at concentrations high enough to increase Cyp1A expression, among other possible effects. As geographical distribution of semi-volatile OC is strongly influenced by air temperatures, future climate modifications will potentially enhance their physiological effects in lake ecosystems. - Altitudinal gradients of hepatic Cyp1A gene expression in mountain trout correlate with geographic and individual organohalogen distribution.

  3. Organohalogen contaminants and metabolites in cerebrospinal fluid and cerebellum gray matter in short-beaked common dolphins and Atlantic white-sided dolphins from the western North Atlantic

    Montie, Eric W.; Reddy, Christopher M.; Gebbink, Wouter A.; Touhey, Katie E.; Hahn, Mark E.; Letcher, Robert J.

    2009-01-01

    Concentrations of several congeners and classes of organohalogen contaminants (OHCs) and/or their metabolites, namely organochlorine pesticides (OCs), polychlorinated biphenyls (PCBs), hydroxylated-PCBs (OH-PCBs), methylsulfonyl-PCBs (MeSO 2 -PCBs), polybrominated diphenyl ether (PBDE) flame retardants, and OH-PBDEs, were measured in cerebrospinal fluid (CSF) of short-beaked common dolphins (n = 2), Atlantic white-sided dolphins (n = 8), and gray seal (n = 1) from the western North Atlantic. In three Atlantic white-sided dolphins, cerebellum gray matter (GM) was also analyzed. The levels of OCs, PCBs, MeSO 2 -PCBs, PBDEs, and OH-PBDEs in cerebellum GM were higher than the concentrations in CSF. 4-OH-2,3,3',4',5-pentachlorobiphenyl (4-OH-CB107) was the only detectable OH-PCB congener present in CSF. The sum (Σ) OH-PCBs/Σ PCB concentration ratio in CSF was approximately two to three orders of magnitude greater than the ratio in cerebellum GM for dolphins. - Organohalogens and/or metabolites in cerebrospinal fluid and cerebellum gray matter in short-beaked common dolphins, Atlantic white-sided dolphins, and gray seal.

  4. Clinical emergency treatment of 68 critical patients with severe organophosphorus poisoning and prognosis analysis after rescue.

    Dong, Hui; Weng, Yi-Bing; Zhen, Gen-Shen; Li, Feng-Jie; Jin, Ai-Chun; Liu, Jie

    2017-06-01

    This study reports the clinical emergency treatment of 68 critical patients with severe organophosphorus poisoning, and analyzes the prognosis after rescue.The general data of 68 patients with severe organophosphorus poisoning treated in our hospital were retrospectively analyzed. These patients were divided into 2 groups: treatment group, and control group. Patients in the control group received routine emergency treatment, while patients in the treatment group additionally received hemoperfusion plus hemodialysis on the basis of routine emergency treatment. The curative effects in these 2 groups and the prognosis after rescue were compared.Compared with the control group, atropinization time, recovery time of cholinesterase activity, recovery time of consciousness, extubation time, and length of hospital stay were shorter (P poisoning rebound rate was significantly lower (P treatment group.Hemoperfusion and hemodialysis on the basis of routine emergency treatment for critical patients with organophosphorus poisoning can improve rescue outcomes and improve the prognosis of patients, which should be popularized.

  5. Organophosphorus reagents in actinide separations: Unique tools for production, cleanup and disposal

    Nash, K. L.

    2000-01-01

    Interactions of actinide ions with phosphate and organophosphorus reagents have figured prominently in nuclear science and technology, particularly in the hydrometallurgical processing of irradiated nuclear fuel. Actinide interactions with phosphorus-containing species impact all aspects from the stability of naturally occurring actinides in phosphate mineral phases through the application of the bismuth phosphate and PUREX processes for large-scale production of transuranic elements to the development of analytical separation and environment restoration processes based on new organophosphorus reagents. In this report, an overview of the unique role of organophosphorus compounds in actinide production, disposal, and environment restoration is presented. The broad utility of these reagents and their unique chemical properties is emphasized

  6. Structure–efficiency relationships of cyclodextrin scavengers in the hydrolytic degradation of organophosphorus compounds

    Sophie Letort

    2017-03-01

    Full Text Available New derivatives of cyclodextrins were prepared in order to determine the relative importance of the structural key elements involved in the degradation of organophosphorus nerve agents. To avoid a competitive inclusion between the organophosphorus substrate and the iodosobenzoate group, responsible for its degradation, the latter group had to be covalently bound to the cyclodextrin scaffold. Although the presence of the α nucleophile iodosobenzoate was a determinant in the hydrolysis process, an imidazole group was added to get a synergistic effect towards the degradation of the agents. The degradation efficiency was found to be dependent on the relative position of the heterocycle towards the reactive group as well as on the nature of the organophosphorus derivative.

  7. A systems-level approach for investigating organophosphorus pesticide toxicity.

    Zhu, Jingbo; Wang, Jing; Ding, Yan; Liu, Baoyue; Xiao, Wei

    2018-03-01

    The full understanding of the single and joint toxicity of a variety of organophosphorus (OP) pesticides is still unavailable, because of the extreme complex mechanism of action. This study established a systems-level approach based on systems toxicology to investigate OP pesticide toxicity by incorporating ADME/T properties, protein prediction, and network and pathway analysis. The results showed that most OP pesticides are highly toxic according to the ADME/T parameters, and can interact with significant receptor proteins to cooperatively lead to various diseases by the established OP pesticide -protein and protein-disease networks. Furthermore, the studies that multiple OP pesticides potentially act on the same receptor proteins and/or the functionally diverse proteins explained that multiple OP pesticides could mutually enhance toxicological synergy or additive on a molecular/systematic level. To the end, the integrated pathways revealed the mechanism of toxicity of the interaction of OP pesticides and elucidated the pathogenesis induced by OP pesticides. This study demonstrates a systems-level approach for investigating OP pesticide toxicity that can be further applied to risk assessments of various toxins, which is of significant interest to food security and environmental protection. Copyright © 2017 Elsevier Inc. All rights reserved.

  8. Detection of Organophosphorus Pesticides with Colorimetry and Computer Image Analysis.

    Li, Yanjie; Hou, Changjun; Lei, Jincan; Deng, Bo; Huang, Jing; Yang, Mei

    2016-01-01

    Organophosphorus pesticides (OPs) represent a very important class of pesticides that are widely used in agriculture because of their relatively high-performance and moderate environmental persistence, hence the sensitive and specific detection of OPs is highly significant. Based on the inhibitory effect of acetylcholinesterase (AChE) induced by inhibitors, including OPs and carbamates, a colorimetric analysis was used for detection of OPs with computer image analysis of color density in CMYK (cyan, magenta, yellow and black) color space and non-linear modeling. The results showed that there was a gradually weakened trend of yellow intensity with the increase of the concentration of dichlorvos. The quantitative analysis of dichlorvos was achieved by Artificial Neural Network (ANN) modeling, and the results showed that the established model had a good predictive ability between training sets and predictive sets. Real cabbage samples containing dichlorvos were detected by colorimetry and gas chromatography (GC), respectively. The results showed that there was no significant difference between colorimetry and GC (P > 0.05). The experiments of accuracy, precision and repeatability revealed good performance for detection of OPs. AChE can also be inhibited by carbamates, and therefore this method has potential applications in real samples for OPs and carbamates because of high selectivity and sensitivity.

  9. Plutonium and americium extraction studies with bifunctional organophosphorus extractants

    Navratil, J.D.

    1985-01-01

    Neutral bifunctional organophosphorus extractants, such as octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and dihexyl-N,N-diethylcarbamoylmethylphosphonate (CMP), are under study at the Rocky Flats Plant (RFP) to remove plutonium and americium from the 7M nitric acid waste. These compounds extract trivalent actinides from strong nitric acid, a property which distinguishes them from monofunctional organiphosphorus reagents. Furthermore, the reagents extract hydroytic plutonium (IV) polymer which is present in the acid waste stream. The compounds extract trivalent actinides with a 3:1 stoichiometry, whereas tetra- and hexavalent actinides extract with a stoichiometry of 2:1. Preliminary studies indicate that the extracted plutonium polymer complex contains one to two molecules of CMP per plutonium ion and the plutonium(IV) maintains a polymeric structure. Recent studies by Horwitz and co-workers conclude that the CMPO and CMP reagents behave as monodentate ligands. At RFP, three techniques are being tested for using CMP and CMPO to remove plutonium and americium from nitric acid waste streams. The different techniques are liquid-liquid extraction, extraction chromatography, and solid-supported liquid membranes. Recent tests of the last two techniques will be briefly described. In all the experiments, CMP was an 84% pure material from Bray Oil Co. and CMPO was 98% pure from M and T Chemicals

  10. Neurotoxicity in Preclinical Models of Occupational Exposure to Organophosphorus Compounds

    Voorhees, Jaymie R.; Rohlman, Diane S.; Lein, Pamela J.; Pieper, Andrew A.

    2017-01-01

    Organophosphorus (OPs) compounds are widely used as insecticides, plasticizers, and fuel additives. These compounds potently inhibit acetylcholinesterase (AChE), the enzyme that inactivates acetylcholine at neuronal synapses, and acute exposure to high OP levels can cause cholinergic crisis in humans and animals. Evidence further suggests that repeated exposure to lower OP levels insufficient to cause cholinergic crisis, frequently encountered in the occupational setting, also pose serious risks to people. For example, multiple epidemiological studies have identified associations between occupational OP exposure and neurodegenerative disease, psychiatric illness, and sensorimotor deficits. Rigorous scientific investigation of the basic science mechanisms underlying these epidemiological findings requires valid preclinical models in which tightly-regulated exposure paradigms can be correlated with neurotoxicity. Here, we review the experimental models of occupational OP exposure currently used in the field. We found that animal studies simulating occupational OP exposures do indeed show evidence of neurotoxicity, and that utilization of these models is helping illuminate the mechanisms underlying OP-induced neurological sequelae. Still, further work is necessary to evaluate exposure levels, protection methods, and treatment strategies, which taken together could serve to modify guidelines for improving workplace conditions globally. PMID:28149268

  11. Preparation of Electrochemical Biosensor for Detection of Organophosphorus Pesticides

    Ashish Gothwal

    2014-01-01

    Full Text Available Polyvinyl chloride (PVC can be used to develop reaction beaker which acts as electrochemical cell for the measurement of OP pesticides. Being chemically inert, corrosion resistant, and easy in molding to various shapes and size, PVC can be used for the immobilization of enzyme. Organophosphorus hydrolase was immobilized covalently onto the chemically activated inner surface of PVC beaker by using glutaraldehyde as a coupling agent. The carbon nanotubes paste working electrode was constructed for amperometric measurement at a potential of +0.8 V. The biosensor showed optimum response at pH 8.0 with incubation temperature of 40°C. Km and Imax for substrate (methyl parathion were 322.58 µM and 1.1 µA, respectively. Evaluation study showed a correlation of 0.985, which was in agreement with the standard method. The OPH biosensor lost 50% of its initial activity after its regular use for 25 times over a period of 50 days when stored in 0.1 M sodium phosphate buffer, pH 8.0 at 4°C. No interference was observed by interfering species.

  12. ANALYSIS OF ORGANOPHOSPHORUS POISONING, AT TERTIARY CARE HOSPITAL: A REPORT

    Shakuntala

    2015-01-01

    Full Text Available BACKGROUND: Organophosphorus (OP compounds are the most common suicidal poison in developing countries and mortality continues to be high. The present study was aimed to know the pattern and outcome of the OP poisoning. METHODOLOGY: A record based retrospective study from January 2013 - December 2013 was Conducted in a tertiary care hospital and data regarding age, gender, domicile, type of poison, manner of poisoning, seasonal trends, marital status, motive behind poisoning , socio - economic status and outcome was collected in a pre - structured Performa. All data were documented, analyzed and interpreted as per the laid down protocol. RESULTS : out of total 1575 cases of OP compound poisoning, 71.73% (1130 were male, 28.27% (445 were female, 34.6% were in the age group 21 - 30 years, 70.95% were of low socio - economic status, Occupation wise agricultural workers were on top of the list (70.07%, The commonest (93.78% motive behind poisoning was suicidal in both males and females, Financial problem was one of the commonest (51.22% reasons of poisoning. The mortality rate in our study was 13.47%. CONCLUSION : Y oung and adult males of Low socio - economic class, rural, both literate and illiterate agriculturists commonly abuse this substance to commit suicide

  13. Differences between organophosphorus insecticides in human self-poisoning: a prospective cohort study.

    Eddleston, Michael; Eyer, Peter; Worek, Franz; Mohamed, Fahim; Senarathna, Lalith; von Meyer, Ludwig; Juszczak, Edmund; Hittarage, Ariyasena; Azhar, Shifa; Dissanayake, Wasantha; Sheriff, M H Rezvi; Szinicz, Ladislaus; Dawson, Andrew H; Buckley, Nick A

    Although more than 100 organophosphorus insecticides exist, organophosphorus poisoning is usually regarded as a single entity, distinguished only by the compound's lethal dose in animals. We aimed to determine whether the three most common organophosphorus insecticides used for self-poisoning in Sri Lanka differ in the clinical features and severity of poisoning they cause. We prospectively studied 802 patients with chlorpyrifos, dimethoate, or fenthion self-poisoning admitted to three hospitals. Blood cholinesterase activity and insecticide concentration were measured to determine the compound and the patients' response to insecticide and therapy. We recorded clinical outcomes for each patient. Compared with chlorpyrifos (35 of 439, 8.0%), the proportion dying was significantly higher with dimethoate (61 of 264, 23.1%, odds ratio [OR] 3.5, 95% CI 2.2-5.4) or fenthion (16 of 99, 16.2%, OR 2.2, 1.2-4.2), as was the proportion requiring endotracheal intubation (66 of 439 for chlorpyrifos, 15.0%; 93 of 264 for dimethoate, 35.2%, OR 3.1, 2.1-4.4; 31 of 99 for fenthion, 31.3%, 2.6, 1.6-4.2). Dimethoate-poisoned patients died sooner than those ingesting other pesticides and often from hypotensive shock. Fenthion poisoning initially caused few symptoms but many patients subsequently required intubation. Acetylcholinesterase inhibited by fenthion or dimethoate responded poorly to pralidoxime treatment compared with chlorpyrifos-inhibited acetylcholinesterase. Organophosphorus insecticide poisoning is not a single entity, with substantial variability in clinical course, response to oximes, and outcome. Animal toxicity does not predict human toxicity since, although chlorpyrifos is generally the most toxic in rats, it is least toxic in people. Each organophosphorus insecticide should be considered as an individual poison and, consequently, patients might benefit from management protocols developed for particular organophosphorus insecticides.

  14. Organophosphorus flame retardants – Toxicity and influence on human health

    Elżbieta Bruchajzer

    2015-06-01

    Full Text Available Organophosphorus flame retardants (flame retardants, FRs have been used for several decades in many industries, including the production of dyes, varnishes, adhesives, synthetic resins, polyvinyl chloride, hydraulic fluids, plastics and textiles. Their importance in recent times has increased due to i.a., significantly reduced use of polybrominated diphenyl ethers (PBDEs – persistent organic pollutants, dangerous for the environment. The aim of this study was to review the available literature data concerning phosphorous FRs primarily for neurotoxic, fertility, reproductive and carcinogenic effects. The analysis concerned the following most commonly used substances: tris(2-ethylhexylphosphate (TEHP, tris(2-butoxyethylphosphate (TBEP, triphenyl phosphate (TPP, tris(2-chloroethylphosphate (TCEP, tetrakis(hydroxymethyl-phosphonium chloride (THPC, tributyl phosphate (TBP, tricresyl phosphate (TCP, tris(2-chloroisopropylphosphate (TCPP, tris(1,3-dichloroisopropylphosphate (TDCP and tetrakis(hydroxymethyl phosphonium sulphate (THPS. In animal studies neurotoxic effects were found after exposure to TBEP, THPC, TBP and TCP, while in humans they were observed only after exposure to TCP. TCEP, THPS, TBP, TCP and TDCP caused disorders in fertility and/or fetal development of animals. Adverse effects on reproduction in humans may be caused by TPP, TCP, and TDCP. In laboratory animals the development of tumors was observed after high doses of TEHP, TCEP, TBP and TDCP. None of these compounds is classified as a human carcinogen. The environmental toxicity of phosphate FRs is low (except for TPP, TCEP and TBEP. They are not stable compounds, in living organisms they are metabolised and quickly excreted. Therefore, they can be used as an alternative to PBDEs. Med. Pr. 2015;66(2:235–264

  15. Degradation of organophosphorus compounds by X-ray irradiation

    Trebse, P.; Arcon, I.

    2002-01-01

    Complete text of publication follows. Our research presented in this contribution aims to elucidate the degradation mechanisms of organophosphate pesticides as organic pollutants by X-ray irradiation. Diazinon, one of the most widely used pesticides in Slovenia, has been chosen as a model compound for the study of radiation induced degradation of organophosphorus pesticides. Recent studies have shown that the degradation of the pesticide at normal conditions (room temperature, exposure to daylight) is strongly enhanced when the pesticide is exposed to UV light (Hg lamp, λ=254 nm, XeCl excimer laser, λ=308 nm). In our study we irradiated the pesticide in aqueous media with a white x-ray beam from a conventional x-ray source. Mo X-ray tube operating at the high voltage of 55 kV and a current of 45 mA was used. The flux of the continuous X-ray beam was stabilized within 1%. Saturated water solution of the pesticide (volume: 4mL, conc. of 40 mg L -1 ) was inserted in 1 cm long lucite cell with 1 mm thick lucite windows. The whole volume of the solution in the cell was exposed to the unfiltered X-ray beam. The dose rate on the sample was about 1 mGy/s. Different irradiation times between 30 min to 120 min were chosen to study the dependence of the pesticide decomposition with the absorbed dose. Solid phase extraction was employed for sample extraction from the solution, and gas chromatography was used for the identification and quantification of the compounds. The results show that the concentration of the pesticide in the solution decreases exponentially with the exposure time, i.e. with the absorbed dose. At irradiation conditions described above, the time constant of the exponential decrease was 74 min

  16. Cognitive decline, mortality, and organophosphorus exposure in aging Mexican Americans.

    Paul, Kimberly C; Ling, Chenxiao; Lee, Anne; To, Tu My; Cockburn, Myles; Haan, Mary; Ritz, Beate

    2018-01-01

    Cognitive impairment is a major health concern among older Mexican Americans, associated with significant morbidity and mortality, and may be influenced by environmental exposures. To investigate whether agricultural based ambient organophosphorus (OP) exposure influences 1) the rate of cognitive decline and mortality and 2) whether these associations are mediated through metabolic or inflammatory biomarkers. In a subset of older Mexican Americans from the Sacramento Area Latino Study on Aging (n = 430), who completed modified mini-mental state exams (3MSE) up to 7 times (1998-2007), we examined the relationship between estimated ambient OP exposures and cognitive decline (linear repeated measures model) and time to dementia or being cognitively impaired but not demented (CIND) and time to mortality (cox proportional hazards model). We then explored metabolic and inflammatory biomarkers as potential mediators of these relationships (additive hazards mediation). OP exposures at residential addresses were estimated with a geographic information system (GIS) based exposure assessment tool. Participants with high OP exposure in the five years prior to baseline experienced faster cognitive decline (β = 0.038, p = 0.02) and higher mortality over follow-up (HR = 1.91, 95% CI = 1.12, 3.26). The direct effect of OP exposure was estimated at 241 (95% CI = 27-455) additional deaths per 100,000 person-years, and the proportion mediated through the metabolic hormone adiponectin was estimated to be 4% 1.5-19.2). No other biomarkers were associated with OP exposure. Our study provides support for the involvement of OP pesticides in cognitive decline and mortality among older Mexican Americans, possibly through biologic pathways involving adiponectin. Copyright © 2017 Elsevier Inc. All rights reserved.

  17. Blood cholinesterases as human biomarkers of organophosphorus pesticide exposure.

    Nigg, H N; Knaak, J B

    2000-01-01

    The organophosphorus pesticides of this review were discovered in 1936 during the search for a replacement for nicotine for cockroach control. The basic biochemical characteristics of RBC AChE and BChE were determined in the 1940s. The mechanism of inhibition of both enzymes and other serine esterases was known in the 1940s and, in general, defined in the 1950s. In 1949, the death of a parathion mixer-loader dictated blood enzyme monitoring to prevent acute illness from organophosphorus pesticide intoxication. However, many of the chemical and biochemical steps for serine enzyme inhibition by OP compounds remain unknown today. The possible mechanisms of this inhibition are presented kinetically beginning with simple (by comparison) Michaelis-Menten substrate enzyme interaction kinetics. As complicated as the inhibition kinetics appear here, PBPK model kinetics will be more complex. The determination of inter- and intraindividual variation in RBC ChE and BChE was recognized early as critical knowledge for a blood esterase monitoring program. Because of the relatively constant production of RBCs, variation in RBC AChE was determined by about 1970. The source of plasma (or serum) BChE was shown to be the liver in the 1960s with the change in BChE phenotype to the donor in liver transplant patients. BChE activity was more variable than RBC AChE, and only in the 1990s have BChE individual variation questions been answered. We have reviewed the chemistry, metabolism, and toxicity of organophosphorus insecticides along with their inhibitory action toward tissue acetyl- and butyrylcholinesterases. On the basis of the review, a monitoring program for individuals mixing-loading and applying OP pesticides for commercial applicators was recommended. Approximately 41 OPs are currently registered for use by USEPA in the United States. Under agricultural working conditions, OPs primarily are absorbed through the skin. Liver P-450 isozymes catalyze the desulfurization of

  18. Organohalogenated contaminants (OHCs) in the serum and hair of pet cats and dogs: Biosentinels of indoor pollution

    Ali, Nadeem; Malik, Riffat Naseem; Mehdi, Toufeer; Eqani, Syed Ali Musstjab Akber Shah; Javeed, Aqeel; Neels, Hugo; Covaci, Adrian

    2013-01-01

    Concentrations of different classes of organohalogenated contaminants (OHCs) viz., polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs), bromophenols (BPs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and their metabolites were determined in cat and dog serum and hair samples from Pakistan. The major DDT metabolite, p,p′-DDE, was the major OHC in cat serum (N = 20) and ranged between 1 and 2150 ng/g lipid weight (lw). p,p′-DDE was not detected in dog serum (N = 16). In contrary to other OHCs, levels of ∑HO-PCBs were significantly higher in dog serum (median = 6.0 ng/g lw) than cat serum (median = 2.2 ng/g lw). Levels of most OHCs were significantly higher (p ∑NBFRs > ∑PBDEs > ∑PCB, with the highest concentrations being around 38 ng/g hair. In paired hair-serum cat samples (N = 12), ∑DDTs (r = 0.65, p = 0.001) were significantly correlated, while for all other OHCs no significant correlations (p < 0.001) were observed in both cats and dogs. Our findings on both hair and serum samples suggested that pet dogs do not bioaccumulate DDTs. Our results are also in agreement with the hypothesis that pets may serve as biosentinels for indoor pollution. This is the first study to document the presence of OHCs in pets from Pakistan and provides baseline information for future monitoring of OHCs in pets. - Highlights: ► Different classes of OHCs were analyzed in pet serum and hair from Pakistan. ► p,p′-DDE was the major pollutant in cat serum, but was < LOQ in dog serum. ► Except HO-PCBs all other classes of OHCs were higher in cat than in dog serum. ► Three of the novel BFRs were detected in pet hair samples. ► Most of OHCs were present at higher levels in cats than humans from the same region

  19. Air-water exchange of anthropogenic and natural organohalogens on International Polar Year (IPY) expeditions in the Canadian Arctic.

    Wong, Fiona; Jantunen, Liisa M; Pućko, Monika; Papakyriakou, Tim; Staebler, Ralf M; Stern, Gary A; Bidleman, Terry F

    2011-02-01

    Shipboard measurements of organohalogen compounds in air and surface seawater were conducted in the Canadian Arctic in 2007-2008. Study areas included the Labrador Sea, Hudson Bay, and the southern Beaufort Sea. High volume air samples were collected at deck level (6 m), while low volume samples were taken at 1 and 15 m above the water or ice surface. Water samples were taken within 7 m. Water concentration ranges (pg L(-1)) were as follows: α-hexachlorocyclohexane (α-HCH) 465-1013, γ-HCH 150-254, hexachlorobenzene (HCB) 4.0-6.4, 2,4-dibromoanisole (DBA) 8.5-38, and 2,4,6-tribromoanisole (TBA) 4.7-163. Air concentration ranges (pg m(-3)) were as follows: α-HCH 7.5-48, γ-HCH 2.1-7.7, HCB 48-71, DBA 4.8-25, and TBA 6.4 - 39. Fugacity gradients predicted net deposition of HCB in all areas, while exchange directions varied for the other chemicals by season and locations. Net evasion of α-HCH from Hudson Bay and the Beaufort Sea during open water conditions was shown by air concentrations that averaged 14% higher at 1 m than 15 m. No significant difference between the two heights was found over ice cover. The α-HCH in air over the Beaufort Sea was racemic in winter (mean enantiomer fraction, EF = 0.504 ± 0.008) and nonracemic in late spring-early summer (mean EF = 0.476 ± 0.010). This decrease in EF was accompanied by a rise in air concentrations due to volatilization of nonracemic α-HCH from surface water (EF = 0.457 ± 0.019). Fluxes of chemicals during the southern Beaufort Sea open water season (i.e., Leg 9) were estimated using the Whitman two-film model, where volatilization fluxes are positive and deposition fluxes are negative. The means ± SD (and ranges) of net fluxes (ng m(-2) d(-1)) were as follows: α-HCH 6.8 ± 3.2 (2.7-13), γ-HCH 0.76 ± 0.40 (0.26-1.4), HCB -9.6 ± 2.7 (-6.1 to -15), DBA 1.2 ± 0.69 (0.04-2.0), and TBA 0.46 ± 1.1 ng m(-2) d(-1) (-1.6 to 2.0).

  20. Organohalogen Compounds in Pet Dog and Cat: Do Pets Biotransform Natural Brominated Products in Food to Harmful Hydroxlated Substances?

    Mizukawa, Hazuki; Nomiyama, Kei; Nakatsu, Susumu; Iwata, Hisato; Yoo, Jean; Kubota, Akira; Yamamoto, Miyuki; Ishizuka, Mayumi; Ikenaka, Yoshinori; Nakayama, Shouta M M; Kunisue, Tatsuya; Tanabe, Shinsuke

    2016-01-05

    There are growing concerns about the increase in hyperthyroidism in pet cats due to exposure to organohalogen contaminants and their hydroxylated metabolites. This study investigated the blood contaminants polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) and their hydroxylated and methoxylated derivatives (OH-PCBs, OH-PBDEs, and MeO-PBDEs), in pet dogs and cats. We also measured the residue levels of these compounds in commercially available pet foods. Chemical analyses of PCBs and OH-PCBs showed that the OH-PCB levels were 1 to 2 orders of magnitude lower in cat and dog food products than in their blood, suggesting that the origin of OH-PCBs in pet dogs and cats is PCBs ingested with their food. The major congeners of OH-/MeO-PBDEs identified in both pet food products and blood were natural products (6OH-/MeO-BDE47 and 2'OH-/MeO-BDE68) from marine organisms. In particular, higher concentrations of 6OH-BDE47 than 2'OH-BDE68 and two MeO-PBDE congeners were observed in the cat blood, although MeO-BDEs were dominant in cat foods, suggesting the efficient biotransformation of 6OH-BDE47 from 6MeO-BDE47 in cats. We performed in vitro demethylation experiments to confirm the biotransformation of MeO-PBDEs to OH-PBDEs using liver microsomes. The results showed that 6MeO-BDE47 and 2'MeO-BDE68 were demethylated to 6OH-BDE47 and 2'OH-BDE68 in both animals, whereas no hydroxylated metabolite from BDE47 was detected. The present study suggests that pet cats are exposed to MeO-PBDEs through cat food products containing fish flavors and that the OH-PBDEs in cat blood are derived from the CYP-dependent demethylation of naturally occurring MeO-PBDE congeners, not from the hydroxylation of PBDEs.

  1. Exposure to mixtures of organohalogen contaminants and associative interactions with thyroid hormones in East Greenland polar bears (Ursus maritimus).

    Villanger, Gro D; Jenssen, Bjørn M; Fjeldberg, Rita R; Letcher, Robert J; Muir, Derek C G; Kirkegaard, Maja; Sonne, Christian; Dietz, Rune

    2011-05-01

    We investigated the multivariate relationships between adipose tissue residue levels of 48 individual organohalogen contaminants (OHCs) and circulating thyroid hormone (TH) levels in polar bears (Ursus maritimus) from East Greenland (1999-2001, n=62), using projection to latent structure (PLS) regression for four groupings of polar bears; subadults (SubA), adult females with cubs (AdF_N), adult females without cubs (AdF_S) and adult males (AdM). In the resulting significant PLS models for SubA, AdF_N and AdF_S, some OHCs were especially important in explaining variations in circulating TH levels: polybrominated diphenylether (PBDE)-99, PBDE-100, PBDE-153, polychlorinated biphenyl (PCB)-52, PCB-118, cis-nonachlor, trans-nonachlor, trichlorobenzene (TCB) and pentachlorobenzene (QCB), and both negative and positive relationships with THs were found. In addition, the models revealed that DDTs had a positive influence on total 3,5,3'-triiodothyronine (TT3) in AdF_S, and that a group of 17 higher chlorinated ortho-PCBs had a positive influence on total 3,5,3',5'-tetraiodothyronine (thyroxine, TT4) in AdF_N. TH levels in AdM seemed less influenced by OHCs because of non-significant PLS models. TH levels were also influenced by biological factors such as age, sex, body size, lipid content of adipose tissue and sampling date. When controlling for biological variables, the major relationships from the PLS models for SubA, AdF_N and AdF_S were found significant in partial correlations. The most important OHCs that influenced TH levels in the significant PLS models may potentially act through similar mechanisms on the hypothalamic-pituitary-thyroid (HPT) axis, suggesting that both combined effects by dose and response addition and perhaps synergistic potentiation may be a possibility in these polar bears. Statistical associations are not evidence per se of biological cause-effect relationships. Still, the results of the present study indicate that OHCs may affect circulating

  2. Dietary cumulative acute risk assessment of organophosphorus, carbamates and pyrethroids insecticides for the Brazilian population.

    Jardim, Andreia Nunes Oliveira; Brito, Alessandra Page; van Donkersgoed, Gerda; Boon, Polly E; Caldas, Eloisa Dutra

    Cumulative acute dietary risk assessments of organophosphorus (OPs), carbamates (CBs) and pyrethroids (PYs) were conducted for the Brazilian population. Residue data for 30786 samples of 30 foods were obtained from two national monitoring programs and one University laboratory, and consumption data

  3. Immobilization of Organophosphorus Acid Anhydrolase Mutant Y212F on Silica Nanospheres

    2016-09-01

    wild type organophosphorus acid anhydrolase (OPAA) for activity on G-type chemical nerve agents and observed increased activity on the most- toxic ...eventual use in determining particle-binding efficiency and enzymatic activity ..................................................4 5. Fluoride assay...7 TABLES 1. Results of Fluoride Release Assay from DFP Testing of Y212F Enzyme, before and after Conjugation to

  4. Infrared Spectroscopic Observations on the Fate of Organophosphorus Compounds Exposed to Atmospheric Moisture. Part 3

    2007-05-01

    FATE OF ORGANOPHOSPHORUS COMPOUNDS EXPOSED TO ATMOSPHERIC MOISTURE PART III. PHOSPHINES, PHOSPHITES , PHOSPHONITES, PHOSPHINITES, PHOSPHORIC ACIDS ...The investigation continues with Phosphines, Phosphites , Phosphonites, Phosphinites, Phosphoric Acids , Phosphonic Acids , Phosphinic Acids , Phosphine...infrared spectrum of di-(2-ethylhexyl) phosphoric acid as a liquid film between KBr windows is given in Figure 104. The band assignments are as follows

  5. Monoclonal antibody-based broad-specificity immunoassay for monitoring organophosphorus pesticides in environmental water samples

    The extensive use of organophosphorus pesticides (OPs) in agriculture and domestic settings can result in widespread water contamination. The development of easy-to-use and rapid-screening immunoassay methods in a class-selective manner is a topic of considerable environmental interest. In this wo...

  6. Determination of organophosphorus acids by thermo-spray liquid chromatography-mass spectrometry

    Wils, E.R.J.; Hulst, A.G.

    1988-01-01

    The determination of thirteen organophosphorus acids, hydrolysis products of nerve agents and pesticides, by a combination of ion-pair liquid chromatography on a reversed-phase C18 column and thermospray mass spectrometry was investigated. Ammonium acetate and three tetraalkylammonium salts with

  7. RESEARCH OF HEAVY METALS, ORGANOCHLORINE AND ORGANOPHOSPHORUS PESTICIDES IN POWDERED INFANT FORMULA

    M.C. Abete

    2009-02-01

    Full Text Available During the period between october 2007 and november 2008 were collected 60 samples of powdered infant formula. The analysis for the detection of heavy metals, organochlorine and organophosphorus pesticides show that the environmental situation is under control and powdered infant formula satisfies this health requisite.

  8. Tracing organophosphorus and brominated flame retardants and plasticizers in an estuarine food web

    Brandsma, S.H.; Leonards, P.E.G.; Leslie, H.A.; de Boer, J.

    2015-01-01

    Nine organophosphorus flame retardants (PFRs) were detected in a pelagic and benthic food web of the Western Scheldt estuary, The Netherlands. Concentrations of several PFRs were an order of magnitude higher than those of the brominated flame retardants (BFRs). However, the detection frequency of

  9. Reproductive performance in East Greenland polar bears (Ursus maritimus) may be affected by organohalogen contaminants as shown by physiologically-based pharmacokinetic (PBPK) modelling

    Sonne, Christian; Gustavson, Kim; Rigét, Frank F.

    2009-01-01

    Polar bears (Ursus maritimus) feed mainly on ringed seal (Phoca hispida) and consume large quantities of blubber and consequently have one of the highest tissue concentrations of organohalogen contaminants (OHCs) worldwide. In East Greenland, studies of OHC time trends and organ system health...... effects, including reproductive, were conducted during 1990–2006. However, it has been difficult to determine the nature of the effects induced by OHC exposures on wild caught polar bears using body burden data and associated changes in reproductive organs and systems. We therefore conducted a risk......, oxychlordane, HCHs, HCB, PBDEs and PFOS in East Greenland polar bears based on known OHC pharmacokinetics and dynamics in laboratory rats (Rattus rattus). The results showed that subcutaneous adipose tissue concentrations of dieldrin (range: 79–1271 ng g−1 lw) and PCBs (range: 4128–53 923 ng g−1 lw) reported...

  10. [On necessity to modify biochemical methods for detecting organophosphorus componds in chemical weapons extinction objects (review of literature)].

    Prokofieva, D S; Shmurak, V I; Sadovnikov, S V; Gontcharov, N V

    2015-01-01

    The article covers problems of biochemical methods assessing organophosphorus toxic compounds in objects of chemical weapons extinction. The authors present results of works developing new, more specific and selective biochemical methods.

  11. Comparison of the Developmental and Acute Neurotoxicity of a Library of Organophosphorus Pesticides Using a Vertebrate Behavioral Assay

    The U.S. Environmental Protection Agency is evaluating methods to screen and prioritize organophosphorus pesticides for neurotoxicity using behavioral tests in an in vivo, vertebrate, medium-throughput model (zebrafish; Danio rerio). Our behavioral testing paradigm assesses the e...

  12. Optimization of Cholinesterase-Based Catalytic Bioscavengers Against Organophosphorus Agents.

    Lushchekina, Sofya V; Schopfer, Lawrence M; Grigorenko, Bella L; Nemukhin, Alexander V; Varfolomeev, Sergei D; Lockridge, Oksana; Masson, Patrick

    2018-01-01

    Organophosphorus agents (OPs) are irreversible inhibitors of acetylcholinesterase (AChE). OP poisoning causes major cholinergic syndrome. Current medical counter-measures mitigate the acute effects but have limited action against OP-induced brain damage. Bioscavengers are appealing alternative therapeutic approach because they neutralize OPs in bloodstream before they reach physiological targets. First generation bioscavengers are stoichiometric bioscavengers. However, stoichiometric neutralization requires administration of huge doses of enzyme. Second generation bioscavengers are catalytic bioscavengers capable of detoxifying OPs with a turnover. High bimolecular rate constants ( k cat / K m > 10 6 M -1 min -1 ) are required, so that low enzyme doses can be administered. Cholinesterases (ChE) are attractive candidates because OPs are hemi-substrates. Moderate OP hydrolase (OPase) activity has been observed for certain natural ChEs and for G117H-based human BChE mutants made by site-directed mutagenesis. However, before mutated ChEs can become operational catalytic bioscavengers their dephosphylation rate constant must be increased by several orders of magnitude. New strategies for converting ChEs into fast OPase are based either on combinational approaches or on computer redesign of enzyme. The keystone for rational conversion of ChEs into OPases is to understand the reaction mechanisms with OPs. In the present work we propose that efficient OP hydrolysis can be achieved by re-designing the configuration of enzyme active center residues and by creating specific routes for attack of water molecules and proton transfer. Four directions for nucleophilic attack of water on phosphorus atom were defined. Changes must lead to a novel enzyme, wherein OP hydrolysis wins over competing aging reactions. Kinetic, crystallographic, and computational data have been accumulated that describe mechanisms of reactions involving ChEs. From these studies, it appears that introducing

  13. Optimization of Cholinesterase-Based Catalytic Bioscavengers Against Organophosphorus Agents

    Sofya V. Lushchekina

    2018-03-01

    Full Text Available Organophosphorus agents (OPs are irreversible inhibitors of acetylcholinesterase (AChE. OP poisoning causes major cholinergic syndrome. Current medical counter-measures mitigate the acute effects but have limited action against OP-induced brain damage. Bioscavengers are appealing alternative therapeutic approach because they neutralize OPs in bloodstream before they reach physiological targets. First generation bioscavengers are stoichiometric bioscavengers. However, stoichiometric neutralization requires administration of huge doses of enzyme. Second generation bioscavengers are catalytic bioscavengers capable of detoxifying OPs with a turnover. High bimolecular rate constants (kcat/Km > 106 M−1min−1 are required, so that low enzyme doses can be administered. Cholinesterases (ChE are attractive candidates because OPs are hemi-substrates. Moderate OP hydrolase (OPase activity has been observed for certain natural ChEs and for G117H-based human BChE mutants made by site-directed mutagenesis. However, before mutated ChEs can become operational catalytic bioscavengers their dephosphylation rate constant must be increased by several orders of magnitude. New strategies for converting ChEs into fast OPase are based either on combinational approaches or on computer redesign of enzyme. The keystone for rational conversion of ChEs into OPases is to understand the reaction mechanisms with OPs. In the present work we propose that efficient OP hydrolysis can be achieved by re-designing the configuration of enzyme active center residues and by creating specific routes for attack of water molecules and proton transfer. Four directions for nucleophilic attack of water on phosphorus atom were defined. Changes must lead to a novel enzyme, wherein OP hydrolysis wins over competing aging reactions. Kinetic, crystallographic, and computational data have been accumulated that describe mechanisms of reactions involving ChEs. From these studies, it appears that

  14. Organohalogenated contaminants (OHCs) in the serum and hair of pet cats and dogs: Biosentinels of indoor pollution

    Ali, Nadeem [Toxicological Centre, University of Antwerp, Universiteitsplein 1, 2610 Wilrijk (Belgium); Malik, Riffat Naseem [Environmental Biology and Ecotoxicology Laboratory, Department of Environmental Sciences, Quiad-i-Azam University, Islamabad 45320 (Pakistan); Mehdi, Toufeer [Institute of Microbiology, University of Agriculture Faisalabad (Pakistan); Eqani, Syed Ali Musstjab Akber Shah [Department of Bio Sciences, COMSATS Institute of Information Technology, Islamabad (Pakistan); Javeed, Aqeel [Department of Pharmacology and Toxicology, University of Veterinary and Animal Sciences, Lahore (Pakistan); Neels, Hugo [Toxicological Centre, University of Antwerp, Universiteitsplein 1, 2610 Wilrijk (Belgium); Covaci, Adrian, E-mail: adrian.covaci@ua.ac.be [Toxicological Centre, University of Antwerp, Universiteitsplein 1, 2610 Wilrijk (Belgium)

    2013-04-01

    Concentrations of different classes of organohalogenated contaminants (OHCs) viz., polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs), bromophenols (BPs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and their metabolites were determined in cat and dog serum and hair samples from Pakistan. The major DDT metabolite, p,p′-DDE, was the major OHC in cat serum (N = 20) and ranged between 1 and 2150 ng/g lipid weight (lw). p,p′-DDE was not detected in dog serum (N = 16). In contrary to other OHCs, levels of ∑HO-PCBs were significantly higher in dog serum (median = 6.0 ng/g lw) than cat serum (median = 2.2 ng/g lw). Levels of most OHCs were significantly higher (p < 0.05) in cat serum than those found in human serum from the same region, in particular for ∑PBDEs (ranged 1–1280 ng/g lw). Significantly lower levels of OCPs (p < 0.05) were detected in dog serum than in human serum. The concentrations of ∑BPs were seven times higher in cat serum (median 112 ng/g lw) than dog serum (median 16 ng/g lw). To the best of our knowledge, this is the first time that NBFRs, e.g. 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), decabromodiphenylethane (DBDPE), and bis(2-ethylhexyl)-3,4,5,6-tetrabromophthalate (TBPH), were detected in cat and dog's hair. BTBPE had the highest detection frequency (30%) in the serum samples. In cat and dog hair samples, the order of importance of OHCs was ∑OCPs > ∑NBFRs > ∑PBDEs > ∑PCB, with the highest concentrations being around 38 ng/g hair. In paired hair-serum cat samples (N = 12), ∑DDTs (r = 0.65, p = 0.001) were significantly correlated, while for all other OHCs no significant correlations (p < 0.001) were observed in both cats and dogs. Our findings on both hair and serum samples suggested that pet dogs do not bioaccumulate DDTs. Our results are also in agreement with the hypothesis that pets may serve as biosentinels for indoor pollution. This is the first study to

  15. Comparative study on cleanup procedures for the determination of organophosphorus pesticides in vegetables

    Alvin, Chai Lian Kuet; Lau, Seng

    2008-01-01

    A study was carried out to compare the cleanup procedures for the determination of organophosphorus pesticides in vegetables. Eleven organophosphorus pesticides were extracted with acetone and methylene chloride. Extracts were cleanup by solid-phase extraction (SPE) mixed-mode column using quaternary amine and aminopropyl (SAX/ NH 2 ) or octadecyl (C 18 ) sorbents. The pesticides were determined by gas chromatography with flame photometric detector. The recovery results obtained from the SPE SAX/ NH 2 and C 18 cleanups in carrot, cucumber and green mustard samples were in the range of 71.0 % to 115 %. Lower recoveries were obtained for polar pesticides, methamidophos and dimethoate. These results were compared to the method currently used in the laboratory which does not include any cleanup. (author)

  16. Calcium uptake by sarcoplasmic reticulum in the presence of organophosphorus insecticide methyl-parathion

    Blasiak, J.

    1995-01-01

    Using an isotope labelling technique it has been shown that an organophosphorus insecticide methyl parathion (0,0-diethyl 0-4-nitrophenyl phosphorothionate) depressed calcium uptake by sarcoplasmic reticulum isolated from rabbit hind leg muscle. The effect was significant for insecticide concentrations of 50 and 100 μM and was dose-dependent. The insecticide exerted a more pronounced effect on calcium uptake in the presence of ATP in the reticulum environment than in the absence of ATP. The inhibitory action of methyl parathion on Ca 2+ accumulation by sarcoplasmic reticulum can cause a rise in myoplasmic free Ca 2+ , the essential prerequisite for contracture activation. Because methyl parathion, as well as other organophosphorus insecticides, is primarily neurotoxic, evidence of non-specific effect could be important for assessing its environmental safety. (author). 20 refs, 2 figs

  17. Organophosphorus insecticides: Toxic effects and bioanalytical tests for evaluating toxicity during degradation processes

    Čolović Mirjana B.

    2013-01-01

    Full Text Available Organophosphorus insecticides have been the most applied group of insecticides for the last two decades. Their main toxic effects are related to irreversible inactivation of acetylcholinesterase (AChE. Actually, they covalently bind to serine OH group in the enzyme active site forming phosphorylated enzyme that cannot hydrolyze acetylcholine. Organophosphorus insecticides in the environment undergo the natural degradation pathway including mainly homogeneous and heterogeneous hydrolysis (especially at high pH generating non-inhibiting products. Additionally, thio organophosphates are easily oxidized by naturally present oxidants and UV light, forming more toxic and stable oxons. Thus, oxidative degradation procedures, generally referred as advanced oxidation processes (AOP, have been applied for their efficient removal from contaminated waters. The most applied bioassays to monitor the organophosphate toxicity i.e. the detoxification degree during AOP are Vibrio fischeri and AChE bioassays. Vibrio fischeri toxicity test exploits bioluminescence as the measure of luciferase activity of this marine bacterium, whereas AChE bioassay is based on AChE activity inhibition. Both bioanalytical techniques are rapid (several minutes, simple, sensitive and reproducible. Vibrio fischeri test seems to be a versatile indicator of toxic compounds generated in AOP for organophosphorus insecticides degradation. However, detection of neurotoxic AChE inhibitors, which can be formed in AOP of some organophosphates, requires AChE bioassays. Therefore, AChE toxicity test is more appropriate for monitoring the degradation processes of thio organophosphates, because more toxic oxo organophosphates might be formed and overlooked by Vibrio fischeri bioluminescence inhibition. In addition, during organophosphates removal by AOP, compounds with strong genotoxic potential may be formed, which cannot be detected by standard toxicity tests. For this reason, determination of

  18. Organophosphorus acid anhydrolase from Alteromonas macleodii: structural study and functional relationship to prolidases

    Štěpánková, Andrea; Dušková, Jarmila; Skálová, Tereza; Hašek, Jindřich; Koval, Tomáš; Ostergaard, L. H.; Dohnálek, Jan

    2013-01-01

    Roč. 69, č. 4 (2013), s. 346-354 ISSN 1744-3091 R&D Projects: GA ČR GA310/09/1407; GA ČR GA305/07/1073; GA MŠk EE2.3.30.0029 Institutional research plan: CEZ:AV0Z40500505 Institutional support: RVO:61389013 Keywords : organophosphorus acid anhydrolase * prolidases * bifunctional Subject RIV: CE - Biochemistry Impact factor: 0.568, year: 2013

  19. A Common Mechanism for Resistance to Oxime Reactivation of Acetylcholinesterase Inhibited by Organophosphorus Compounds

    2013-01-01

    reactivated than AChE conjugates inhibited by the corresponding Rp enantiomers and this effect is enhanced as the size of the O-alkyl substituents of OP...Organophosphates and Carbamates, Butterworth & Heinemann , Oxford, 1992. pp. 555–577. [2] P. Taylor, Anticholinesterase agents, in: L.L. Brunton, J.S...application of the Hammett equation with the constants rph in the chemistry of organophosphorus compounds, Russ. Chem. Rev. 38 (1969) 795–811. [13

  20. Long Alkyl Chain Organophosphorus Coupling Agents for in Situ Surface Functionalization by Reactive Milling

    Annika Betke

    2014-08-01

    Full Text Available Innovative synthetic approaches should be simple and environmentally friendly. Here, we present the surface modification of inorganic submicrometer particles with long alkyl chain organophosphorus coupling agents without the need of a solvent, which makes the technique environmentally friendly. In addition, it is of great benefit to realize two goals in one step: size reduction and, simultaneously, surface functionalization. A top-down approach for the synthesis of metal oxide particles with in situ surface functionalization is used to modify titania with long alkyl chain organophosphorus coupling agents. A high energy planetary ball mill was used to perform reactive milling using titania as inorganic pigment and long alkyl chain organophosphorus coupling agents like dodecyl and octadecyl phosphonic acid. The final products were characterized by IR, NMR and X-ray fluorescence spectroscopy, thermal and elemental analysis as well as by X-ray powder diffraction and scanning electron microscopy. The process entailed a tribochemical phase transformation from the starting material anatase to a high-pressure modification of titania and the thermodynamically more stable rutile depending on the process parameters. Furthermore, the particles show sizes between 100 nm and 300 nm and a degree of surface coverage up to 0.8 mmol phosphonate per gram.

  1. A STUDY OF PREDICTING THE NEED FOR VENTILATOR SUPPORT AND OUTCOME IN ORGANOPHOSPHORUS POISONING

    Kalinga Bommankatte Eranaik

    2017-04-01

    Full Text Available BACKGROUND Organophosphorus compound poisoning is the most common poisonings in India because of easy availability, often requiring ICU care and ventilator support. Clinical research has indicated that respiratory failure is the most important cause of death due to Organophosphorus poisoning. It results in respiratory muscle weakness, pulmonary oedema, respiratory depression, increased secretions and bronchospasm. These complications and death can be prevented with timely Institution of ventilator support. The aim of present study was to identify the factors and predicting the need for ventilator support and outcome. Aim of the Study- To predict the need for ventilator support and outcome in organophosphate poisoning. MATERIALS AND METHODS Seventy consecutive patients admitted with a history of organophosphorus poisoning at KIMS, Hubli were taken for study after considering the inclusion and exclusion criteria. Detailed history, confirmation of poisoning, examination and other than routine investigations serum pseudocholinesterase and arterial blood gas analysis was done. The severity of organophosphorus poisoning was graded as mild, moderate and severe based on the factors which influence the need for ventilator support. RESULTS This study was conducted in 70 patients, out of which 48 (68.6% were male patients and 22 (31.4% were female patients. Among them 37 (53% patients required ventilation and 33 (47% expired. Chlorpyrifos, Dichlorvos and Monocrotophos were most commonly consumed poisons. 74% patients who consumed these compounds required ventilator support and 73% patients expired. 100% of patients presented with pin point pupil, fasciculation score > 4, respiratory rate > 20, GCS score < 7 and severe grade of poisoning required ventilator support and pseudocholinesterase < 900 U/L, 70% of metabolic acidosis and atropine requirement more than 180 mg within 48 hours required ventilator support and associated with high mortality. CONCLUSION

  2. Organohalogen contamination in passerine birds from three metropolises in China: Geographical variation and its implication for anthropogenic effects on urban environments

    Yu, Le-Huan; Luo, Xiao-Jun; Liu, Hong-Ying; Zeng, Yan-Hong; Zheng, Xiao-Bo; Wu, Jiang-Ping; Yu, Yun-Jiang; Mai, Bi-Xian

    2014-01-01

    Contamination of organohalogen pollutants (OHPs), including dichlorodiphenyl trichloroethane and its metabolites (DDTs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), decabromodiphenylethane (DBDPE), hexabromocyclododecanes (HBCDs), and dechlorane plus (DP) in three metropolises of China, Beijing, Wuhan, and Guangzhou, and a reference rural site were determined using terrestrial residential passerine species as bioindicator. DDTs dominated in Wuhan whereas flame retardants dominated in Guangzhou and Beijing. No geographical variation was found for PCB levels but it exhibited different homologue profiles among different sites which could be attributed to different dietary sources of birds. Industry characteristics of the sampling location contributed to the geographical differences in the occurrence and contamination profile of OHPs. The transformation of traditional agriculture characterized contamination profiles to industry characterized profiles in Beijing and Guangzhou implicates significantly environmental concern on the flame retardants contamination in non-hot-spot regions of China. - Highlights: • Various OHPs were determined in passerine birds from three metropolises of China. • Geographical variations of OHPs levels and contamination profiles were observed. • More concern should be taken on the dominance of FRs in Chinese developed cities. • Diet source characterized by δ 13 C plays a key role in PCB pattern determination. - Geographical variations of OHPs contamination profiles indicate significant impact of industrialization and urbanization on Chinese urban environment

  3. Organo-halogenated contaminants (OHCs) in the sediments from the Soan River, Pakistan: OHCs(adsorbed TOC) burial flux, status and risk assessment.

    Malik, Riffat Naseem; Mehboob, Fouzia; Ali, Usman; Katsoyiannis, Athanasios; Schuster, Jasmin K; Moeckel, Claudia; Jones, Kevin C

    2014-05-15

    In this study, regression analysis revealed that TOC is the principal factor in controlling the fate of organo-halogenated contaminants (OHCs: PCBs, PBDEs, OCPs) in Soan River, Pakistan. The OHCs(adsorbed TOC) burial flux (OHCs(adsorbed TOC)Bf; mg/cm(2)·yr) was calculated in the following ranges: ∑PCBs (0.07-0.31), ∑PBDEs (0.005-0.029), ∑HCHs (0.015-0.046) and ∑DDTs (0.007-0.039). Apart from OHCs(adsorbed TOC)Bf, the levels of OHCs were in the following order: PCBs>DDTs>PBDEs>HCH>Chlordane>HCB. PBDEs and PCB congener patterns showed following order respectively: BDE-149>-153>-18>-138>-44 and PCB-149>-153>-18>-138>-44. DDT isomers and metabolites' pattern were p,p'-DDT>p,p'-DDD>p,p'-DDE>o,p'-DDT>o,p'-DDD>o,p'-DDE and HCHs were β-HCH>α-HCH>γ-HCH>δ-HCH. PBDE composition had similarities to penta-BDE and DE-71 mixtures and PCBs with commercial products Aroclor-1254 and -1260. (DDE+DDD)/∑DDTs and p,p'-DDT/p,p'-DDE suggested the recent input of DDTs in sediments while α/γ-HCH indicated past usage of lindane and technical mixtures. Risk assessment suggested that Soan River and its tributaries are potentially at risk against most of the OHCs. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. Levels and distribution of organophosphorus flame retardants and plasticizers in fishes from Manila Bay, the Philippines

    Kim, Joon-Woo; Isobe, Tomohiko; Chang, Kwang-Hyeon; Amano, Atsuko; Maneja, Rommel H.; Zamora, Peter B.; Siringan, Fernando P.; Tanabe, Shinsuke

    2011-01-01

    Organophosphorus compounds (OPCs) and stable isotope ratios (δ 13 C and δ 15 N) were determined in 58 fishes belonging to 20 species collected from Manila Bay, the Philippines. OPCs were detected in most of the samples and found up to μg/g lw (lipid weight) level, suggesting their ubiquitous presence in the coastal marine environment of the Philippines. Higher levels (>1000 ng/g lw) of total OPCs were determined in yellowstriped goatfish, silver sillago, tripletail wrasse and bumpnose trevally indicates either their active uptake from ambient water or lower metabolic capacity of these species. Levels of triphenyl phosphate (TPhP) in demersal species showed a positive correlation with δ 15 N, indicating that TPhP was adsorbed onto the particle, settled down to the bottom sediment and accumulated through the benthic food web rather than the pelagic. Estimated dietary intake of OPCs in Manila Bay fishes were four to five orders of magnitude lower than the proposed reference dose (RfD). - Highlights: → Organophosphorus compounds (OPCs) were determined in fish from Manila Bay. → OPCs were detected up to μg/g lw, suggesting ubiquitous environmental contamination. → Among the 9 targeted OPCs, TEHP and TEP were found as the predominant compounds. → Estimated dietary intake through fish consumption was 4-5 orders of magnitude lower than RfD. → This is the first report on OPCs pollution in marine environment of Southeast Asia. - Occurrence and bioaccumulation of organophosphorus compounds (OPCs) were determined in fishes from Manila Bay.

  5. Determination of Twenty Organophosphorus Pesticides in Wheat Samples from Different Regions of Iran

    Attaollah Shakoori *

    2017-09-01

    Full Text Available Background: Organophosphorus pesticides are widely used in agriculture, homes, gardens, and veterinary practices. Extensive application of pesticides in agriculture often results in residues of these compounds being absorbed into the foods, including wheat. The aim of this study was to evaluate the residue levels of 20 organophosphorus pesticides in wheat samples collected from different regions of Iran. Methods: This research reports a rapid, specific and sensitive multiresidue method based on the Quick Easy Cheap Effective Rugged and Safe (QuEChERS sample preparation method and gas chromatography with mass spectrometric detection in the selected ion monitoring mode (GC–SIM–MS to evaluate 20 organophosphorus pesticides in wheat samples. Results: In the concentration range of 20-200 ng/g, the calibration curves for each analyte was linear with a determination coefficient (R2 of 0.993 to 0.999. The limits of detection (LODs and quantitation (LOQs were between 2.5-6.7 and 7.5-20 ng/g, respectively. The mean recoveries obtained for three fortification levels (25, 50 and 100 ng/g, five replicates each were 80-114% with a satisfactory precision (RSD<20%. 31.1% samples contained residues of one or more target compounds. Chlorpyrifos was the most common residue (17.8%, followed by pirimiphos-methyl (6.7%, diazinon (4.4%, chlorpyrifos-methyl (1.1% and malathion (1.1%. Conclusion: Among the detected pesticides, only diazinon and malathion are permitted pesticides for wheat production in Iran. However, their concentrations were below the maximum residue levels (MRLs established by the Iranian National Standard Organization (INSO.

  6. Simple, specific analysis of organophosphorus and carbamate pesticides in sediments using column extraction and gas chromatography

    Belisle, A.A.; Swineford, D.M.

    1988-01-01

    A simple, specific procedure was developed for the analysis of organophosphorus and carbamate pesticides in sediment. The wet soil was mixed with anhydrous sodium sulfate to bind water and the residues were column extracted in acetone:methylene chloride (1:l,v/v). Coextracted water was removed by additional sodium sulfate packed below the sample mixture. The eluate was concentrated and analyzed directly by capillary gas chromatography using phosphorus and nitrogen specific detectors. Recoveries averaged 93 % for sediments extracted shortly after spiking, but decreased significantly as the samples aged.

  7. Pralidoxime in acute organophosphorus insecticide poisoning--a randomised controlled trial.

    Michael Eddleston

    2009-06-01

    Full Text Available Poisoning with organophosphorus (OP insecticides is a major global public health problem, causing an estimated 200,000 deaths each year. Although the World Health Organization recommends use of pralidoxime, this antidote's effectiveness remains unclear. We aimed to determine whether the addition of pralidoxime chloride to atropine and supportive care offers benefit.We performed a double-blind randomised placebo-controlled trial of pralidoxime chloride (2 g loading dose over 20 min, followed by a constant infusion of 0.5 g/h for up to 7 d versus saline in patients with organophosphorus insecticide self-poisoning. Mortality was the primary outcome; secondary outcomes included intubation, duration of intubation, and time to death. We measured baseline markers of exposure and pharmacodynamic markers of response to aid interpretation of clinical outcomes. Two hundred thirty-five patients were randomised to receive pralidoxime (121 or saline placebo (114. Pralidoxime produced substantial and moderate red cell acetylcholinesterase reactivation in patients poisoned by diethyl and dimethyl compounds, respectively. Mortality was nonsignificantly higher in patients receiving pralidoxime: 30/121 (24.8% receiving pralidoxime died, compared with 18/114 (15.8% receiving placebo (adjusted hazard ratio [HR] 1.69, 95% confidence interval [CI] 0.88-3.26, p = 0.12. Incorporating the baseline amount of acetylcholinesterase already aged and plasma OP concentration into the analysis increased the HR for patients receiving pralidoxime compared to placebo, further decreasing the likelihood that pralidoxime is beneficial. The need for intubation was similar in both groups (pralidoxime 26/121 [21.5%], placebo 24/114 [21.1%], adjusted HR 1.27 [95% CI 0.71-2.29]. To reduce confounding due to ingestion of different insecticides, we further analysed patients with confirmed chlorpyrifos or dimethoate poisoning alone, finding no evidence of benefit.Despite clear reactivation of

  8. Steroid hormones in blood plasma from Greenland sledge dogs (Canis familiaris) dietary exposed to organohalogen polutted minke whale (Balanenoptera acuterostrata) blubber

    Sonne, Christian; Dietz, Rune; Letcher, J.

    2014-01-01

    , respectively, for 321–576 days. In the exposed group, this constituted a mean daily intake of 128 μg ∑PCBs (5 μg/kg/day). At the end of the study, organohalogen contaminant (OHC) were measured in adipose tissue and hormone levels in blood of sledge dogs. The hormones included 11 products of the steroidogenesis......, which were ∑Androgen (dehydroepiandrosterone, androstenedione, testosterone, and dehydrotestosterone), ∑Estrogen (estrone, 17α-estradiol and 17β-estradiol), and ∑Progestagen (pregnenolone, progesterone, 17-OH-pregnenolone, and 17-OH-progesterone) concentrations. This allowed us to study the mechanisms...

  9. Construction of genetically engineered bacteria that degrades organophosphorus pesticide residues and can be easily detected by the fluorescence.

    Li, Qin; Wang, Pan; Chen, Rui; Li, Wei; Wu, Yi-Jun

    2014-01-01

    Organophosphorus compounds (OPs) are widely used in agriculture and industry and there is increased concern about their toxicological effects in the environment. Bioremediation can offer an efficient and cost-effective option for the removal of OPs. Herein, we describe the construction of a genetically engineered microorganism (GEM) that can degrade OPs and be directly detected and monitored in the environment using an enhanced green fluorescent protein (EGFP) fusion strategy. The coding regions of EGFP, a reporter protein that can fluoresce by itself, and organophosphorus hydrolase (OPH), which has a broad substrate specificity and is able to hydrolyse a number of organophosphorus pesticides, were cloned into the expression vector pET-28b. The fusion protein of EGFP-OPH was expressed in E. coli BL21 (DE3) and the protein expression reached the highest level at 11 h after isopropyl beta-D-thiogalactopyranoside induction. The fluorescence of the GEM was detected by fluorescence spectrophotometry and microscopy, and its ability to degrade OPs was determined by OPH activity assay. Those GEM that express the fusion protein (EGFP and OPH) exhibited strong fluorescence intensity and also potent hydrolase activity, which could be used to degrade organophosphorus pesticide residues in the environment and can also be directly monitored by fluorescence.

  10. AMPEROMETRIC THICK-FILM STRIP ELECTRODES FOR MONITORING ORGANOPHOSPHATE NERVE AGENTS BASED ON IMMOBILIZED ORGANOPHOSPHORUS HYDROLASE. (R823663)

    An amperometric biosensor based on the immobilization of organophosphorus hydrolase(OPH) onto screen-printed carbon electrodes is shown useful for the rapid, sensitive, and low-costdetection of organophosphate (OP) nerve agents. The sensor relies upon the sensitive and ra...

  11. DEVELOPMENT OF A RISK ASSESSMENT MODEL FOR THE EFFECTS OF ORGANOPHOSPHORUS PESTICIDES ON INFECTIOUS DISEASE SUSCEPTIBILITY AND THE IMMUNE SYSTEM

    There is increased concern about the sublethal effects of organophosphorus (OP) pesticides on human and animal health. This class of chemicals has been shown to affect the immune function of macrophages and lymphocytes. Malathion, an OP compound, is one of the most widely used ...

  12. Structural Analysis and Bioengineering of Thermostable Pyrococcus furiosus Prolidase for the Optimization of Organophosphorus Nerve Agent Detoxification

    2012-04-26

    organophosphorus acid anhydrase from a halophilic bacterial isolate. J Bacteriol, 173, 1938-1943. Du, X., Tove, S., Kast -Hutcheson, K. & Grunden, A. M...1938-1943. Du, X., Tove, S., Kast -Hutcheson, K. & Grunden, A. M. 2005. Characterization of the dinuclear metal center of Pyrococcus furiosus

  13. Confirmed organophosphorus and carbamate pesticide poisonings in South African wildlife (2009–2014

    Christo J. Botha

    2015-12-01

    Full Text Available During a six-year period (from January 2009 to December 2014, specimens collected from 344 cases of suspected organophosphorus and carbamate pesticide poisonings in wildlife, including birds, were submitted to the Toxicology Laboratory (ARC-OVI for analysis. A positive diagnosis was made in 135 (39% of these cases. The majority of cases were from birds, which included Cape vultures (Gyps coprotheres and African white-backed vultures (Gyps africanus and bateleur eagles (Terathopius ecaudatus. In one incident 49 vultures were killed when a farmer intentionally laced carcasses with carbofuran in an attempt to control jackal predation. There were 22 incidents of poisoning in helmeted guineafowl (Numida meleagris. On nine different occasions blue cranes (Anthropoides paradiseus were poisoned, in one incident 14 birds were reported to have been killed. Over the period of investigation, there were 20 cases of poisoning involving mammalian species, the majority being vervet monkeys (Chlorocebus pygerythrus. The carbamate pesticides were responsible for 57 incidents of poisoning. Aldicarb, carbofuran and methomyl were detected in 26, 18 and 12 cases respectively. The majority of organophosphorus pesticide poisonings were caused by diazinon (n = 19, monocrotophos (n = 13 and methamidophos (n = 10.

  14. In vivo tracing of organophosphorus pesticides in cabbage (Brassica parachinensis) and aloe (Barbadensis)

    Qiu, Junlang; Chen, Guosheng; Zhou, Hong; Xu, Jianqiao; Wang, Fuxin; Zhu, Fang, E-mail: ceszf@mail.sysu.edu.cn; Ouyang, Gangfeng, E-mail: cesoygf@mail.sysu.edu.cn

    2016-04-15

    In vivo solid-phase microextraction (SPME) sampling method coupled with gas chromatography–mass spectrometry (GC–MS) analysis was employed to trace the uptake and elimination of organophosphorus pesticides (OPPs) in two kinds of edible plants, cabbage (Brassica parachinensis) and aloe (Barbadensis). The metabolism of fenthion in aloe was also investigated by the liquid chromatography tandem mass spectrometry analysis (LC–MS/MS) to understand the fate of OPPs in living plants better. Transpiration stream concentration factor (TSCF) and depuration rate constants of the OPPs in living plants were obtained therein. The health risk of the OPPs treated aloe was estimated by the maximum residue limit (MRL) approach, and it revealed that the OPPs were rather safe for their fast degradable property. However, peak concentration of fenthion-sulfoxide was found to exceed the MRL and was higher than that of the parent fenthion, which indicated the potential risk of pesticide metabolites. This study highlighted the application of in vivo SPME for contaminant tracing in different living edible plants. The in vivo tracing method is very convenient and can provide more data to evaluate the risk of different pesticides, which are very important for the safety of agriculture production. - Highlights: • In vivo SPME was employed to sample organophosphorus pesticides in vegetables. • Uptake and elimination of OPPs were traced in cabbage and aloe. • In vivo tracing of fenthion demonstrated its metabolites could be rather dangerous. • The risks of OPPs were assessed based on the in vivo tracing data.

  15. Metagenomic Functional Potential Predicts Degradation Rates of a Model Organophosphorus Xenobiotic in Pesticide Contaminated Soils

    Thomas C. Jeffries

    2018-02-01

    Full Text Available Chemical contamination of natural and agricultural habitats is an increasing global problem and a major threat to sustainability and human health. Organophosphorus (OP compounds are one major class of contaminant and can undergo microbial degradation, however, no studies have applied system-wide ecogenomic tools to investigate OP degradation or use metagenomics to understand the underlying mechanisms of biodegradation in situ and predict degradation potential. Thus, there is a lack of knowledge regarding the functional genes and genomic potential underpinning degradation and community responses to contamination. Here we address this knowledge gap by performing shotgun sequencing of community DNA from agricultural soils with a history of pesticide usage and profiling shifts in functional genes and microbial taxa abundance. Our results showed two distinct groups of soils defined by differing functional and taxonomic profiles. Degradation assays suggested that these groups corresponded to the organophosphorus degradation potential of soils, with the fastest degrading community being defined by increases in transport and nutrient cycling pathways and enzymes potentially involved in phosphorus metabolism. This was against a backdrop of taxonomic community shifts potentially related to contamination adaptation and reflecting the legacy of exposure. Overall our results highlight the value of using holistic system-wide metagenomic approaches as a tool to predict microbial degradation in the context of the ecology of contaminated habitats.

  16. Separating esterase targets of organophosphorus compounds in the brain by preparative chromatography.

    Mangas, I; Vilanova, E; Benabent, M; Estévez, J

    2014-02-10

    Low level exposure to organophosphorus esters (OPs) may cause long-term neurological effects and affect specific cognition domains in experimental animals and humans. Action on known targets cannot explain most of these effects by. Soluble carboxylesterases (EC 3.1.1.1) of chicken brain have been kinetically discriminated using paraoxon, mipafox and phenylmethyl sulfonylfluoride as inhibitors and phenyl valerate as a substrate. Three different enzymatic components were discriminated and called Eα, Eβ and Eγ. In this work, a fractionation procedure with various steps was developed using protein native separation methods by preparative HPLC. Gel permeation chromatography followed by ion exchange chromatography allowed enriched fractions with different kinetic behaviors. The soluble chicken brain fraction was fractionated, while total esterase activity, proteins and enzymatic components Eα, Eβ and Eγ were monitored in each subfraction. After the analysis, 13 fractions were pooled and conserved. Preincubation of the soluble chicken brain fraction of with the organophosphorus mipafox gave rise to a major change in the ion exchange chromatography profile, but not in the molecular exchanged chromatography profile, which suggest that mipafox permanently modifies the ionic properties of numerous proteins. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

  17. Osmoregulatory function in ducks following ingestion of the organophosphorus insecticide fenthion

    Rattner, B.A.; Fleming, W.J.; Murray, H.C.

    1983-01-01

    Salt gland function and osmoregulation in aquatic birds drinking hyperosmotic water has been suggested to be impaired by organophosphorus insecticides. To test this hypothesis, adult black ducks (Anas rubripes) were provided various regimens of fresh or salt (1.5% NaCl) water before, during, and after ingestion of mash containing 21 ppm fenthion. Ducks were bled by jugular venipuncture after I, 7. and 12 days of treatment, and were then killed. Brain and salt gland acetylcholinesterase activities were substantially inhibited (44-61% and 14-36%) by fenthion. However, salt gland weight and Na + -K + -ATPase activity, and plasma Na + , CI- , and osmolality, were uniformly elevated in all groups receiving salt water including those ingesting fenthion. In a second study, salt gland Na + -K + -ATPase activity in mallards (A. platyrhynchos) was not affected after in vitro incubation with either fenthion or fenthion oxon at concentrations ranging from 0.04 to 400 ?M, but was reduced in the presence of 40 and 400 ?M DDE (positive control). These findings suggest that environmentally realistic concentrations of organophosphorus insecticides do not markedly affect osmoregulatory function in adult black ducks.

  18. Organophosphorus and Organochlorine Pesticides Bioaccumulation by Eichhornia crassipes in Irrigation Canals in an Urban Agricultural System.

    Mercado-Borrayo, B M; Cram Heydrich, Silke; Pérez, Irma Rosas; Hernández Quiroz, Manuel; De León Hill, Claudia Ponce

    2015-01-01

    A natural wetland in Mexico City Metropolitan Area is one of the main suppliers of crops and flowers, and in consequence its canals hold a high concentration of organochlorine (OC) and organophosphorus (OP) pesticides. There is also an extensive population of water hyacinth (Eichhornia crassipes), which is considered a plague; but literature suggests water hyacinth may be used as a phytoremediator. This study demonstrates bioaccumulation difference for the OC in vivo suggesting their bioaccumulation is ruled by their log K(ow), while all the OP showed bioaccumulation regardless of their log K(ow). The higher bioaccumulation factors (BAF) of the accumulated OC pesticides cannot be explained by their log K(ow), suggesting that the OC pesticides may also be transported passively into the plant. Translocation ratios showed that water hyacinth is an accumulating plant with phytoremediation potential for all organophosphorus pesticides studied and some organochlorine pesticides. An equation for free water surface wetlands with floating macrophytes, commonly used for the construction of water-cleaning wetlands, showed removal of the pesticides by the wetland with room for improvement with appropriate management.

  19. The analysis of common metabolites of organophosphorus pesticides in urine by gas chromatography/mass spectrometry

    Park, Seong Soo; Pyo, Hee Soo; Lee, Kang Jin; Park, Song Ja; Park, Taek Kyu

    1998-01-01

    Most organophosphorus pesticides may be metabolized to yield some common phosphates in human or in animals, and these metabolites may be used as the exposure biomarkers to pesticides. In this study, we developed the extraction method of four phosphate metabolites from the spiked human urine in high recovery by the solid phase extraction with a reverse-phase cartridge (cyclohexyl silica) followed by the elution with methanol. The extracted urinary metabolites were derivatized with hexamethyldisilazane/trimethyl-chlorosilane/pyridine (2:1:10, v/v/v) and identified by gas chromatography/mass spectrometry. Calibration curve obtained from each metabolite standard using by GC/MS/SIM has shown good linearity and detection limits of metabolites were the range of 0.05-0.1 μg/ml in urine. Phenthoate, one of the organophosphorus pesticides, was orally administrated to rats. Four metabolites were detected in the rat urine. The results of this study may be applied to development of exposure biomarkers for monitoring of environmental pollutants

  20. Organochlorine and organophosphorus pesticide residues in fodder and milk samples along Musi river belt, India

    Korrapati Kotinagu

    2015-04-01

    Full Text Available Aim: The present study was conducted to find the organochlorine pesticide (OCP and organophosphorus pesticide (OPP residues in fodder and milk samples along Musi river belt, India. Materials and Methods: Fodder and milk samples collected from the six zones of Musi river belt, Hyderabad India were analyzed by gas chromatography with electron capture detector for OCP residues and pulsated flame photometric detector for the presence of OPP residues. Results: The gas chromatographic analysis of fodder samples of Zone 5 of Musi river showed the residues of dicofol at concentration of 0.07±0.0007 (0.071-0.077. Among organophosphorus compounds, dimetheoate was present in milk samples collected from Zone 6 at a level of 0.13±0.006 (0.111-0.167. The residues of OCPs, OPPs and cyclodies were below the detection limit in the remaining fodder and milk samples collected from Musi river belt in the present study. Conclusion: The results indicate that the pesticide residues in fodder and milk samples were well below the maximum residue level (MRL values, whereas dicofol in fodder and dimethoate in milk were slightly above the MRL values specified by EU and CODEX.

  1. Organochlorine and organophosphorus pesticide residues in fodder and milk samples along Musi river belt, India.

    Kotinagu, Korrapati; Krishnaiah, Nelapati

    2015-04-01

    The present study was conducted to find the organochlorine pesticide (OCP) and organophosphorus pesticide (OPP) residues in fodder and milk samples along Musi river belt, India. Fodder and milk samples collected from the six zones of Musi river belt, Hyderabad India were analyzed by gas chromatography with electron capture detector for OCP residues and pulsated flame photometric detector for the presence of OPP residues. The gas chromatographic analysis of fodder samples of Zone 5 of Musi river showed the residues of dicofol at concentration of 0.07±0.0007 (0.071-0.077). Among organophosphorus compounds, dimetheoate was present in milk samples collected from Zone 6 at a level of 0.13±0.006 (0.111-0.167). The residues of OCPs, OPPs and cyclodies were below the detection limit in the remaining fodder and milk samples collected from Musi river belt in the present study. The results indicate that the pesticide residues in fodder and milk samples were well below the maximum residue level (MRL) values, whereas dicofol in fodder and dimethoate in milk were slightly above the MRL values specified by EU and CODEX.

  2. Intensification of Organophosphorus Hydrolase Synthesis by Using Substances with Gas-Transport Function

    Olga Senko

    2017-12-01

    Full Text Available We have performed studies and comparative analysis of the biosynthesis characteristics of intracellular recombinant enzyme, such as hexahistidine-containing organophosphorus hydrolase (His6-OPH in Escherichia coli SG13009[pREP4] cells when various perfluorocarbon compounds (PFC were introduced into the medium for cell cultivation. The PFC were found to facilitate the biosynthesis of His6-OPH: increased levels of the total OPH-activity (up to 37% were measured upon introduction of 1,1,1,2,2,3,3,4,4,5,5,6,6,6-tetradecafluorohexane (PFH and 4,7,10,13,16,19,22,25,28,31-decaoxaperfluoro-5,8,11,14,17,18,21,24,27,30-decamethyl tetratriacontane (Polyether II into culture medium. We have demonstrated the possibility of effective and multiple (at least five-fold use of PFH for biosynthesis of intracellular recombinant protein His6-OPH, which catalyzes the hydrolysis of organophosphorus pesticides (OP, is widely used in agriculture and can be applied as new antidote for OP-detoxification in vivo. The multiple use of PFH was achieved through recycling of this substance: sediment of Escherichia coli SG13009[pREP4] cell biomass was collected at the end of each culture growing step and disintegrated with ultrasound, and obtained residue containing almost all of the initially introduced PFC was then added to the medium at the start of the following culture growing step.

  3. ACUTE EXOGENOUS INTOXICATIONS WITH ORGANOPHOSPHORUS PESTICIDES: DURATION OF THE HOSPITAL TREATMENT AND CLINICAL CRITERIA FOR PROGNOSIS

    Petko Marinov

    2017-05-01

    Full Text Available Purpose: Several criteria have been suggested to estimate the intoxication severity, yet so far no system of clinical criteria has been developed to determine the duration of hospitalisation. The forecast is linked to the influence of the extended corrected QT interval and GCS (Glasgow Coma Scale on the frequency of the developing acute pulmonary insufficiency and lethality. The average duration of hospital treatment is also crucial. First of all, it is determined by the intoxication severity and lasts from 3 to 26 days. The aim of this study is to develop an individual forecast about the duration of hospitalisation for patients suffering from acute exogenous intoxication with organophosphorus pesticides (OPP. Materials/Methods: The subjects are 160 patients. We use statistical regression analysis to study the significance of 5 of the most typical clinical indicators of organophosphorus intoxication on the duration of hospitalisation: type of conscience, presence of spasms, pulmonary oedema, shock and multi-organ insufficiency syndrome (MOIS. To forecast the treatment length, we obtain simplified mathematical expressions in the form of score estimates. Results: The significance of the clinical indicators “MOIS”, “conscience” and “spasm” has been confirmed. A forecast matrix that gives the opportunity to forecast the personal duration of hospital treatment for each patient has been built.

  4. In vivo tracing of organophosphorus pesticides in cabbage (Brassica parachinensis) and aloe (Barbadensis)

    Qiu, Junlang; Chen, Guosheng; Zhou, Hong; Xu, Jianqiao; Wang, Fuxin; Zhu, Fang; Ouyang, Gangfeng

    2016-01-01

    In vivo solid-phase microextraction (SPME) sampling method coupled with gas chromatography–mass spectrometry (GC–MS) analysis was employed to trace the uptake and elimination of organophosphorus pesticides (OPPs) in two kinds of edible plants, cabbage (Brassica parachinensis) and aloe (Barbadensis). The metabolism of fenthion in aloe was also investigated by the liquid chromatography tandem mass spectrometry analysis (LC–MS/MS) to understand the fate of OPPs in living plants better. Transpiration stream concentration factor (TSCF) and depuration rate constants of the OPPs in living plants were obtained therein. The health risk of the OPPs treated aloe was estimated by the maximum residue limit (MRL) approach, and it revealed that the OPPs were rather safe for their fast degradable property. However, peak concentration of fenthion-sulfoxide was found to exceed the MRL and was higher than that of the parent fenthion, which indicated the potential risk of pesticide metabolites. This study highlighted the application of in vivo SPME for contaminant tracing in different living edible plants. The in vivo tracing method is very convenient and can provide more data to evaluate the risk of different pesticides, which are very important for the safety of agriculture production. - Highlights: • In vivo SPME was employed to sample organophosphorus pesticides in vegetables. • Uptake and elimination of OPPs were traced in cabbage and aloe. • In vivo tracing of fenthion demonstrated its metabolites could be rather dangerous. • The risks of OPPs were assessed based on the in vivo tracing data.

  5. Radiolytic investigations of solutions of organophosphorus compounds in cyclohexane and benzene

    Otrebski, W.

    1981-01-01

    Organphosphorus compounds are used in various branches of the chemical industry, but in many cases the reaction mechanisms are not well elucidated and less is known about the intermediates of organophosphines. In order to learn more about these rather complicated processes several organophosphorus compounds were used as model substrates in cyclohexane or benzene solution. The systems have been investigated applying the pulse radiolysis technique and steady-state irradiation methods. As representative solutes were chosen diphenylphosphinous chloride, diphenylmethylphosphine, and triphenylphosphine. By means of the pulse radiolysis it was possible to obtain spectroscopic and kinetic data for characterization of the various transients. The final radiolytic products have been analyzed following steady-state and multipulse radiolysis. Since some of the rate constants were not directly accessible by the applied kinetic method, they have been determined by simulation computation. Thereby the experimental data obtained by pulse radiolysis were used. Based on the kinetic, spectroscopic and computed data as well as on the identification of final products, it was possible to elucidate the reaction mechanism of the diphenylphosphinous chloride/cyclohexane system. As a main primary specie was identified the diphenylphoshorus radical. Its spectral and kinetic data have been determined. The reactions of diphenylmethylphosphine involve the same radical, but only to a lesser extent. The reactions of the primary radiolysis products with triphenylphosphine yield mainly adducts. The results represent a contribution in the field of reaction kinetics of organophosphorus compounds. (author)

  6. Potentiation of ecological factors on the disruption of thyroid hormones by organo-halogenated contaminants in female polar bears (Ursus maritimus) from the Barents Sea.

    Bourgeon, Sophie; Riemer, Astrid Kolind; Tartu, Sabrina; Aars, Jon; Polder, Anuschka; Jenssen, Bjørn Munro; Routti, Heli

    2017-10-01

    As apex predators, polar bears (Ursus maritimus) are among the most heavily polluted organisms in the Arctic. In addition to this anthropogenic stressor, climate warming has been shown to negatively affect their body condition, reproductive output and survival. Among potential underlying physiological mechanisms, thyroid hormones (THs), which control thermoregulation, metabolism and reproduction, can be affected by a variety of both natural and anthropogenic factors. While THs have been extensively used as proxies for pollution exposure in mammals, including polar bears, there is a lack of knowledge of their natural variations. In this context, we examined seasonal variations in body condition and circulating TH concentrations in free-ranging female polar bears. Females with variable reproductive status (i.e., solitary, with cubs of the year or with yearlings) were sampled from locations with contrasted sea ice conditions. Furthermore, we studied THs in relation to levels of organo-halogenated contaminants. As predicted, solitary females were in better condition than females caring for offspring, especially in spring. In addition, TH levels were lower in autumn compared to spring, although this seasonal effect was mainly observed in solitary females. Finally, the negative relationships between organochlorine and perfluoroalkyl substances and some THs suggest a possible alteration of homeostasis of THs. Since the latter relationships were only observed during spring, we emphasize the importance of considering the ecological factors when using THs as proxies for pollution exposure. Yet, the combined effects of natural and anthropogenic stressors on THs might impair the ability of polar bears to adapt to ongoing climate changes. Copyright © 2017 Elsevier Inc. All rights reserved.

  7. Species-specific differences in the accumulation features of organohalogen contaminants and their metabolites in the blood of Japanese terrestrial mammals

    Mizukawa, Hazuki; Nomiyama, Kei; Nakatsu, Susumu; Yachimori, Shuuji; Hayashi, Terutake; Tashiro, Yutaka; Nagano, Yasuko; Tanabe, Shinsuke

    2013-01-01

    Residue levels and patterns of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), their hydroxylated metabolites (OH-PCBs, OH-PBDEs), and methoxylated PBDEs (MeO-PBDEs) in the blood of various terrestrial mammals in Japan, including cats, raccoon dogs, dogs, masked palm civets, foxes, raccoons, badgers, and mongooses were determined. Tri- through penta-chlorinated OH-PCBs were predominant in cat blood, whereas hexa- through octa-chlorinated OH-PCBs were found in other species. High proportion of BDE209 was found in all species, suggesting exposure to municipal waste and soil containing higher levels of deca-BDE products. 6OH-/MeO-BDE47 and 2′OH-/MeO-BDE68 were dominant in all terrestrial mammals. This is first report on the detection of OH-/MeO-PBDEs in the blood of terrestrial mammals. High concentrations of OH-/MeO-PBDEs were found in cats, suggesting the intake of these compounds from seafood. Cats exhibited higher accumulation and specific patterns of OH-PCBs, OH-PBDEs, and MeO-PBDEs, they may be at a high risk from these metabolites. -- Highlights: ► Analysis of organohalogen metabolites in the blood of Japanese terrestrial mammals. ► First study on analysis of OH-/MeO-PBDEs in terrestrial mammals. ► Cats showed specific residue pattern of OH-PCBs compare to other species. ► Metabolic capacities of PCBs in carnivore were higher than marine mammals. ► Marine natural occurrence OH-/MeO-PBDEs were found in terrestrial mammals. -- Cats showed specific residue pattern of OH-PCBs compare to other species and marine natural occurrence OH-/MeO-PBDEs were detected in terrestrial mammals

  8. Thyroid hormones and deiodinase activity in plasma and tissues in relation to high levels of organohalogen contaminants in East Greenland polar bears (Ursus maritimus).

    Gabrielsen, Kristin Møller; Krokstad, Julie Stene; Villanger, Gro Dehli; Blair, David A D; Obregon, Maria-Jesus; Sonne, Christian; Dietz, Rune; Letcher, Robert J; Jenssen, Bjørn Munro

    2015-01-01

    Previous studies have shown relationships between organohalogen contaminants (OHCs) and circulating levels of thyroid hormones (THs) in arctic wildlife. However, there is a lack of knowledge concerning the possible functional effects of OHCs on TH status in target tissues for TH-dependent activity. The relationships between circulating (plasma) levels of OHCs and various TH variables in plasma as well as in liver, muscle and kidney tissues from East Greenland sub-adult polar bears (Ursus maritimus) sampled in 2011 (n=7) were therefore investigated. The TH variables included 3.3',5.5'-tetraiodothyronine or thyroxine (T4), 3.3',5-triiodothyronine (T3) and type 1 (D1) and type 2 (D2) deiodinase activities. Principal component analysis (PCA) combined with correlation analyses demonstrated negative relationships between individual polychlorinated biphenyls (PCBs) and their hydroxylated (OH-) metabolites and T4 in both plasma and muscle. There were both positive and negative relationships between individual OHCs and D1 and D2 activities in muscle, liver and kidney tissues. In general, PCBs, OH-PCBs and polybrominated dipehenyl ethers (PBDEs) were positively correlated to D1 and D2 activities, whereas organochlorine pesticides and byproducts (OCPs) were negatively associated with D1 and D2 activities. These results support the hypothesis that OHCs can affect TH status and action in the target tissues of polar bears. TH levels and deiodinase activities in target tissues can be sensitive endpoints for exposure of TH-disrupting compounds in arctic wildlife, and thus, tissue-specific responses in target organs should be further considered when assessing TH disruption in wildlife studies. Copyright © 2014 Elsevier Inc. All rights reserved.

  9. Reproductive performance in East Greenland polar bears (Ursus maritimus) may be affected by organohalogen contaminants as shown by physiologically-based pharmacokinetic (PBPK) modelling.

    Sonne, Christian; Gustavson, Kim; Rigét, Frank F; Dietz, Rune; Birkved, Morten; Letcher, Robert J; Bossi, Rossana; Vorkamp, Katrin; Born, Erik W; Petersen, Gitte

    2009-12-01

    Polar bears (Ursus maritimus) feed mainly on ringed seal (Phoca hispida) and consume large quantities of blubber and consequently have one of the highest tissue concentrations of organohalogen contaminants (OHCs) worldwide. In East Greenland, studies of OHC time trends and organ system health effects, including reproductive, were conducted during 1990-2006. However, it has been difficult to determine the nature of the effects induced by OHC exposures on wild caught polar bears using body burden data and associated changes in reproductive organs and systems. We therefore conducted a risk quotient (RQ) evaluation to more quantitatively evaluate the effect risk on reproduction (embryotoxicity and teratogenicity) based on the critical body residue (CBR) concept and using a physiologically-based pharmacokinetic (PBPK) model. We applied modelling approaches to PCBs, p,p'-DDE, dieldrin, oxychlordane, HCHs, HCB, PBDEs and PFOS in East Greenland polar bears based on known OHC pharmacokinetics and dynamics in laboratory rats (Rattus rattus). The results showed that subcutaneous adipose tissue concentrations of dieldrin (range: 79-1271 ng g(-1) lw) and PCBs (range: 4128-53,923 ng g(-1) lw) reported in bears in the year 1990 were in the range to elicit possible adverse health effects on reproduction in polar bears in East Greenland (all RQs > or = 1). Similar results were found for PCBs (range: 1928-17,376 ng g(-1) lw) and PFOS (range: 104-2840 ng g(-1) ww) in the year 2000 and for dieldrin (range: 43-640 ng g(-1) lw), PCBs (range: 3491-13,243 ng g(-1) lw) and PFOS (range: 1332-6160 ng g(-1) ww) in the year 2006. The concentrations of oxychlordane, DDTs, HCB and HCHs in polar bears resulted in RQspolar bears correlated to OHC exposure are supported by the present study. This study also indicates that PBPK models may be a supportive tool in the evaluation of possible OHC-mediated health effects for Arctic wildlife.

  10. Novel Developments in Organonitrogen Fluorine Chemistry from Carbon- Nitrogen

    1991-11-21

    ref. 2 and references therein.3 2 U 392 CFI T (*C) NF __ -1003 -20 3 - 3d ’ -50 -7°° Fig. 1. 19F NMR OF CF3NFH2+AsF6- in HOSO 2F. 1000 Hz sweep width...zunAchst un- gen bei einemn Druck von etwa 10-: mbar Millimol- tersuchte Difluormethylazid F2HC-N-, liefert jedoch Mengen. urn innerhalb weniger Stunden in... Druck und mit etwa 10" cps registriert. die Nachweis ungeeignet: hier bildet sich aus FC-N, Auflosung betrug 30 rneV. Alle Spektren sind mit emn Gemisch

  11. Recent Developments in Organophosphorus Flame Retardants Containing P-C Bond and Their Applications

    Sophie Wendels

    2017-07-01

    Full Text Available Organophosphorus compounds containing P-C bonds are increasingly developed as flame retardant additives due to their excellent thermal and hydrolytic stability and ease of synthesis. The latest development (since 2010 in organophosphorus flame retardants containing P-C bonds summarized in this review. In this review, we have broadly classified such phosphorus compounds based on the carbon unit linked to the phosphorus atom i.e., could be a part of either an aliphatic or an aromatic unit. We have only considered those published literature where a P-C bond was created as a part of synthetic strategy to make either an intermediate or a final organophosphorus compound with an aim to use it as a flame retardant. General synthetic strategies to create P-C bonds are briefly discussed. Most popular synthetic strategies used for developing P-C containing phosphorus based flame retardants include Michael addition, Michaelis–Arbuzov, Friedels–Crafts and Grignard reactions. In general, most flame retardant derivatives discussed in this review have been prepared via a one- to two-step synthetic strategy with relatively high yields greater than 80%. Specific examples of P-C containing flame retardants synthesized via suitable synthetic strategy and their applications on various polymer systems are described in detail. Aliphatic phosphorus compounds being liquids or low melting solids are generally applied in polymers via coatings (cellulose or are incorporated in the bulk of the polymers (epoxy, polyurethanes during their polymerization as reactive or non-reactive additives. Substituents on the P atoms and the chemistry of the polymer matrix greatly influence the flame retardant behavior of these compounds (condensed phase vs. the gas phase. Recently, aromatic DOPO based phosphinate flame retardants have been developed with relatively higher thermal stabilities (>250 °C. Such compounds have potential as flame retardants for high temperature processable

  12. Trace Detection of Organophosphorus Chemical Warfare Agents in Wastewater and Plants by Luminescent UIO-67(Hf) and Evaluating the Bioaccumulation of Organophosphorus Chemical Warfare Agents.

    Lian, Xiao; Yan, Bing

    2018-05-02

    Organophosphorus chemical warfare agents (OPCWAs) are a group of organic pollutants characterized by high toxicity and chemical stability, and they are very difficult to be degraded. The trace quality of OPCWAs in water and food will cause great harm to the human body. Therefore, the detection of OPCWAs is a difficult challenge, which has become the research hotspot over the world. In this work, a Hf-based luminescent metal-organic framework (Eu@1) is prepared, and the reactivity of Hf 12 results in a methanephosphonic acid (MPA)-induced luminescence quenching and the charge transfer from MPA to Hf(IV) and generated exciplexes which are responsible for this quenching effect. The excellent performance of Eu@1 in the detection of MPA, with its finer selectivity, high sensitivity (LOD = 0.4 ppm), and large linear range (10 -7 to 10 -3 M), is encouraging for application in wastewater detection. Importantly, MPA is a pollutant that can be absorbed by plants and causes the bioaccumulation effect, and thus, the detection of MPA in real plant samples is a purposeful topic. Eu@1 also achieved satisfactory results in actual plant sample testing, and the bioaccumulation of MPA in onions, turnips, and cabbages is determined via our sensor. This fabricated detector provides a feasible path for the detection of ppm-level OPCWAs in a complex environment, which will help humans to avoid OPCWA-contaminated foods.

  13. Estimation of solubility of organo-phosphorus extractants by P determination using molybdovanadophosphoric acid method

    Gill, J.S.; Kotekar, M.K.; Singh, H.

    2005-01-01

    Solvent extraction processes have been found to be suitable for uranium recovery from phosphoric acid. Various extractants like di-2-ethyl hexylphosphoric acid (D2EHPA), di-nonylphenyl phosphoric acid (DNPPA) and synergistic agents like tri-butyl phosphate (TBP), tri-octyl phosphine oxide (TOPO) have been used in liquid-liquid extraction of uranium from phosphoric acid. Contents of these organo-phosphorus compounds in aqueous raffinates need estimation for process requirements. Solubility of Tri-butyl phosphate (TBP) and Di-2-ethylhexyl phosphoric acid (D2EHPA) extractants have been determined in different media of water, oxalic acid (0.6M) and sulphuric acid (3.75M) solutions. These compounds were estimated by determining their phosphorus (P) contents employing molybdovanadophosphoric acid method, after digesting and solubalizing them in nitric and perchloric acid. (author)

  14. Concentration of Organochlorine and Organophosphorus Pesticides in Different Molluscs from Tighra Reservoir, Gwalior, India.

    Mamta; Rao, R J; Wani, Khursheed Ahmad

    2015-09-01

    Concentration of organochlorine and organophosphorus pesticides and their metabolites were determined in whole body homogenate of L. acuminata, I. exustus, V. dissimilis, V. bengalensis, from Tighra Reservoir during summer and post monsoon season using GC-MS technique. The different types of pesticides viz., HCB, heptachlor, aldrin, endosulfan, dieldrin, p,p-DDT, choloropyrifos, methyl parathion, dicholorovos, ethion, malathion, parathion were found in resident molluscs studied. Concentration of these pesticides varied independently during the summer and the post monsoon season at monitored sites. The study concluded that presence of pesticides in Tighra Reservoir is a major concern on public and ecosystem health and use of biopesticides in the adjacent area of Reservoir is highly recommended.

  15. Electrochemical process for the treatment of water contaminated with organophosphorus pesticides

    Samet, Youssef; Agengui, Lamia; Abdelhedi, Ridha

    2009-01-01

    The aim of this work is the use of electrochemical process for the total mineralization of water contaminated with organophosphorus pesticides like chloropyrifos. This pesticide is widely used both for agricultural pest control and in households as a termiticide. The process was studied under galvanostatic polarization mode using Ta/PbO 2 anodes and graphite carbon bar as cathode. The kinetic of organic matter decay and the mineralization efficiency were evaluated by means of the chemical oxygen demand (COD) measurement. The influence of the experimental parameters such as the initial concentration of chloropyrifos, temperature, and current density, on the electrochemical process performance was investigated. The experimental results showed that COD removal always follows a pseudo-first-order kinetics. The degradation rate increased drastically with increasing current density and temperature. However, it decreased with the increase of the initial pollutant concentrations. Very high organic matter degradation, approximately 90 pour cent in 10 h experiments, was obtained.

  16. Degradation kinetics of seven organophosphorus pesticides in milk during yoghurt processing

    LI-YING BO

    2011-03-01

    Full Text Available Bovine milk spiked with seven organophosphorus pesticides, i.e., dimethoate, fenthion, malathion, methyl parathion, monocrotophos, phorate and trichlorphon, was fermented at 42 °C with commercial directed vat set (DVS starters to investigate the degradation kinetics of the pesticides during yoghurt processing. The spiked pesticides were extracted from the prepared samples with an organic solvent and analyzed by gas chromatography after purification. Based on published results that the degradation kinetics of pesticides is first order, the rate constant of degradation and the half live period of the pesticides were calculated. The results indicated that degradation of the pesticides in milk during yoghurt processing were enhanced by one or both starters, except for malathion, and the two commercial DVS starters had different influences on the degradation kinetics of the pesticides.

  17. Assessment of some biochemical and hematological parameters in treated with the organophosphorus insecticide cyanox

    ElMahdy, A.A.; Fayz, V.; Hassanin, M.M.

    2002-01-01

    The effect of single acute oral doses of 29 and 58 mg/kg of cyanox (an organophosphorus pesticide) on selected biochemical and hematological parameters in male rats were investigated. This compound inhibited blood acetylcholine esterase (AChE) significantly, over 72 hours post-treatment with the higher dose level. Serum alkaline phosphatase (ALP) was significantly depressed, 48 hr after treatment with 58 mg/kg. Serum bilirubin was elevated significantly after 48 and 24 hr of treatment with 29 and 58 mg/kg, respectively. Serum cholesterol increased significantly over 48 hr post-treatment with both dose levels.Hypertriglyceridemia was noticed only in the higher dose group. Serum total lipids were increased significantly at both dose levels. A slight treatment-related effect was observed in serum creatinine level. The hematological investigations revealed the occurrence of macrocytic normochromic anemia that was more evident in the lower dose group

  18. Is the stoichiometry of the europium nitrate complexes with neutral organophosphorus extractants be anticipated?

    Beudaert, Ph.; Lamare, V.; Wipff, G.

    2001-01-01

    Molecular dynamics simulations have been performed in water on europium nitrate complexes with three neutral organophosphorus extractants (TBP, TPPO and CMPO) in order to determine on what criteria it is possible to obtain by simulations the experimental 1:3 stoichiometry in organic solution. This stoichiometry was investigated by progressive saturation of the cation coordination sphere. When the nitrate counter-ions are bidentate, the 1:3 stoichiometry corresponds to the degree of saturation where the interaction energy between europium and water becomes repulsive. Beyond this stoichiometry, complexes with TPPO and CMPO are unstable, although a 1:4 complex with TBP may exist but its formation appears to be energetically unfavored. (author)

  19. Influence of modifiers on the separation of dysprosium from neodymium using organophosphorus acid derivates

    Elwert, Tobias; Schwarz, Sabrina; Goldmann, Daniel [TU Clausthal, Clausthal-Zellerfeld (Germany). Lehrstuhl fuer Rohstoffaufbereitung und Recycling

    2016-01-15

    The aim of this study was to investigate the applicability of three organophosphorus acid derivates (D2EHPA, EHEHPA and Cyanex 572) for the separation of terbium and dysprosium from praseodymium and neodymium from NdFeB magnets in chloride solution. A special focus was put on the effect of phase modifiers. The investigations revealed that all extractants show in general a similar extraction behavior but the extraction is shifted to higher pH values in the order D2EHPA < EHEHPA < Cyanex 572. Therefore, and due to higher realizable loadings, EHEHPA and Cyanex 572 are more suitable for the investigated separation problem than D2EHPA. Whereas EHEHPA requires 1-decanol as phase modifier, Cyanex 572 can be employed without modifier addition.

  20. Nicotine And The Risk Of Exposure To The Organophosphorus Insecticide Cyolane

    Hassanin M, M.; Bahig Mervat, E.

    1999-01-01

    The present investigation was undertaken to show the effect of repeated oral doses of nicotine (0.5 mg/kg) on rats pretreated or during treatment with cyolane (0.5 mg/kg 1/20 LD 5 0). The results revealed that exposure of smokers to organophosphorus pesticides exerted slight changes in GOT and GPT. Alkaline phosphatase was significantly increased to reach maximal (228.54 and 148.64%) after nicotine + cyolane and/or nicotine were given for a week to rats pretreated with cyolane for 2 weeks. Total protein, albumin and Albumin/Globulin (A/G) ratio were also affected. Administration of nicotine along with cyolane to rats showed a significant increase in cholesterol content compared to that of cyolane treated rats. Values of thyroxine (T 4 ) and triiodothyronine (T 3 ) also fluctuated

  1. Multipathway organophosphorus pesticide exposures of preschool children living in agricultural and nonagricultural communities

    Lu Chensheng; Kedan, Golan; Fisker-Andersen, Jennifer; Kissel, J.C.; Fenske, R.A.

    2004-01-01

    Environmental measurements of organophosphorus (OP) pesticides were conducted in the homes of 13 children, who lived either in the Seattle metropolitan area or in the agricultural region of Washington State, to ascertain exposure through multiple pathways. Each home was sampled for two 24-h periods during two seasons, summer and fall. Samples included 24-h indoor air, drinking water, soil, house dust, and hand and toy wipes and 24-h duplicate diets. At least one OP pesticide was found in each of the matrices sampled except for drinking water. Half of the indoor air samples contained detectable levels of chlorpyrifos or diazinon. Detectable levels of diazinon and azinphosmethyl in house dust were found in most of the agricultural homes, whereas only diazinon was found in the Seattle homes in the summer. Quantifiable chlorpyrifos and azinphosmethyl were found on either agricultural children's hands or their toys. These findings suggest different exposure pathways for children living in agricultural and nonagricultural regions

  2. Engineering and introduction of de novo disulphide bridges in organophosphorus hydrolase enzyme for thermostability improvement.

    Farnoosh, Gholamreza; Khajeh, Khosro; Latifi, Ali Mohammad; Aghamollaei, Hossein

    2016-12-01

    The organophosphorus hydrolase (OPH) has been used to degrade organophosphorus chemicals, as one of the most frequently used decontamination methods. Under chemical and thermal denaturing conditions, the enzyme has been shown to unfold. To utilize this enzyme in various applications, the thermal stability is of importance. The engineering of de novo disulphide bridges has been explored as a means to increase the thermal stability of enzymes in the rational method of protein engineering. In this study, Disulphide by Design software, homology modelling and molecular dynamics simulations were used to select appropriate amino acid pairs for the introduction of disulphide bridge to improve protein thermostability. The thermostability of the wild-type and three selected mutant enzymes were evaluated by half-life, delta G inactivation (ΔGi) and structural studies (fluorescence and far-UV CD analysis). Data analysis showed that half-life of A204C/T234C and T128C/E153C mutants were increased up to 4 and 24 min, respectively; however, for the G74C/A78C mutant, the half-life was decreased up to 9 min. For the T128C/E124C mutant, both thermal stability and Catalytic efficiency (kcat) were also increased. The half-life and ΔGi results were correlated to the obtained information from structural studies by circular dichroism (CD) spectrometry and extrinsic fluorescence experiments; as rigidity increased in A204C/T2234C and T128C/E153C mutants, half-life and ΔGi also increased. For G74C/A78C mutant, these parameters decreased due to its higher flexibility. The results were submitted a strong evidence for the possibility to improve the thermostability of OPH enzyme by introducing a disulphide bridge after bioinformatics design, even though this design would not be always successful.

  3. The solvent extraction of zinc, iron, and indium from chloride solutions by neutral organophosphorus compounds

    Preston, J.S.; Du Preez, A.C.

    1985-01-01

    The preparation of several neutral organophosphorus compounds and their evaluation as selective extractants for zinc in chloride media are described. The compounds belong to the series trialkyl phosphates (RO) 3 PO, dialkyl alkylphosphonates R'PO(OR) 2 , alkyl dialkylphosphinates R 2 'PO(OR), and trialkyl-phosphine oxides R 3 'PO. They were characterized by measurement of their physical properties (melting and boiling points, refractive indices, and densities), and their purities were confirmed by osmometric determination of their molecular masses; by carbon and hydrogen microanalysis; by the titrimetric determination of acidic impurities; and, for liquid products, by comparison of their experimental molar refractivities with empirical values. Metal-distribution equilibria were determined for solutions of the extractants in xylene and aqueous phase containing 0,5 to 5,0 M sodium chloride. Moderately good selectivities were shown for zinc(II) over iron(III), and excellent selectivities were shown for zinc(II) over iron(II), copper(II), lead(II), and cadmium(II). The extraction of indium(III) was similar to that of zinc(II). The extraction of zinc(III), iron(III), and indium(III) increased markedly through the series. (RO) 3 PO 2 2 'PO(OR) 3 'PO. The incorporation of phenyl groups into the compounds led to weaker extraction. The extracted complexes of zinc(II), iron(III), and indium(III) have the stoichiometries ZnCl 2 L 2 ,FeCl 3 L 2 (H 2 O), and InCl 3 L 2 (H 2 O) respectively, where L represents the neutral organophosphorus compound

  4. Current status, between-year comparisons and maternal transfer of organohalogenated compounds (OHCs) in Arctic char (Salvelinus alpinus) from Bjørnøya, Svalbard (Norway)

    Bytingsvik, J., E-mail: jenny.bytingsvik@akvaplan.niva.no [Akvaplan-niva AS, The Fram Centre, N-9296 Tromsø Norway (Norway); Frantzen, M. [Akvaplan-niva AS, The Fram Centre, N-9296 Tromsø Norway (Norway); Götsch, A.; Heimstad, E.S. [NILU (Norwegian Institute for Air Research), The Fram Centre, N-9296 Tromsø Norway (Norway); Christensen, G. [Akvaplan-niva AS, The Fram Centre, N-9296 Tromsø Norway (Norway); Evenset, A. [Akvaplan-niva AS, The Fram Centre, N-9296 Tromsø Norway (Norway); University of Tromsø, The Arctic University of Norway, Pb 6050 Langnes, N-9037 Tromsø (Norway)

    2015-07-15

    High levels of organohalogenated compounds (OHCs) have been found in Arctic char from Lake Ellasjøen at Bjørnøya (Svalbard, Norway) compared to char from other arctic lakes. The first aim of the study was to investigate the OHC status, contaminant profile, and partitioning of OHCs between muscle and ovary tissue in spawning female char from the high-polluted Lake Ellasjøen and the low-polluted Lake Laksvatn. The second aim was to investigate if OHC levels in muscle tissue have changed over time. Between-lake comparisons show that the muscle levels (lipid weight) of hexachlorobenzene (HCB), chlordanes (∑ CHLs), mirex, dichlorodiphenyltrichloroethanes (∑ DDTs) and polychlorinated biphenyls (∑ PCBs) were up to 36 times higher in char from Ellasjøen than in Laksvatn, and confirm that the char from Ellasjøen are still heavily exposed compared to char from neighboring lake. A higher proportion of persistent OHCs were found in Ellasjøen compared to Laksvatn, while the proportion of the less persistent OHCs was highest in Laksvatn. A between-year comparison of OHC levels (i.e., HCB, DDTs, PCBs) in female and male char shows higher levels of HCB in female char from Ellasjøen in 2009/2012 compared to in 1999/2001. No other between-year differences in OHC levels were found. Due to small study groups, findings associated with between-year differences in OHC levels should be interpreted with caution. OHCs accumulate in the lipid rich ovaries of spawning females, resulting in up to six times higher levels of OHCs in ovaries compared to in muscle (wet weight). The toxic equivalent (TEQ)-value for the dioxin-like PCBs (PCB-105 and -118) in ovaries of the Ellasjøen char exceeded levels associated with increased egg mortality in rainbow trout (Oncorhynchus mykiss). Hence, we suggest that future studies should focus on the reproductive health and performance abilities of the high-exposed population of char inhabiting Lake Ellasjøen. - Highlights: • Examine levels

  5. Current status, between-year comparisons and maternal transfer of organohalogenated compounds (OHCs) in Arctic char (Salvelinus alpinus) from Bjørnøya, Svalbard (Norway)

    Bytingsvik, J.; Frantzen, M.; Götsch, A.; Heimstad, E.S.; Christensen, G.; Evenset, A.

    2015-01-01

    High levels of organohalogenated compounds (OHCs) have been found in Arctic char from Lake Ellasjøen at Bjørnøya (Svalbard, Norway) compared to char from other arctic lakes. The first aim of the study was to investigate the OHC status, contaminant profile, and partitioning of OHCs between muscle and ovary tissue in spawning female char from the high-polluted Lake Ellasjøen and the low-polluted Lake Laksvatn. The second aim was to investigate if OHC levels in muscle tissue have changed over time. Between-lake comparisons show that the muscle levels (lipid weight) of hexachlorobenzene (HCB), chlordanes (∑ CHLs), mirex, dichlorodiphenyltrichloroethanes (∑ DDTs) and polychlorinated biphenyls (∑ PCBs) were up to 36 times higher in char from Ellasjøen than in Laksvatn, and confirm that the char from Ellasjøen are still heavily exposed compared to char from neighboring lake. A higher proportion of persistent OHCs were found in Ellasjøen compared to Laksvatn, while the proportion of the less persistent OHCs was highest in Laksvatn. A between-year comparison of OHC levels (i.e., HCB, DDTs, PCBs) in female and male char shows higher levels of HCB in female char from Ellasjøen in 2009/2012 compared to in 1999/2001. No other between-year differences in OHC levels were found. Due to small study groups, findings associated with between-year differences in OHC levels should be interpreted with caution. OHCs accumulate in the lipid rich ovaries of spawning females, resulting in up to six times higher levels of OHCs in ovaries compared to in muscle (wet weight). The toxic equivalent (TEQ)-value for the dioxin-like PCBs (PCB-105 and -118) in ovaries of the Ellasjøen char exceeded levels associated with increased egg mortality in rainbow trout (Oncorhynchus mykiss). Hence, we suggest that future studies should focus on the reproductive health and performance abilities of the high-exposed population of char inhabiting Lake Ellasjøen. - Highlights: • Examine levels

  6. Divergent effects of postmortem ambient temperature on organophosphorus- and carbamate-inhibited brain cholinesterase activity in birds

    Hill, E.F.

    1989-01-01

    Time- and temperature-dependent postmortem changes in inhibited brain cholinesterase (ChE) activity may confound diagnosis of field poisoning of wildlife by anticholinesterase pesticide. Carbamate-inhibited ChE activity may return to normal within 1 to 2 days of exposure of intact carcass to moderate ambient temperature (18-32C). Organophosphorus-inhibited ChE activity becomes more depressed over the same time. Uninhibited ChE activity was resilient to above freezing temperature to 32C for 1 day and 25C for 3 days. Carbamate- and organophosphorus-inhibited ChE can be separated by incubation of homogenate for 1 hour at physiological temperatures; carbamylated ChE can be readily reactivated while phosphorylated ChE cannot.

  7. Increased fetal endocardial echogenicity mimicking endocardial fibroelastosis following maternal organophosphorus poisoning and its complete regression in utero

    Balakumar, Karippaliyil; Misha, Kannan; Milind, Karippaliyil

    2013-01-01

    Fetal endocardial fibroelastosis (EFE) has been diagnosed by antenatal ultrasonography in the past few years. A typical case of isolated endocardial fibroelastosis is illustrated here, in a fetus of 22 weeks of gestational age exposed to maternal organophosphorus poisoning at 20 weeks. No other structural cardiac or other systemic anomalies were detected in this fetus. The abnormal fetal echocardiographic features mimicking endocardial fibroelastosis completely regressed after 14 weeks and a normal full-term baby was delivered. Postnatal echocardiogram showed normal cardiac parameters. The diagnostic features mimicking EFE following maternal organophosphorus poisoning at 20 weeks of gestational age and the subsequent complete reversal of these changes after 14 weeks of diagnosis are reported for the first time in the literature

  8. Synergistic Extraction of Copper from Nitrate Solutions Using β-Hydroxy-Naphthaldoxime and Organophosphorus Compounds into Carbon-Tetrachloride

    Dey, Pulak; Basu, Sukalyan

    2011-12-01

    The extraction behavior of Cu(II) from an aqueous nitrate medium employing β-hydroxy-naphthaldoxime in carbon tetrachloride has been investigated in the presence of several organophosphorus donors like tri-octyl phosphine oxide, tri-butyl phosphine oxide, and tri-butyl phosphate at pH 1.5. The concentration of the metal was measured by atomic absorption spectrophotometry. Synergism was observed when neutral donor was added because of the formation of the adduct [Cu(L)2.(S)] in CCl4 (S denotes neutral donor). The equilibrium constants of the binary system using β-hydroxy-naphthaldoxime and the ternary system involving another addition of an organophosphorus compound were calculated from the extraction date obtained. Furthermore, the temperature dependence of the equilibrium constants was also investigated to evaluate standard enthalpy (Δ H°), entropy (Δ S°), and free energy (Δ G°) of the reactions proposed.

  9. Expression of organophosphorus-degradation gene ( opd) in aggregating and non-aggregating filamentous nitrogen-fixing cyanobacteria

    Li, Qiong; Tang, Qing; Xu, Xudong; Gao, Hong

    2010-11-01

    Genetic engineering in filamentous N2-fixing cyanobacteria usually involves Anabaena sp. PCC 7120 and several other non-aggregating species. Mass culture and harvest of such species are more energy consuming relative to aggregating species. To establish a gene transfer system for aggregating species, we tested many species of Anabaena and Nostoc, and identified Nostoc muscorum FACHB244 as a species that can be genetically manipulated using the conjugative gene transfer system. To promote biodegradation of organophosphorus pollutants in aquatic environments, we introduced a plasmid containing the organophosphorus-degradation gene ( opd) into Anabaena sp. PCC 7120 and Nostoc muscorum FACHB244 by conjugation. The opd gene was driven by a strong promoter, P psbA . From both species, we obtained transgenic strains having organophosphorus-degradation activities. At 25°C, the whole-cell activities of the transgenic Anabaena and Nostoc strains were 0.163±0.001 and 0.289±0.042 unit/μg Chl a, respectively. However, most colonies resulting from the gene transfer showed no activity. PCR and DNA sequencing revealed deletions or rearrangements in the plasmid in some of the colonies. Expression of the green fluorescent protein gene from the same promoter in Anabaena sp. PCC 7120 showed similar results. These results suggest that there is the potential to promote the degradation of organophosphorus pollutants with transgenic cyanobacteria and that selection of high-expression transgenic colonies is important for genetic engineering of Anabaena and Nostoc species. For the first time, we established a gene transfer and expression system in an aggregating filamentous N2-fixing cyanobacterium. The genetic manipulation system of Nostoc muscorum FACHB244 could be utilized in the elimination of pollutants and large-scale production of valuable proteins or metabolites.

  10. [Determination of 44 organophosphorus pesticides in food by SPE disk extraction-capillary gas chromatography with pulsed flame photometric detection].

    Luo, Xiao-Fei; Yang, Yuan; Sun, Cheng-Jun

    2012-01-01

    To develop a method for the simultaneous determination of 44 organophosphorus pesticides in food by SPE disk extraction-capillary gas chromatography with pulsed flame photometric detection. Organophosphorus pesticides in food were extracted ultrasonically with water. Then the extract was cleaned-up with SPE disk and eluted with ethyl acetate. Finally the eluent was condensed to 1mL under N2 at 55 degrees C. Gas chromatography was applied for quantitative detection of the organophosphorus pesticides in the sample. The linear range of the method for all the pesticides were in the range of 0.01-0.5 mg/kg with correlation coefficients of 0.992-1.000. The detection limits of the method were in the range of 0.0005-0.01 mg/kg. The recoveries for most pesticides were 60%-120% with relative standard deviations of less than 15%. The method is simple, sensitive, environmentally friendly and suitable for the determination of organophosphorous pesticides in food.

  11. Identification and isolation of bacteria containing OPH enzyme for biodegradation of organophosphorus pesticide diazinon from contaminated agricultural soil

    Sara Mobarakpoor

    2015-04-01

    Full Text Available Background: Organophosphorus insecticide diazinon has been widely used in agriculture and has the ability to transfer and accumulate in soil, water and animal tissues, and to induce toxicity in plants, animals and humans. In humans, diazinon inhibits nerve transmission by inactivating acetylcholinesterase enzyme. The present study was carried out to identify bacteria containing OPH enzyme for biodegradation of diazinon from contaminated agricultural soil. Methods: In this study, 8 contaminated agricultural soil samples that were exposed to pesticides, especially diazinon in the last two decades, were collected from the farms of Hamedan province. After preparing the media, for isolation of several bacterial strains containing OPH enzyme that are capable of biodegrading organophosphorus pesticides by diazinon enzymatic hydrolysis, bacterial genomic DNA extraction, plasmid product sequencing, phylogenetic sequence processing and phylogenetic tree drawing were carried out. Results: Eight bacterial strains, capable of secreting OPH enzyme, were isolated from soil samples, one of which named BS-1 with 86% similarity to Bacillus safensis displayed the highest organophosphate-hydrolyzing capability and can be used as a source of carbon and phosphorus. Conclusion: It can be concluded that the isolated bacterial strain identified in this study with OPH enzyme secretion has the potential for biodegradation of organophosphorus pesticides, especially diazinon in invitro conditions. Also, further studies such as the environmental stability and interaction, production strategies, safety, cost-benefit, environmental destructive parameters, and, toxicological, genetic and biochemical aspects are recommended prior to the application of bacterial strains in the field-scale bioremediation.

  12. STUDY OF CLINICAL PROFILE AND OUTCOME OF ORGANOPHOSPHORUS POISONING IN RELATION TO PSEUDOCHOLINESTERASE LEVEL

    Rajyalakshmi

    2017-11-01

    Full Text Available BACKGROUND The state of Andhra Pradesh, particularly the coastal districts are an area of intensive agricultural production. Pesticide use is high, and the state has one of the highest reported rates of pesticide poisoning in India. The resources for treating this number of cases in government hospitals are limited and likely to have an impact on patient outcome. The present study was carried out in one such hospital of the state. Amongst these pesticides, insecticides constitute an important group, and organophosphorus compounds are possibly the insecticides widely used, all over the world. MATERIALS AND METHODS Hundred patients of pesticide poisoning admitted into the medical ward of Government General Hospital, Kakinada during the period of August 2010 to July 2014 were studied. Detailed history was taken in each case from patient and attendants. A meticulous physical examination was done on each of them at the time of admission. The diagnosis of poisoning was suspected from the characteristic garlic and kerosene like odour, characteristic signs and symptoms of poisoning and corroborative evidence collected in the form of packets or containers obtained from the site by family members or bystanders. RESULTS Out of the 14 patients who died, 11 died due to organophosphate poisoning, 2 patients died due to organochlorine poisoning and 1 patient died due to herbicide poisoning. Out of the 11 patients who expired due to organophosphate poisoning, 10 patients had pseudocholinesterase value ≤1 unit/mL. The remaining one (1 patient who died, had a pseudocholinesterase value of 2.2 units/mL. Of the 11 patients who died due to organophosphate poisoning, Monocrotophos recorded highest number of deaths (6 cases, followed by dimethoate, which was responsible for 2 deaths. Methyl parathion, Profenophos and Chlorpyriphos caused 1 death each. An organochlorine compound, Endosulfan caused 2 deaths. Paraquat, a herbicide was responsible for 1 death

  13. [Research on rapid and quantitative detection method for organophosphorus pesticide residue].

    Sun, Yuan-Xin; Chen, Bing-Tai; Yi, Sen; Sun, Ming

    2014-05-01

    The methods of physical-chemical inspection is adopted in the traditional pesticide residue detection, which require a lot of pretreatment processes, are time-consuming and complicated. In the present study, the authors take chlorpyrifos applied widely in the present agricultural field as the research object and propose a rapid and quantitative detection method for organophosphorus pesticide residues. At first, according to the chemical characteristics of chlorpyrifos and comprehensive chromogenic effect of several colorimetric reagents and secondary pollution, the pretreatment of the scheme of chromogenic reaction of chlorpyrifos with resorcin in a weak alkaline environment was determined. Secondly, by analyzing Uv-Vis spectrum data of chlorpyrifos samples whose content were between 0. 5 and 400 mg kg-1, it was confirmed that the characteristic information after the color reaction mainly was concentrated among 360 approximately 400 nm. Thirdly, the full spectrum forecasting model was established based on the partial least squares, whose correlation coefficient of calibration was 0. 999 6, correlation coefficient of prediction reached 0. 995 6, standard deviation of calibration (RMSEC) was 2. 814 7 mg kg-1, and standard deviation of verification (RMSEP) was 8. 012 4 mg kg-1. Fourthly, the wavelengths whose center wavelength is 400 nm was extracted as characteristic region to build a forecasting model, whose correlation coefficient of calibration was 0. 999 6, correlation coefficient of prediction reached 0. 999 3, standard deviation of calibration (RMSEC) was 2. 566 7 mg kg-1 , standard deviation of verification (RMSEP) was 4. 886 6 mg kg-1, respectively. At last, by analyzing the near infrared spectrum data of chlorpyrifos samples with contents between 0. 5 and 16 mg kg-1, the authors found that although the characteristics of the chromogenic functional group are not obvious, the change of absorption peaks of resorcin itself in the neighborhood of 5 200 cm

  14. Gastric Lavage in Acute Organophosphorus Pesticide poisoning (GLAOP – a randomised controlled trial of multiple vs. single gastric lavage in unselected acute organophosphorus pesticide poisoning

    Cao YuPing

    2006-10-01

    Full Text Available Abstract Background Organophosphorus (OP pesticide poisoning is the most common form of pesticide poisoning in many Asian countries. Guidelines in western countries for management of poisoning indicate that gastric lavage should be performed only if two criteria are met: within one hour of poison ingestion and substantial ingested amount. But the evidence on which these guidelines are based is from medicine overdoses in developed countries and may be irrelevant to OP poisoning in Asia. Chinese clinical experience suggests that OP remains in the stomach for several hours or even days after ingestion. Thus, there may be reasons for doing single or multiple gastric lavages for OP poisoning. There have been no randomised controlled trials (RCTs to assess this practice of multiple lavages. Since it is currently standard therapy in China, we cannot perform a RCT of no lavage vs. a single lavage vs. multiple lavages. We will compare a single gastric lavage with three gastric lavages as the first stage to assess the role of gastric lavage in OP poisoning. Methods/Design We have designed an RCT assessing the effectiveness of multiple gastric lavages in adult OP self-poisoning patients admitted to three Chinese hospitals within 12 hrs of ingestion. Patients will be randomised to standard treatment plus either a single gastric lavage on admission or three gastric lavages at four hour intervals. The primary outcome is in-hospital mortality. Analysis will be on an intention-to-treat basis. On the basis of the historical incidence of OP at the study sites, we expect to enroll 908 patients over three years. This projected sample size provides sufficient power to evaluate the death rate; and a variety of other exposure and outcome variables, including particular OPs and ingestion time. Changes of OP level will be analyzed in order to provide some toxic kinetic data. Discussion the GLAOP study is a novel, prospective cohort study that will explore to the toxic

  15. Organophosphorus flame retardants in mangrove sediments from the Pearl River Estuary, South China.

    Hu, Yong-Xia; Sun, Yu-Xin; Li, Xiao; Xu, Wei-Hai; Zhang, Ying; Luo, Xiao-Jun; Dai, Shou-Hui; Xu, Xiang-Rong; Mai, Bi-Xian

    2017-08-01

    Forty-eight surface sediments were collected from three mangrove wetlands in the Pearl River Estuary (PRE) of South China to investigate the distribution of organophosphorus flame retardants (OPFRs) and the relationship between OPFRs and microbial community structure determined by phospholipid fatty acid. Concentrations of ΣOPFRs in mangrove sediments of the PRE ranged from 13.2 to 377.1 ng g -1 dry weight. Levels of ΣOPFRs in mangrove sediments from Shenzhen and Guangzhou were significantly higher than those from Zhuhai, indicating that OPFRs were linked to industrialization and urbanization. Tris(chloropropyl)phosphate was the predominant profile of OPFRs in mangrove sediments from Shenzhen (38.9%) and Guangzhou (35.0%), while the composition profile of OPFRs in mangrove sediments from Zhuhai was dominated by tris(2-chloroethyl) phosphate (25.5%). The mass inventories of OPFRs in the mangrove sediments of Guangzhou, Zhuhai and Shenzhen were 439.5, 133.5 and 662.3 ng cm -2 , respectively. Redundancy analysis revealed that OPFRs induced a shift in the structure of mangrove sediment microbial community and the variations were significantly correlated with tris(1,3-dichloro-2-propyl)phosphate and tris(2-butoxyethyl) phosphate. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Sensitive spectrophotometric methods for determination of some organophosphorus pesticides in vegetable samples

    MAGDA A. AKL

    2010-03-01

    Full Text Available Three rapid, simple, reproducible and sensitive spectrophotometric methods (A, B and C are described for the determination of two organophosphorus pesticides, (malathion and dimethoate in formulations and vegetable samples. The methods A and B involve the addition of an excess of Ce4+ into sulphuric acid medium and the determination of the unreacted oxidant by decreasing the red color of chromotrope 2R (C2R at a suitable lmax = 528 nm for method A, or a decrease in the orange pink color of rhodamine 6G (Rh6G at a suitable lmax = = 525 nm. The method C is based on the oxidation of malathion or dimethoate with the slight excess of N-bromosuccinimide (NBS and the determination of unreacted oxidant by reacting it with amaranth dye (AM in hydrochloric acid medium at a suitable lmax = 520 nm. A regression analysis of Beer-Lambert plots showed a good correlation in the concentration range of 0.1-4.2 μg mL−1. The apparent molar absorptivity, Sandell sensitivity, the detection and quantification limits were calculated. For more accurate analysis, Ringbom optimum concentration ranges are 0.25-4.0 μg mL−1. The developed methods were successfully applied to the determination of malathion, and dimethoate in their formulations and environmental vegetable samples.

  17. Partitioning of organophosphorus pesticides into phosphatidylcholine small unilamellar vesicles studied by second-derivative spectrophotometry.

    Takegami, Shigehiko; Kitamura, Keisuke; Ohsugi, Mayuko; Ito, Aya; Kitade, Tatsuya

    2015-06-15

    In order to quantitatively examine the lipophilicity of the widely used organophosphorus pesticides (OPs) chlorfenvinphos (CFVP), chlorpyrifos-methyl (CPFM), diazinon (DZN), fenitrothion (FNT), fenthion (FT), isofenphos (IFP), profenofos (PFF) and pyraclofos (PCF), their partition coefficient (Kp) values between phosphatidylcholine (PC) small unilamellar vesicles (SUVs) and water (liposome-water system) were determined by second-derivative spectrophotometry. The second-derivative spectra of these OPs in the presence of PC SUV showed a bathochromic shift according to the increase in PC concentration and distinct derivative isosbestic points, demonstrating the complete elimination of the residual background signal effects that were observed in the absorption spectra. The Kp values were calculated from the second-derivative intensity change induced by addition of PC SUV and obtained with a good precision of R.S.D. below 10%. The Kp values were in the order of CPFM>FT>PFF>PCF>IFP>CFVP>FNT⩾DZN and did not show a linear correlation relationship with the reported partition coefficients obtained using an n-octanol-water system (R(2)=0.530). Also, the results quantitatively clarified the effect of chemical-group substitution in OPs on their lipophilicity. Since the partition coefficient for the liposome-water system is more effective for modeling the quantitative structure-activity relationship than that for the n-octanol-water system, the obtained results are toxicologically important for estimating the accumulation of these OPs in human cell membranes. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. Susceptibility of nine organophosphorus pesticides in skimmed milk towards inoculated lactic acid bacteria and yogurt starters.

    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.

  19. A portable liquid crystal-based polarized light system for the detection of organophosphorus nerve gas

    He, Feng Jie; Liu, Hui Long; Chen, Long Cong; Xiong, Xing Liang

    2018-03-01

    Liquid crystal (LC)-based sensors have the advantageous properties of being fast, sensitive, and label-free, the results of which can be accessed directly only through the naked eye. However, the inherent disadvantages possessed by LC sensors, such as relying heavily on polarizing microscopes and the difficulty to quantify, have limited the possibility of field applications. Herein, we have addressed these issues by constructing a portable polarized detection system with constant temperature control. This system is mainly composed of four parts: the LC cell, the optics unit, the automatic temperature control unit, and the image processing unit. The LC cell was based on the ordering transitions of LCs in the presence of analytes. The optics unit based on the imaging principle of LCs was designed to substitute the polarizing microscope for the real-time observation. The image processing unit is expected to quantify the concentration of analytes. The results have shown that the presented system can detect dimethyl methyl phosphonate (a stimulant for organophosphorus nerve gas) within 25 s, and the limit of detection is about 10 ppb. In all, our portable system has potential in field applications.

  20. Determination of organophosphorus pesticides using molecularly imprinted polymer solid phase extraction

    Mohd Marsin Sanagi; Syairah Salleh; Wan Aini Wan Ibrahim

    2011-01-01

    Molecularly imprinted polymer solid phase extraction (MIP-SPE) method has been developed for the determination of organophosphorus pesticides (OPPs) in water samples. The MIP was prepared by thermo-polymerization method using methacrylic acid (MAA) as functional monomer, ethylene glycol dimethacrylate (EGDMA) as crosslinker, acetonitrile as porogenic solvent and quinalphos as the template molecule. The three OPPs (diazinon, quinalphos and chloropyrifos) were selected as target analytes as they are widely used in agriculture sector. Various parameters affecting the extraction efficiency of the imprinted polymers have been evaluated to optimize the selective preconcentration of OPPs from aqueous samples. The characteristics of the MIP-SPE method were validated by high performance liquid chromatography (HPLC). The accuracy and selectivity of the MIP-SPE process developed were verified using non-imprinted polymer solid phase extraction (NIP-SPE) and a commercial C 18 -SPE was used for comparison. The recoveries of the target analytes obtained using the MIPs as the solid phase sorbent ranged from 83% to 98% (RSDs 1.05 - 1.98 %; n=3) for water sample. The developed MIP-SPE method demonstrates that it could be applied for the determination of OPPs in water samples. (author)

  1. Competitive immunochromatographic assay for the detection of the organophosphorus pesticide chlorpyrifos

    Kim, Young Ah; Lee, Eun-Hye; Kim, Kwang-Ok; Lee, Yong Tae; Hammock, Bruce D.; Lee, Hye-Sung

    2014-01-01

    An immunochromatographic assay (ICA) based on competitive antigen-coated format using colloidal gold as the label was developed for the detection of the organophosphorus insecticide chlorpyrifos. The ICA test strip consisted of a membrane with a detection zone, a sample pad and an absorbent pad. The membrane was separately coated with chlorpyrifos hapten-OVA conjugate (test line) and anti-mouse IgG (control line). Based on the fact that the competition is between the migrating analyte in the sample and the analyte hapten immobilized on the test strip for the binding sites of the antibody-colloidal gold (Ab-CG) conjugate migrating on the test strip, this study suggests that the relative migration speed between the two migrating substances is a critically important factor for the sensitive detection by competitive ICA. This criterion was utilized for the confirmation of appropriateness of a nitrocellulose (NC) membrane for chlorpyrifos ICA. The detection limit of the ICA for chlorpyrifos standard and chlorpyrifos spiked into agricultural samples were 10 and 50 ng mL−1, respectively. The assay time for the ICA test was less than 10 min, suitable for rapid on-site testing of chlorpyrifos. PMID:21504817

  2. Removal of actinides from nuclear fuel reprocessing waste solutions with bidentate organophosphorus extractants

    Schulz, W.W.; McIsaac, L.D.

    1975-08-01

    The neutral bidentate organophosphorus reagents DBDECMP (dibutyl-N,N-diethylcarbamylmethylenephosphonate) and its dihexyl analogue DHDECMP are candidate extractants for removal of actinides from certain acidic waste streams produced at the U. S. ERDA Hanford and Idaho Falls sites. Various chemical and physical properties including availability, cost, purification, alpha radiolysis, and aqueous phase solubility of DBDECMP and DHDECMP are reviewed. A conceptual flowsheet employing a 15 percent DBDECMP (or DHDECMP)--CCl 4 extractant for removal (and recovery) of Am and Pu from Hanford's Plutonium Reclamation Facility acid waste stream (CAW solution) was successfully demonstrated in laboratory-scale mixer-settler tests; this extraction scheme can be used to produce an actinide-free waste. A 30 percent DBDECMP-xylene flowsheet is being tested at the Idaho Falls site for removal of U, Np, Pu, and Am from Idaho Chemical Processing Plant first-cycle high-level raffinate to produce an actinide-free (less than 10 nCi alpha activity/gram) waste. (auth)

  3. Improvement of Some Biochemical Activities of Rats Treated with The Organophosphorus Insecticide Cytrolane Using Soyabean

    Abdel-Fattah, A.M.; Elmahdy, A.A.

    2005-01-01

    This Study aims to evaluate the role of soyabean diet in improvement of some biochemical activities of female rats received daily oral dose 0.89 mg/kg (1/10 LD 50 )of cytrolane as organophosphorus insecticide on some biochemical activities in female rats for ten consecutive days. Prior pesticide administration, female rats received soyabean at dose 58 g/kg body weight for 2 and 4 weeks. Under the effect of cytrolane administration, the results showed significant increase in serum triglycerides, total cholesterol, HDL-cholesterol and CPK mean levels. Total serum protein and progesterone levels were significantly decreased compared to the control. On the other hand, by the administration of soyabean prior cytrolane, it reduced considerably the changes produced by cytrolane on levels of serum cholesterol, triglyceride, HDL-cholesterol which decreased more or less compared to control, total protein level was within normal value. Also, serum progesterone concentration increased. Therefore, soyabean administration accelerated the normalization and improvement processes of the altered lipid profiles, protein and progesterone hormone

  4. A ratiometric fluorescent quantum dots based biosensor for organophosphorus pesticides detection by inner-filter effect.

    Yan, Xu; Li, Hongxia; Han, Xiaosong; Su, Xingguang

    2015-12-15

    In this work, we develop a novel and sensitive sensor for the detection of organophosphorus pesticides based on the inner-filter effect (IFE) between gold nanoparticles (AuNPs) and ratiometric fluorescent quantum dots (RF-QDs). The RF-QDs has been designed by hybridizing two differently colored CdTe QDs, in which the red emissive QDs entrapped in the silica sphere acting as the reference signal, and the green emissive QDs covalently attached on the silica surface serving as the response signal.The fluorescence of RF-QDs could be quenched by AuNPs based on IFE. Protamine could effectively turn on the fluorescence due to the electrostatic attraction between protamine and AuNPs. Trypsin can easily hydrolyze protamine, leading to the quench of the fluorescence. Then, the fluorescence could be recovered again by the addition of parathion-methyl (PM) which could inhibit the activity of trypsin. By measuring the fluorescence of RF-QDs, the inhibition efficiency of PM to trypsin activity was evaluated. Under the optimized conditions, the inhibition efficiency was proportional to the logarithm of PM concentration in the range of 0.04-400 ng mL(-1), with a detection limit of 0.018 ng mL(-1). Furthermore, the simple and convenient method had been used for PM detection in environmental and agricultural samples with satisfactory results. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. Organophosphorus pesticides effect on early stages of the axolotl Ambystoma mexicanum (Amphibia: Caudata).

    Robles-Mendoza, C; García-Basilio, C; Cram-Heydrich, S; Hernández-Quiroz, M; Vanegas-Pérez, C

    2009-02-01

    Ambystoma mexicanum is an endemic salamander of Xochimilco, a wetland of the basin of Mexico valley. Nowadays, axolotl populations are decreasing due environmental stressors. Particularly, studies about organophosphorus pesticides (OPPs; i.e. chlorpyrifos and malathion) toxicity are of great importance due to their intensive use in agricultural activities in Xochimilco. Thus, the aim of this study was to evaluate under controlled conditions the toxicity of chlorpyrifos (CPF) and malathion (MLT) on embryos and larvae (stage 44 and 54) of A. mexicanum. Embryos and larvae were exposure 96h from 0.5 to 3mg CPFL(-1) and from 10 to 30mg MLTL(-1) in independent tests. Embryos at the end of this period were maintained 9d without pesticide in order to identify possible recuperation. Differences obtained in mortality, hatching success, development, morphological abnormalities, behaviour and activity, suggest that toxicity of CPF and MLT differs in embryos and larval stages. Embryos were less sensitive to OPPs acute exposure than axolotl larvae; additionally, toxicity of CPF in larval stages was greater than MLT. On the other hand, data obtained in axolotl embryos during the period of recuperation to CPF in particular as delay and inhibition of development, malformations and success of hatching, indicated that these responses turned out more sensitive than mortality. This study allowed to identify the toxicological potential of OPPs on early developmental stages of A. mexicanum and it is a valuable contribution for the future management of the axolotl wild population.

  6. Biosensors and their applications in detection of organophosphorus pesticides in the environment.

    Hassani, Shokoufeh; Momtaz, Saeideh; Vakhshiteh, Faezeh; Maghsoudi, Armin Salek; Ganjali, Mohammad Reza; Norouzi, Parviz; Abdollahi, Mohammad

    2017-01-01

    This review discusses the past and recent advancements of biosensors focusing on detection of organophosphorus pesticides (OPs) due to their exceptional use during the last decades. Apart from agricultural benefits, OPs also impose adverse toxicological effects on animal and human population. Conventional approaches such as chromatographic techniques used for pesticide detection are associated with several limitations. A biosensor technology is unique due to the detection sensitivity, selectivity, remarkable performance capabilities, simplicity and on-site operation, fabrication and incorporation with nanomaterials. This study also provided specifications of the most OPs biosensors reported until today based on their transducer system. In addition, we highlighted the application of advanced complementary materials and analysis techniques in OPs detection systems. The availability of these new materials associated with new sensing techniques has led to introduction of easy-to-use analytical tools of high sensitivity and specificity in the design and construction of OPs biosensors. In this review, we elaborated the achievements in sensing systems concerning innovative nanomaterials and analytical techniques with emphasis on OPs.

  7. New Cinchona Oximes Evaluated as Reactivators of Acetylcholinesterase and Butyrylcholinesterase Inhibited by Organophosphorus Compounds

    Maja Katalinić

    2017-07-01

    Full Text Available For the last six decades, researchers have been focused on finding efficient reactivators of organophosphorus compound (OP-inhibited acetylcholinesterase (AChE and butyrylcholinesterase (BChE. In this study, we have focused our research on a new oxime scaffold based on the Cinchona structure since it was proven to fit the cholinesterases active site and reversibly inhibit their activity. Three Cinchona oximes (C1, C2, and C3, derivatives of the 9-oxocinchonidine, were synthesized and investigated in reactivation of various OP-inhibited AChE and BChE. As the results showed, the tested oximes were more efficient in the reactivation of BChE and they reactivated enzyme activity to up to 70% with reactivation rates similar to known pyridinium oximes used as antidotes in medical practice today. Furthermore, the oximes showed selectivity towards binding to the BChE active site and the determined enzyme-oxime dissociation constants supported work on the future development of inhibitors in other targeted studies (e.g., in treatment of neurodegenerative disease. Also, we monitored the cytotoxic effect of Cinchona oximes on two cell lines Hep G2 and SH-SY5Y to determine the possible limits for in vivo application. The cytotoxicity results support future studies of these compounds as long as their biological activity is targeted in the lower micromolar range.

  8. Catalytic Characteristics of New Antibacterials Based on Hexahistidine-Containing Organophosphorus Hydrolase

    Olga Maslova

    2017-09-01

    Full Text Available Catalytic characteristics of hexahistidine-containing organophosphorus hydrolase (His6-OPH and its enzyme-polyelectrolyte complexes with poly-l-glutamic acid or poly-l-aspartic acid (His6-OPH/PLD50, hydrolyzing organophosphorous compounds, and N-acyl homoserine lactones were studied in the presence of various antibiotics (ampicillin, gentamicin, kanamycin, and rifampicin. The antibiotics at concentrations below 1 g·L−1 had a negligible inhibiting effect on the His6-OPH activity. Mixed inhibition of His6-OPH was established for higher antibiotic concentrations, and rifampicin was the most potent inhibitor. Stabilization of the His6-OPH activity was observed in the presence of antibiotics at a concentration of 0.2 g·L−1 during exposure at 25–41 °C. Molecular docking of antibiotics to the surface of His6-OPH dimer revealed the antibiotics binding both to the area near active centers of the enzyme subunits and to the region of contact between subunits of the dimer. Such interactions between antibiotics and His6-OPH were verified with Fourier-transform infrared (FTIR spectroscopy. Considering all the results of the study, the combination of His6-OPH/PLD50 with β-lactam antibiotic ampicillin was established as the optimal one in terms of exhibition and persistence of maximal lactonase activity of the enzyme.

  9. Degradation of Organophosphorus and Pyrethroid Insecticides in Beverages: Implications for Risk Assessment

    Samantha A. Radford

    2018-02-01

    Full Text Available Since urinary insecticide metabolites are commonly used as biomarkers of exposure, it is important that we quantify whether insecticides degrade in food and beverages in order to better perform risk assessment. This study was designed to quantify degradation of organophosphorus and pyrethroid insecticides in beverages. Purified water, white grape juice, orange juice, and red wine were fortified with 500 ng/mL diazinon, malathion, chlorpyrifos, permethrin, cyfluthrin, cypermethrin, and deltamethrin, and aliquots were extracted several times over a 15-day storage period at 2.5 °C. Overall, statistically significant loss of at least one insecticide was observed in each matrix, and at least five out of seven insecticides demonstrated a statistically significant loss in all matrices except orange juice. An investigation of an alternative mechanism of insecticide loss—adsorption onto the glass surface of the storage jars—was carried out, which indicated that this mechanism of loss is insignificant. Results of this work suggest that insecticides degrade in these beverages, and this degradation may lead to pre-existing insecticide degradates in the beverages, suggesting that caution should be exercised when using urinary insecticide metabolites to assess exposure and risk.

  10. Gas chromatography with flame photometric detection of 31 organophosphorus pesticide residues in Alpinia oxyphylla dried fruits.

    Zhao, Xiangsheng; Kong, Weijun; Wei, Jianhe; Yang, Meihua

    2014-11-01

    A simple, rapid and effective gas chromatography-flame photometric detection method was established for simultaneous multi-component determination of 31 organophosphorus pesticides (OPPs) residues in Alpinia oxyphylla, which is widely consumed as a traditional medicine and food in China. Sample preparation was completed in a single step without any clean-up procedure. All pesticides expressed good linear relationships between 0.004 and 1.0 μg/mL with correlation coefficients higher than 0.9973. The method gave satisfactory recoveries for most pesticides. The limits of detection varied from 1 to 10 ng/mL, and the limits of quantification (LOQs) were between 4 and 30 ng/mL. The proposed method was successfully applied to 55 commercial samples purchased from five different areas. Five pesticide residues were detected in four (7.27%) samples. The positive samples were confirmed by gas chromatography with tandem mass spectrometry (GC-MS/MS). Copyright © 2014 Elsevier Ltd. All rights reserved.

  11. Theoretical and experimental study of actinide complexes with monoamides and organophosphorus ligands in solution

    Ribokaite, Kristina

    2013-01-01

    Monoamides and organophosphate are of great interest for the nuclear fuel cycle. Such ligands can selectively extract actinides in liquid-liquid extraction processes. The structure of the extractant (its functional group and its alkyl substituents) has a predominant role in the selective separation of actinides. This thesis concerns the theoretical and experimental studies of model systems in the aim of better understanding of the effect on molecular structures of the complexes. Structures of actinides complexes formed with model ligands in simple media (water or methanol in the presence of nitrate ions) have been characterized. At first, the complexation of uranyl by monoamide and phosphine oxide was studied in water and methanol. Molecular Dynamics simulations and DFT calculations were used to quantify the stability of uranyl complexes with those ligands, and to determine their structural properties. The theoretical results were then compared with experimental results obtained by UV-visible, infrared, Raman and EXAFS on the same chemical systems. The results were used to highlight the greater stability of uranyl complexes with phosphine oxide and monoamides. Further spectroscopic measurements combined with molecular modeling were used to gain a better understanding of the coordination mode of nitrate ion around the uranyl in both water and methanol. Finally, DFT calculations were used to study the influence of the structure of the monoamide or organophosphorus ligand and their interaction with the actinides (IV, VI) including steric effects in the first coordination sphere. (author) [fr

  12. Pharmacological treatment of organophosphorus insecticide poisoning: the old and the (possible) new.

    Eddleston, Michael; Chowdhury, Fazle Rabbi

    2016-03-01

    Despite being a major clinical and public health problem across the developing world, responsible for at least 5 million deaths over the last three decades, the clinical care of patients with organophosphorus (OP) insecticide poisoning has little improved over the last six decades. We are still using the same two antidotes - atropine and oximes - that first came into clinical use in the late 1950s. Clinical research in South Asia has shown how improved regimens of atropine can prevent deaths. However, we are still unsure about which patients are most likely to benefit from the use of oximes. Supplemental antidotes, such as magnesium, clonidine and sodium bicarbonate, have all been proposed and studied in small trials without production of definitive answers. Novel antidotes such as nicotinic receptor antagonists, beta-adrenergic agonists and lipid emulsions are being studied in large animal models and in pilot clinical trials. Hopefully, one or more of these affordable and already licensed antidotes will find their place in routine clinical care. However, the large number of chemically diverse OP insecticides, the varied poisoning they produce and their varied response to treatment might ultimately make it difficult to determine definitively whether these antidotes are truly effective. In addition, the toxicity of the varied solvents and surfactants formulated with the OP active ingredients complicates both treatment and studies. It is possible that the only effective way to reduce deaths from OP insecticide poisoning will be a steady reduction in their agricultural use worldwide. © 2015 The British Pharmacological Society.

  13. Cholinesterase reactivators and bioscavengers for pre- and post-exposure treatments of organophosphorus poisoning.

    Masson, Patrick; Nachon, Florian

    2017-08-01

    Organophosphorus agents (OPs) irreversibly inhibit acetylcholinesterase (AChE) causing a major cholinergic syndrome. The medical counter-measures of OP poisoning have not evolved for the last 30 years with carbamates for pretreatment, pyridinium oximes-based AChE reactivators, antimuscarinic drugs and neuroprotective benzodiazepines for post-exposure treatment. These drugs ensure protection of peripheral nervous system and mitigate acute effects of OP lethal doses. However, they have significant limitations. Pyridostigmine and oximes do not protect/reactivate central AChE. Oximes poorly reactivate AChE inhibited by phosphoramidates. In addition, current neuroprotectants do not protect the central nervous system shortly after the onset of seizures when brain damage becomes irreversible. New therapeutic approaches for pre- and post-exposure treatments involve detoxification of OP molecules before they reach their molecular targets by administrating catalytic bioscavengers, among them phosphotriesterases are the most promising. Novel generation of broad spectrum reactivators are designed for crossing the blood-brain barrier and reactivate central AChE. This is an article for the special issue XVth International Symposium on Cholinergic Mechanisms. © 2017 International Society for Neurochemistry.

  14. Effects of organophosphorus flame retardant TDCPP on normal human corneal epithelial cells: Implications for human health.

    Xiang, Ping; Liu, Rong-Yan; Li, Chao; Gao, Peng; Cui, Xin-Yi; Ma, Lena Q

    2017-11-01

    Tris(1,3-dichloro-2-propyl) phosphate (TDCPP) is one of the most detected organophosphorus flame retardants (OPFRs) in the environment, especially in indoor dust. Continuous daily exposure to TDCPP-containing dust may adversely impact human cornea. However, its detrimental effects on human corneal epithelium are largely unknown. In this study, we investigated the cell apoptosis in normal human corneal epithelial cells (HCECs) after TDCPP exposure and elucidated the underlying molecular mechanisms. Our data indicated a dose-dependent decrease of cell viability after TDCPP exposure with LC 50 at 202 μg/mL. A concentration-dependent apoptotic sign was observed in HCECs after exposing to ≥2 μg/mL TDCPP. Endoplasmic reticulum stress induction was evidenced by up-regulation of its biomarker genes (ATF-4, CHOP, BiP, and XBP1). Furthermore, alternation of Bcl-2/Bax expression, mitochondrial membrane potential loss, cellular ATP content decrease, and caspase-3 and -9 activity increase were observed after exposing to 2 or 20 μg/mL TDCPP. Taken together, the data implicated the involvement of endoplasmic reticulum stress in TDCPP-induced HCEC apoptosis, probably mediated by mitochondrial apoptotic pathway. Our findings showed TDCPP exposure induced toxicity to human cornea. Due to TDCPP's presence at high levels in indoor dust, further study is warranted to evaluate its health risk on human corneas. Published by Elsevier Ltd.

  15. Suicidal Death due to Organophosphorus Compound Poisoning ─ an Experience of 67 Cases

    Nashid Tabassum Khan

    2016-05-01

    Full Text Available Background: Bangladesh is an agro-based country. Suicide by agrochemical compounds are increasing day by day in this country. Organophosphorus compounds (OPC are commonly used for suicide. Mostly these are used for suicidal purpose in rural areas in our country due to low cost, toxicity and availability. Objective: To find out the relationship of age and sex variation along with the causes that influenced different income group people to ingest OPC for committing suicide. Materials and Methods: This study was conducted in the Department of Forensic Medicine, Dhaka Medical College during January to December 2010. Data were collected at the time of autopsy and from postmortem examination report of viscera. Viscera were preserved and sent to the Chief Chemical Examiner’s Office, Dhaka for toxicological analysis. Results: In this study, middle aged subjects (20–30 years were found to commit suicide using OPC in comparison to other age groups. Among the cases male were 57% and female 43%. Poverty was found as the most common cause (20% of OPC poisoning. Conclusion: Poverty is the leading cause of death of OPC poisoning followed by failure in love and adultery. Business failure, unhappiness in conjugal life, demand for dowry and violence against women are other causes to commit suicide by OPC.

  16. Organophosphorus pesticide exposure in agriculture: effects of temperature, ultraviolet light and abrasion on PVC gloves

    ISMAIL, Ismaniza; GASKIN, Sharyn; PISANIELLO, Dino; EDWARDS, John W.

    2017-01-01

    Elbow length PVC gloves are often recommended for protection against organophosphorus pesticide (OP) exposure in agriculture. However, performance may be reduced due to high temperature, UV exposure and abrasion. We sought to assess these impacts for two OPs under normal use and reasonable worst-case scenarios. Glove permeation tests were conducted using ASTM cells with two PVC glove brands at 23°C and 45°C for up to 8 h. Technical grade dichlorvos and formulated diazinon were used undiluted and at application strength. Breakthough of undiluted dichlorvos occurred at both 23°C and 45°C, but only at 45°C for application strength. Breakthrough of diazinon was not achieved, except when undiluted at 45°C. UV-exposed and abraded gloves showed reduced performance, with the effect being approximately two-fold for dichlorvos. Only small differences were noted between glove brands. Extra precautions should be taken when handling concentrated OPs at high temperature, or when using abraded or sunlight-exposed gloves. PMID:29199264

  17. Effect of diluents on the extraction of actinides and nitric acid by bidentate organophosphorus compounds

    Rozen, A.M.

    1986-01-01

    The effect of dilutents on extraction by bidentate organophosphorus compounds (diphosphine dioxides, carbamoyl phosphonates, and phosphine oxides) was studied. Figures show the effect of dilutents on the extraction of americium by TOPO and by carbamoylmethylene phosphonate, and the effect of dilutents on the extraction of nitric acid and americium by carbamoylphosphine oxide. Also shown is the effect of dilutents on the extraction of americium by diphenyldioctyl methylenediphosphine dioxide, and the effect of dilutents on the extraction of americium by tetraphenylmethylenediphosphine dioxide. It was concluded that when TBP is added the distribution coefficient of Am increases but the effect of TBP may not be represented by the usual power relationship between the distribution coefficient and the TBP concentration, which would be expected if TBP was found to be very strong but for dilution by DCE it was relatively weak. The observed facts can be explained if it is assumed that TBP reacts with the bridging protons in the complex, which are free for dilution by benzene and are partially occupied when dichlorethane is used

  18. Organophosphorus esters in the oceans and possible relation with ocean gyres

    Cheng, Wenhan; Xie, Zhouqing; Blais, Jules M.; Zhang, Pengfei; Li, Ming; Yang, Chengyun; Huang, Wen; Ding, Rui; Sun, Liguang

    2013-01-01

    Four organophosphorus esters (OPEs) were detected in aerosol samples collected in the West Pacific, the Indian Ocean and the Southern Ocean from 2009 to 2010, suggesting their circumpolar and global distribution. In general, the highest concentrations were detected near populated regions in China, Australia and New Zealand. OPE concentrations in the Southern Ocean were about two orders of magnitude lower than those near major continents. Additionally, relatively high OPE concentrations were detected at the Antarctic Peninsula, where several scientific survey stations are located. The four OPEs investigated here are significantly correlated with each other, suggesting they may derive from the same source. In the circumpolar transect, OPE concentrations were associated with ocean gyres in the open ocean. Their concentrations were positively related with average vorticity in the sampling area suggesting that a major source of OPEs may be found in ocean gyres where plastic debris is known to accumulate. -- Highlights: •We provide OPE concentrations in aerosols in a circumpolar expedition. •We find strong anthropogenic source of OPE pollution. •We suggest potential relationship between ocean gyres and OPE pollution. -- Our work provides a circumpolar investigation on OPEs in the Southern Ocean and we suggest a possibility that ocean currents and gyres may act as important roles in global transport of OPEs

  19. Computational Enzymology and Organophosphorus Degrading Enzymes: Promising Approaches Toward Remediation Technologies of Warfare Agents and Pesticides.

    Ramalho, Teodorico C; de Castro, Alexandre A; Silva, Daniela R; Silva, Maria Cristina; Franca, Tanos C C; Bennion, Brian J; Kuca, Kamil

    2016-01-01

    The re-emergence of chemical weapons as a global threat in hands of terrorist groups, together with an increasing number of pesticides intoxications and environmental contaminations worldwide, has called the attention of the scientific community for the need of improvement in the technologies for detoxification of organophosphorus (OP) compounds. A compelling strategy is the use of bioremediation by enzymes that are able to hydrolyze these molecules to harmless chemical species. Several enzymes have been studied and engineered for this purpose. However, their mechanisms of action are not well understood. Theoretical investigations may help elucidate important aspects of these mechanisms and help in the development of more efficient bio-remediators. In this review, we point out the major contributions of computational methodologies applied to enzyme based detoxification of OPs. Furthermore, we highlight the use of PTE, PON, DFP, and BuChE as enzymes used in OP detoxification process and how computational tools such as molecular docking, molecular dynamics simulations and combined quantum mechanical/molecular mechanics have and will continue to contribute to this very important area of research.

  20. Toxicology of organophosphorus compounds in view of an increasing terrorist threat.

    Worek, Franz; Wille, Timo; Koller, Marianne; Thiermann, Horst

    2016-09-01

    The implementation of the Chemical Weapon Convention (CWC), prohibiting the development, production, storage and use of chemical weapons by 192 nations and the ban of highly toxic OP pesticides, especially class I pesticides according to the WHO classification, by many countries constitutes a great success of the international community. However, the increased interest of terrorist groups in toxic chemicals and chemical warfare agents presents new challenges to our societies. Almost seven decades of research on organophosphorus compound (OP) toxicology was mainly focused on a small number of OP nerve agents despite the fact that a huge number of OP analogues, many of these agents having comparable toxicity to classical nerve agents, were synthesized and published. Only limited physicochemical, toxicological and medical information on nerve agent analogues is available in the open literature. This implies potential gaps of our capabilities to detect, to decontaminate and to treat patients if nerve agent analogues are disseminated and may result in inadequate effectiveness of newly developed countermeasures. In summary, our societies may face new, up to now disregarded, threats by toxic OP which calls for increased awareness and appropriate preparedness of military and civilian CBRN defense, a broader approach for new physical and medical countermeasures and an integrated system of effective detection, decontamination, physical protection and treatment.

  1. Determinants of Organophosphorus Pesticide Urinary Metabolite Levels in Young Children Living in an Agricultural Community

    Brenda Eskenazi

    2011-04-01

    Full Text Available Organophosphorus (OP pesticides are used in agriculture and several are registered for home use. As young children age they may experience different pesticide exposures due to varying diet, behavior, and other factors. We measured six OP dialkylphosphate (DAP metabolites (three dimethyl alkylphosphates (DMAP and three diethyl alkylphosphates (DEAP in urine samples collected from ~400 children living in an agricultural community when they were 6, 12, and 24 months old. We examined bivariate associations between DAP metabolite levels and determinants such as age, diet, season, and parent occupation. To evaluate independent impacts, we then used generalized linear mixed multivariable models including interaction terms with age. The final models indicated that DMAP metabolite levels increased with age. DMAP levels were also positively associated with daily servings of produce at 6- and 24-months. Among the 6-month olds, DMAP metabolite levels were higher when samples were collected during the summer/spring versus the winter/fall months. Among the 12-month olds, DMAP and DEAP metabolites were higher when children lived ≤60 meters from an agricultural field. Among the 24-month-olds, DEAP metabolite levels were higher during the summer/spring months. Our findings suggest that there are multiple determinants of OP pesticide exposures, notably dietary intake and temporal and spatial proximity to agricultural use. The impact of these determinants varied by age and class of DAP metabolite.

  2. Specificity of carboxylesterase protection against the toxicity of organophosphorus compounds. (Reannouncement with new availability information)

    Maxwell, D.M.

    1992-12-31

    The ability of endogenous carboxylesterase (CaE) to protect against the lethal effects of a variety of organophosphorus (OP) compounds was examined in rats. The in vivo protection provided by endogenous CaE was measured by the difference in the LD50 values of OP compounds in controlrats and rats whose CaE activity had been inhibited by sc injection with2 mg/kg of 2-(O cresyl)-4H-1,3,2-benzodi oxaphosphorin-2-oxide. Endogenous CaE provided significant protection against the in vivo toxicity of soman, sarin, tabun, and paraoxon, but not against dichlorvos, diisopropyl fluorophosphate, or ethoxymethyl-S-2- (DIISOPROPYLAMINO)ETHYL THIOPHOSPHONATE (VX). The relationship between the in vivo CaE protection against OP compounds and their relative reactivities with CaE and acetylcholinesterase (AChE) was evaluated by measuring the in vitro bimolecular rate constants (ki) for inhibition of plasma CaE and brain AChE. Except for VX, ki values for CaE inhibition varied <10-fold while ki values for AChE inhibition varied 105-fold. Chemical warfare agents, Nerve agents, Organophosphoruscompound soman, VX, Carboxylesterase, Protection, Pretreatment.

  3. [ACTIVITY OF Ca2+,Mg(2+)-ATPase OF SARCOPLASMIC RETICULUM AND CONTRACTION STRENGTH OF THE FROG SKELETAL MUSCLES UNDER THE EFFECT OF ORGANOPHOSPHORUS INSECTICIDES].

    Nozdrenko, D M; Korchinska, L V; Soroca, V M

    2015-01-01

    The results of an experimental study of organophosphorus insecticides, including pirimiphosmethyl, diazinon and chlorpyrifos caused a decline of the contraction properties in m. tibialis anterior fiber bundles of Rana temporaria, as well as sarcoplasmic reticulum Ca2+, Mg(2+)-ATPase enzymatic activity reduction are outlined in this paper. Concentration-dependent strengths response diminishing in isolated skeletal muscle fiber bundles as a result of non-cholinergic influence of organophosphorus insecticides were found. A decrease of Ca2+, Mg(2+)-ATPase enzymatic activity in sarcoplasmic reticulum was observed after administration of each insecticide. The most significant inhibition of this enzyme was observed when using chlorpyrifos.

  4. Effects of the organophosphorus pesticide Folisuper 600 (methyl parathion on the heart function of bullfrog tadpoles, Lithobates catesbeianus (Shaw, 1802

    M. J. Costa

    Full Text Available Abstract The aim of this work was to evaluate whether the heart function of bullfrog tadpoles (25 Gosner stage is affected by their acute exposure (48 h to a sub-lethal concentration (10 µg.L–1 of the active principle of the organophosphorus pesticide Folisuper 600R (methyl parathion - MP. Our results demonstrated that MP causes not only a reduction in tadpoles’ cardiac ventricular mass, resulting in a marked reduction in their cardiac twitch force, but also impairs their swimming performance, irrespective of increasing their heart rate. Together, these findings indicate that low and realistic concentration of MP have a negative impact on tadpoles’ performance, jeopardizing their survival.

  5. Phytase production by Aspergillus niger NCIM 563 for a novel application to degrade organophosphorus pesticides.

    Shah, Parin C; Kumar, V Ravi; Dastager, Syed G; Khire, Jayant M

    2017-12-01

    The production of phytase using Aspergillus niger NCIM 563 under submerged fermentation conditions was studied using protein rich chickpea flour as substrate. Employing a hybrid statistical media optimization strategy of Plackett-Burman and Box-Behnken experimental designs in shake-flasks gave an increased phytase activity from an initial 66 IU/mL in 216 h to 160 IU/mL in a reduced time of 132 h. Productivity, thus increased by 3.97 times from 7.3 to 29 IU/mL/day. Using the optimized media, the production was successfully scaled-up further and improved up to 164 IU/mL in 96 h by studies carried out employing 2 and 10-L fermenters. The enzyme supernatant was recovered using centrifugal separation of biomass and the stability of the produced phytase was tested for animal feed applications under gastric conditions. In vitro degradation studies of water soluble monocrotophos, methyl parathion and water insoluble chlorpyrifos, pesticides used extensively in agriculture was carried out. It was observed by HPLC analysis that phytase could degrade 72% of chlorpyrifos at pH 7.0, 35 °C. Comparable results were obtained with monocrotophos and methyl parathion. With chlorpyrifos at higher temperature 50 °C as much as 91% degradation could be obtained. The degradation of chlorpyrifos was further validated by spraying phytase on harvested green chilli (Capsicum annuum L) under normal conditions of pH 7.0, 35 °C and the degradation products obtained analyzed by LCMS. Thus, the present study brings out a potentially novel application of phytase for biodegradation of organophosphorus pesticides.

  6. Determination of Organophosphorus Pesticides in Soil by Dispersive Liquid–Liquid Microextraction and Gas Chromatography

    Yang, Zhonghua; Liu, Yu; Liu, Donghui; Zhou, Zhiqiang

    2012-01-01

    In this article, a rapid and sensitive sample pretreatment technique for the determination of organophosphorus pesticides (OPPs) in soil samples is developed by using dispersive liquid–liquid microextraction (DLLME) combined with gas chromatography–flame photometric detection. Experimental conditions, including the kind of extraction and disperser solvent and their volumes, the extraction time, and the salt addition, are investigated, and the following experiment factors are used: 20 µL chlorobenzene as the extraction solvent; 1.0 mL acetonitrile as the disperser solvent; no addition of salt; and an extraction time of 1 min. Under the optimum conditions, the linearities for the three target OPPs (ethoprophos, chlorpyriphos, and profenofos) are obtained by five points in the concentration range of 2.5–1500 µg/kg, and three replicates are used for each point. Correlation coefficients vary from 0.9987 to 0.9997. The repeatability is tested by spiking soil samples at a concentration level of 5.0 µg/kg. The relative standard deviation (n = 3) varied between 2.0% and 6.6%. The limits of detection, based on a signal-to-noise ratio (S/N) of 3, range from 200 to 500 pg/g. This method is applied to the analysis of the spiked samples S1, S2, and S3, which are collected from the China Agriculture University's orchard, lawn, and garden, respectively. The recoveries for each target analyte are in the range between 87.9% and 108.0%, 87.4% and 108.0%, and 86.7% and 107.2%, respectively. PMID:22291051

  7. Zirconium(IV) functionalized magnetic nanocomposites for extraction of organophosphorus pesticides from environmental water samples.

    Jiang, Li; Huang, Tengjun; Feng, Shun; Wang, Jide

    2016-07-22

    The widespread use of organophosphate pesticides (OPPs) in agriculture leads to residue accumulation in the environment which is dangerous to human health and disrupts the ecological balance. In this work, one nanocomposite immobilized zirconium (Zr, IV) was prepared and used as the affinity probes to quickly and selectively extract organophosphorus pesticides (OPPs) from water samples. The Fe3O4-ethylenediamine tetraacetic acid (EDTA)@Zr(IV) nanocomposites (NPs) were prepared by simply mixing Zr(IV) ions with Fe3O4-EDTA NPs synthesized by one-pot chemical co-precipitation method. The immobilized Zr(IV) ions were further utilized to capture OPPs based on their high affinity for the phosphate moiety in OPPs. Coupled with GC-MS, four OPPs were used as models to demonstrate the feasibility of this approach. Under the optimum conditions, the limits of detection for target OPPs were in the range of 0.10-10.30ngmL(-1) with relative standard deviations (RSDs) of 0.61-4.40% (n=3), respectively. The linear ranges were over three orders of magnitudes (correlation coefficients, R(2)>0.9995). The Fe3O4-EDTA@Zr(IV) NPs were successfully applied to extract OPPs samples with recoveries of 86.95-112.60% and RSDs of 1.20-10.42% (n=3) from two spiked real water. By the proposed method, the matrix interference could be effectively eliminated. We hope our finding can provide a promising alternative for the fast extraction of OPPs from complex real samples. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Spatial learning impairment in prepubertal guinea pigs prenatally exposed to the organophosphorus pesticide chlorpyrifos: Toxicological implications

    Mamczarz, Jacek; Pescrille, Joseph D.; Gavrushenko, Lisa; Burke, Richard D.; Fawcett, William P.; DeTolla, Louis J.; Chen, Hegang; Pereira, Edna F.R.; Albuquerque, Edson X.

    2017-01-01

    Exposure of the developing brain to chlorpyrifos (CPF), an organophosphorus (OP) pesticide used extensively in agriculture worldwide, has been associated with increased prevalence of cognitive deficits in children, particularly boys. The present study was designed to test the hypothesis that cognitive deficits induced by prenatal exposure to sub-acute doses of CPF can be reproduced in precocial small species. To address this hypothesis, pregnant guinea pigs were injected daily with CPF (25 mg/kg, s.c.) or vehicle (peanut oil) for 10 days starting on presumed gestation day (GD) 53–55. Offspring were born around GD 65, weaned on postnatal day (PND) 20, and subjected to behavioral tests starting around PND 30. On the day of birth, butyrylcholinesterase (BuChE), an OP bioscavenger used as a biomarker of OP exposures, and acetylcholinesterase (AChE), a major molecular target of OP compounds, were significantly inhibited in the blood of CPF-exposed offspring. In their brains, BuChE, but not AChE, was significantly inhibited. Prenatal CPF exposure had no significant effect on locomotor activity or on locomotor habituation, a form of non-associative memory assessed in open fields. Spatial navigation in the Morris water maze (MWM) was found to be sexually dimorphic among guinea pigs, with males outperforming females. Prenatal CPF exposure impaired spatial learning more significantly among male than female guinea pigs and, consequently, reduced the sexual dimorphism of the task. The results presented here, which strongly support the test hypothesis, reveal that the guinea pig is a valuable animal model for preclinical assessment of the developmental neurotoxicity of OP pesticides. These findings are far reaching as they lay the groundwork for future studies aimed at identifying therapeutic interventions to treat and/or prevent the neurotoxic effects of CPF in the developing brain. PMID:27296654

  9. Effect of organophosphorus insecticides and their metabolites on astroglial cell proliferation

    Guizzetti, Marina; Pathak, Shantha; Giordano, Gennaro; Costa, Lucio G.

    2005-01-01

    Though little attention has been given to the possibility that glial cells may represent a target for the developmental neurotoxicity of organophosphorus (OP) insecticides, recent evidence, obtained in particular with chlorpyrifos (CP), suggests that developmental exposure to this compound may indeed target astrocytes. To substantiate and expand these observations, we carried out a series of in vitro studies utilizing fetal rat astrocytes and a human astrocytoma cell line, 1321N1 cells, to investigate the effect of the OPs CP, diazinon (DZ) and parathion (P), their oxygen analogs chlorpyrifos oxon (CPO), diazoxon (DZO) and paraoxon (PO), and their metabolites 3,5,6-trichloro-2-pyridinol (TCP), 2-isopropyl-6-methyl-4-pyrimidol (IMP) and para-nitrophenol (PNP), on cell proliferation. In fetal rat astrocytes and astrocytoma cells maintained in serum, CP, DZ, P, CPO, DZO, and PO induced a concentration-dependent inhibition in [ 3 H]thymidine incorporation with a very similar potency (IC 50 between 45 and 57 μM). Among the other metabolites, PNP was the most potent (IC 50 = 70-80 μM), while TCP and IMP were much less effective (IC 50 > 100 μM). Cytotoxicity appears to account only for a small part of the effect on DNA synthesis. OP insecticides and their oxons were three- to six-fold more potent in inhibiting [ 3 H]thymidine incorporation when cells were synchronized in the G 0 /G 1 phase of the cell cycle and re-stimulated by carbachol or epidermal growth factor. These results suggest that OP insecticides and their oxons affect astroglial cell proliferation and that the transition from the G 0 /G 1 to the S/G 2 phase of the cell cycle may be particularly sensitive to the action of these compounds

  10. Modulatory Effect Of Olive Oil On Toxicity Induced By Organophosphorus Pesticides In Male Rat

    AFIFI, E.A.A.; ALI, S.E.

    2009-01-01

    The present study was carried out to investigate the modulatory effect of olive oil (5 ml/kg b.wt.) against the toxicological effects of repeated daily oral administration of the organophosphorus pesticides malaphos (137.5 mg/kg), mephosfolan (0.89 mg/kg) and phosfolan (1.0 mg/kg) for one, two and four weeks on certain biochemical parameters such as serum albumin, globulin and A/G ratio, low density lipoprotein-cholesterol (LDL-cholesterol), high density lipoprotein-cholesterol (HDL-cholesterol), total cholesterol, total protein, gamma glutamyl transferase ( GT) and plasma triglycerides. In addition, modulation of blood urea, creatinine and uric acid were observed through all the experimental intervals. Also, the serum concentration of triiodothyronine (T 3 ), thyroxine (T 4 ) and thyroid stimulating hormone (TSH) were determined.The data obtained revealed significant decrease in serum total protein, albumin, globulin and HDL-cholesterol while significant increase in serum albumin to globulin ratio (A/G), triglycerides, creatinine, urea, uric acid, LDL-cholesterol, total cholesterol and GT in all treated groups was observed. On the other hand, the data recorded imbalance in thyroid function as a result of pesticides treatments, which donated that each of the three pesticides increased TSH secretion, while malaphos caused significant decrease in both T 3 and T 4 levels, mephosfolan increased T 4 and decreased T 3 levels, whereas phosfolan pesticide decreased T 4 and increased T 3 levels after one, two and four weeks post-treatment.Administration of olive oil during treatment with malaphos, mephosfolan and phosfolan pesticides attenuates to a great extent the destructive effects of pesticides on the assayed parameters, this effect is attributed to the beneficial properties whom olive oil possess as anti-oxidative potential that may act to protect the body organs against the pesticides toxicity and also due to the amelioration of oxidative stress of free radicals.

  11. Organophosphorus pesticides decrease M2 muscarinic receptor function in guinea pig airway nerves via indirect mechanisms.

    Becky J Proskocil

    Full Text Available BACKGROUND: Epidemiological studies link organophosphorus pesticide (OP exposures to asthma, and we have shown that the OPs chlorpyrifos, diazinon and parathion cause airway hyperreactivity in guinea pigs 24 hr after a single subcutaneous injection. OP-induced airway hyperreactivity involves M2 muscarinic receptor dysfunction on airway nerves independent of acetylcholinesterase (AChE inhibition, but how OPs inhibit neuronal M2 receptors in airways is not known. In the central nervous system, OPs interact directly with neurons to alter muscarinic receptor function or expression; therefore, in this study we tested whether the OP parathion or its oxon metabolite, paraoxon, might decrease M2 receptor function on peripheral neurons via similar direct mechanisms. METHODOLOGY/PRINCIPAL FINDINGS: Intravenous administration of paraoxon, but not parathion, caused acute frequency-dependent potentiation of vagally-induced bronchoconstriction and increased electrical field stimulation (EFS-induced contractions in isolated trachea independent of AChE inhibition. However, paraoxon had no effect on vagally-induced bradycardia in intact guinea pigs or EFS-induced contractions in isolated ileum, suggesting mechanisms other than pharmacologic antagonism of M2 receptors. Paraoxon did not alter M2 receptor expression in cultured cells at the mRNA or protein level as determined by quantitative RT-PCR and radio-ligand binding assays, respectively. Additionally, a biotin-labeled fluorophosphonate, which was used as a probe to identify molecular targets phosphorylated by OPs, did not phosphorylate proteins in guinea pig cardiac membranes that were recognized by M2 receptor antibodies. CONCLUSIONS/SIGNIFICANCE: These data indicate that neither direct pharmacologic antagonism nor downregulated expression of M2 receptors contributes to OP inhibition of M2 function in airway nerves, adding to the growing evidence of non-cholinergic mechanisms of OP neurotoxicity.

  12. Evaluation of the organophosphorus hydrolase enzyme activity in creams and investigation of its stability

    Mariye Rajaie

    2016-06-01

    Full Text Available The main purpose of this project is investigation of the organophosphorus hydrolase (OPH enzyme activity in water in oil (w/o and oil in water (o/w creams and investigation of the OPH enzyme stability in formulated creams. OPH enzyme was extracted and purified from strain flavobacterium. The w/o and o/w creams were prepared using different formulations. In order to achieve an emulsion with maximum stability, appropriate percentage of the cream components was selected by studying different formulations and the physical and chemical stability of the produced cream were considered. 5Uenzyme/90gcream enzyme was used for each formulation. To measure the enzyme activity in creams, extraction method was used and enzyme activity was determined based on parathion hydrolysis. The thermal stability of OPH in both types of w/o and o/w creams was studied at 4 and 30  °C for various time periods. The average enzyme activity was about 0.0065 U/gcream and 0.018 U/gcream for w/o and o/w creams respectivly. According to the results, the relative activity at 4 °C was reduced to 50% after 26 and 45 days in w/o and o/w creams, respectivly. The results showed that the OPH enzyme activity in o/w cream was 2.6 times more than that of w/o cream, because of the higher hydrophobicity of o/w cream compared to w/o. The OPH enzyme stability in o/w cream was greater in comparison to w/o cream. The OPH enzyme was active for nearly 2 months on o/w creams at 4 °C .

  13. Dialkyl phosphate metabolites of organophosphorus in applicators of agricultural pesticides in Majes – Arequipa (Peru

    Chung Arturo

    2006-12-01

    Full Text Available Abstract Background Organophosphorus (OPs pesticides are the most commonly used pesticides in Peruvian agriculture. The population at risk for OPs exposure includes formulators, applicators and farmers. Majes Valley is the most important agricultural center of the Southern region of Peru. The present study was aimed to determine the knowledge about using OPs, safety practice and urinary dialkylphosphate metabolites on OP applicators in the Majes Valley, Peru. Methods This study was based on a questionnaire which included socio-demographic characteristics, knowledge of safety practices to handling OPs, characteristics of pesticide application and use of protective measures to avoid pesticide contamination. Exposure was assessed by measuring six urinary OP metabolites (DMP, DMTP, DMDTP, DEP, DETP, and DEDTP by gas chromatography using a single flame photometric detector. The sample consisted of 31 men and 2 women aged 20 – 65 years old. Results 76% of applicators had at least one urinary dialkylphosphate metabolite above the limit of detection. The geometric mean (GM and the geometric standard deviation (GSD of DMP and DEP were 5.73 ug/g cr. (GSD 2.51, and 6.08 ug/g cr. (GSD 3.63, respectively. The percentage of applicators with detectable DMP, DMDTP, and DMTP in urine was 72.72%, 3.03%, and 15.15%, respectively, while the corresponding figures for DEP, DETP, and DEDTP were 48.48%, 36.36% and 15.15%, respectively. There was no significant association between the use of protection practices and the absence of urine OPs metabolites suggesting inadequate protection practices. Conclusion The pesticide applicators in Majes Valley have significant exposure to OP pesticides, probably due to inappropriate protective practices. Future work should evaluate possible health effects.

  14. Organophosphorus pollutants (OPP) in aquatic environment at Damietta Governorate, Egypt: implications for monitoring and biomarker responses.

    Abdel-Halim, K Y; Salama, A K; El-Khateeb, E N; Bakry, N M

    2006-06-01

    The study was carried out from spring 1999 to spring 2001 to monitor the residue levels of organophosphorus pollutants (OPP) in aquatic environment of the drainage canal surrounding a pesticide factory at Damietta Governorate. Water, sediment, and fish samples were collected at six different seasonal periods. OPPs were analyzed by GLC and confirmed using GC-MS. Chlorpyrifos, chlorpyrifos-methyl, malathion, diazinon, pirimiphos-methyl and profenofos were detected in most samples. Chlorpyrifos was dominant in all water and sediment samples. It was ranged from 24.5 to 303.8 and 0.9 to 303.8 ppb in water and sediment samples, respectively. Diazinon level was slightly similar to chlorpyrifos in fish samples. Data based on the grand total concentration of OPP showed that the most polluted samples were collected either at spring 1999 or autumn 2000. They were 675.5 and 303.8 ppb in water samples and 43.0 and 52.2 ppb in fish collected at spring 1999 and autumn 2000, respectively. The obtained results are in parallel to that found in case of cholinesterase activity where the activity of both acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE) was declined at these seasonal period. The activity levels of AChE and BuChE were found to be 77.18% and 59.67% of control at spring 1999 and 78.62% and 85.80% of control, at autumn 2000, respectively. Thus, AChE and BuChE could be used as biomarkers for tracing and biomonitoring OPP pollution.

  15. Antioxidant Role of Pomegranates on Liver and Brain Tissues of Rats Exposed to an Organophosphorus Insecticide

    Abd Elmonem, H.A.

    2014-01-01

    Toxicities of organophosphorus insecticides cause oxidative damage on many organs such as the liver and brain due to generation of reactive oxygen species. Pomegranate is among the richest fruit in poly - phenols. The aim of this study was to compare between the antioxidant strength of pomegranate juice (PJ) and pomegranate molasses (PM) and their effects on alanine transferase (ALT), aspartate aminotransferase (AST), Alkaline phosphatase (ALP) and total protein (TP) in liver and levels of malondialdehyde (MAD), reduced glutathione (GSH) and nitric oxide (NO) in rat liver and brain tissues exposed to 1/10 LD 50 diazinon (DI). Six groups each of 6 male albino rats were used comprising control, DI, PJ, PM, PJ + DI and PM + DI for 15 days. The activities of ALT, AST, and TP concentration in liver have been increased due to treatment of rats with DI. These increases restored to normalcy when rats were supplemented with PJ or PM with DI. The results demonstrate that treatment with DI induced significant increase in MDA and NO concentrations and significant decrease in GSH levels of liver and brain tissues. The administration of PJ or PM along with DI significant decrease in MDA and NO levels and significant increase in GSH level compared to DI-group. The present study suggest that PJ or PM has a potential protective effect as it can elevate antioxidant defense system, lessens induced oxidative dam - ages and protect the brain and liver tissue against DI-induced toxicity. In addition, comaring PJ with PM it was noticed that PJ had higher antioxidant activity as evidenced by increased GSH content and decreased NO level in the liver by greater extend than PM.

  16. Evaluation of medical countermeasures against organophosphorus compounds: the value of experimental data and computer simulations.

    Worek, Franz; Aurbek, Nadine; Herkert, Nadja M; John, Harald; Eddleston, Michael; Eyer, Peter; Thiermann, Horst

    2010-09-06

    Despite extensive research for more than six decades on medical countermeasures against poisoning by organophosphorus compounds (OP) the treatment options are meagre. The presently established acetylcholinesterase (AChE) reactivators (oximes), e.g. obidoxime and pralidoxime, are insufficient against a number of nerve agents and there is ongoing debate on the benefit of oxime treatment in human OP pesticide poisoning. Up to now, the therapeutic efficacy of oximes was mostly evaluated in animal models but substantial species differences prevent direct extrapolation of animal data to humans. Hence, it was considered essential to establish relevant experimental in vitro models for the investigation of oximes as antidotes and to develop computer models for the simulation of oxime efficacy in different scenarios of OP poisoning. Kinetic studies on the various interactions between erythrocyte AChE from various species, structurally different OP and different oximes provided a basis for the initial assessment of the ability of oximes to reactivate inhibited AChE. In the present study, in vitro enzyme-kinetic and pharmacokinetic data from a minipig model of dimethoate poisoning and oxime treatment were used to calculate dynamic changes of AChE activities. It could be shown that there is a close agreement between calculated and in vivo AChE activities. Moreover, computer simulations provided insight into the potential and limitations of oxime treatment. In the end, such data may be a versatile tool for the ongoing discussion of the pros and cons of oxime treatment in human OP pesticide poisoning. Copyright (c) 2009 Elsevier Ireland Ltd. All rights reserved.

  17. Developmental neurotoxicity of the organophosphorus insecticide chlorpyrifos: from clinical findings to preclinical models and potential mechanisms.

    Burke, Richard D; Todd, Spencer W; Lumsden, Eric; Mullins, Roger J; Mamczarz, Jacek; Fawcett, William P; Gullapalli, Rao P; Randall, William R; Pereira, Edna F R; Albuquerque, Edson X

    2017-08-01

    Organophosphorus (OP) insecticides are pest-control agents heavily used worldwide. Unfortunately, they are also well known for the toxic effects that they can trigger in humans. Clinical manifestations of an acute exposure of humans to OP insecticides include a well-defined cholinergic crisis that develops as a result of the irreversible inhibition of acetylcholinesterase (AChE), the enzyme that hydrolyzes the neurotransmitter acetylcholine (ACh). Prolonged exposures to levels of OP insecticides that are insufficient to trigger signs of acute intoxication, which are hereafter referred to as subacute exposures, have also been associated with neurological deficits. In particular, epidemiological studies have reported statistically significant correlations between prenatal subacute exposures to OP insecticides, including chlorpyrifos, and neurological deficits that range from cognitive impairments to tremors in childhood. The primary objectives of this article are: (i) to address the short- and long-term neurological issues that have been associated with acute and subacute exposures of humans to OP insecticides, especially early in life (ii) to discuss the translational relevance of animal models of developmental exposure to OP insecticides, and (iii) to review mechanisms that are likely to contribute to the developmental neurotoxicity of OP insecticides. Most of the discussion will be focused on chlorpyrifos, the top-selling OP insecticide in the United States and throughout the world. These points are critical for the identification and development of safe and effective interventions to counter and/or prevent the neurotoxic effects of these chemicals in the developing brain. This is an article for the special issue XVth International Symposium on Cholinergic Mechanisms. © 2017 International Society for Neurochemistry.

  18. Dust Measurement of Two Organophosphorus Flame Retardants, Resorcinol Bis(diphenylphosphate) (RBDPP) and Bisphenol A Bis(diphenylphosphate) (BPA-BDPP), Used as Alternatives for BDE-209

    Brandsma, S.H.; Sellström, U.; de Wit, C.A.; de Boer, J.; Leonards, P.E.G.

    2013-01-01

    Resorcinol bis(diphenylphosphate) (RBDPP) and bisphenol A bis(diphenylphosphate) (BPA-BDPP) are two halogen-free organophosphorus flame retardant (PFRs) that are used as an alternative for the decabromodiphenyl ether (Deca-BDE) technical mixture in TV/flatscreen housing and other electronic consumer

  19. Monitoring of organochlorine and organophosphorus pesticide residues in water during different seasons of Tighra reservoir Gwalior, Madhya Pradesh, India.

    Mamta; Rao, R J; Wani, Khursheed Ahmad

    2015-11-01

    Analysis of pesticides during different seasons for pesticidal contamination in water samples of Tighra reservoir was carried out on gas chromatograph-electron capture detector with capillary columns following multiresidual analytical technique. Organochlorine pesticides, viz., hexachlorobenzene (HCB), alpha-benzene hexachloride (BHC), beta-BHC, γ-BHC, heptachlor, aldrin, alpha-endosulfan, beta-endosulfan, p,p-DDE, dieldrin, o,p-dichlorodiphenyldichloroethane (DDD), p,p-DDD, p,p-dichlorodiphenyltrichloroethane (DDT), and endrin, and organophosphorus pesticides, viz., choloropyrifos, methyl parathion, diazion, dicholorovos, ethion, malathion, and parathion, were detected in water samples during different seasons. However, the pesticide concentration varied during different seasons at different sites. The prominent reason of contamination is the use of pesticides (both organochlorine and organophosphorus) in the agricultural fields near Tighra reservoir. On the basis of our observations, more extensive monitoring studies need to be carried out, covering all wetlands of Madhya Pradesh to enforce the policies for the restricted application of pesticides in agricultural fields adjacent to wetlands.

  20. Pharmacokinetics and effects on serum cholinesterase activities of organophosphorus pesticides acephate and chlorpyrifos in chimeric mice transplanted with human hepatocytes.

    Suemizu, Hiroshi; Sota, Shigeto; Kuronuma, Miyuki; Shimizu, Makiko; Yamazaki, Hiroshi

    2014-11-01

    Organophosphorus pesticides acephate and chlorpyrifos in foods have potential to impact human health. The aim of the current study was to investigate the pharmacokinetics of acephate and chlorpyrifos orally administered at lowest-observed-adverse-effect-level doses in chimeric mice transplanted with human hepatocytes. Absorbed acephate and its metabolite methamidophos were detected in serum from wild type mice and chimeric mice orally administered 150mg/kg. Approximately 70% inhibition of cholinesterase was evident in plasma of chimeric mice with humanized liver (which have higher serum cholinesterase activities than wild type mice) 1day after oral administrations of acephate. Adjusted animal biomonitoring equivalents from chimeric mice studies were scaled to human biomonitoring equivalents using known species allometric scaling factors and in vitro metabolic clearance data with a simple physiologically based pharmacokinetic (PBPK) model. Estimated plasma concentrations of acephate and chlorpyrifos in humans were consistent with reported concentrations. Acephate cleared similarly in humans and chimeric mice but accidental/incidental overdose levels of chlorpyrifos cleared (dependent on liver metabolism) more slowly from plasma in humans than it did in mice. The data presented here illustrate how chimeric mice transplanted with human hepatocytes in combination with a simple PBPK model can assist evaluations of toxicological potential of organophosphorus pesticides. Copyright © 2014 Elsevier Inc. All rights reserved.

  1. Novel organophosphorus scaffolds of urease inhibitors obtained by substitution of Morita-Baylis-Hillman adducts with phosphorus nucleophiles.

    Ntatsopoulos, Vassilis; Vassiliou, Stamatia; Macegoniuk, Katarzyna; Berlicki, Łukasz; Mucha, Artur

    2017-06-16

    The reactivity of Morita-Baylis-Hillman allyl acetates was employed to introduce phosphorus-containing functionalities to the side chain of the cinnamic acid conjugated system by nucleophilic displacement. The proximity of two acidic groups, the carboxylate and phosphonate/phosphinate groups, was necessary to form interactions in the active site of urease by recently described inhibitor frameworks. Several organophosphorus scaffolds were obtained and screened for inhibition of the bacterial urease, an enzyme that is essential for survival of urinary and gastrointestinal tract pathogens. α-Substituted phosphonomethyl- and 2-phosphonoethyl-cinnamate appeared to be the most potent and were further optimized. As a result, one of the most potent organophosphorus inhibitors of urease, α-phosphonomethyl-p-methylcinnamic acid, was identified, with K i  = 0.6 μM for Sporosarcina pasteurii urease. High complementarity to the enzyme active site was achieved with this structure, as any further modifications significantly decreased its affinity. Finally, this work describes the challenges faced in developing ligands for urease. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  2. Synthesis of organophosphorus modified nanoparticles and their reinforcements on the fire safety and mechanical properties of polyurea

    Qian, Xiaodong [State Key Laboratory of Fire Science, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui 230026 (China); USTC-CityU Joint Advanced Research Centre, Suzhou Key Laboratory of Urban Public Safety, Suzhou Institute for Advanced Study, University of Science and Technology of China, 166 Ren’ai Road Suzhou, Jiangsu 215123 (China); Song, Lei, E-mail: leisong@ustc.edu.cn [State Key Laboratory of Fire Science, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui 230026 (China); Wang, Bibo [State Key Laboratory of Fire Science, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui 230026 (China); Hu, Yuan, E-mail: yuanhu@ustc.edu.cn [State Key Laboratory of Fire Science, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui 230026 (China); USTC-CityU Joint Advanced Research Centre, Suzhou Key Laboratory of Urban Public Safety, Suzhou Institute for Advanced Study, University of Science and Technology of China, 166 Ren’ai Road Suzhou, Jiangsu 215123 (China); Yuen, Richard K.K., E-mail: Richard.Yuen@cityu.edu.hk [USTC-CityU Joint Advanced Research Centre, Suzhou Key Laboratory of Urban Public Safety, Suzhou Institute for Advanced Study, University of Science and Technology of China, 166 Ren’ai Road Suzhou, Jiangsu 215123 (China); Department of Building and Construction, City University of Hong Kong, Tat Chee Avenue Kowloon (Hong Kong)

    2013-05-15

    Novel organophosphorus modified nanoparticles (FRs-nanoparticles) were synthesized by the hydrolysis and condensation of both 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide modified vinyl trimethoxy silane (DOPO-VTS) and 3-triethoxysilylpropylamine. FRs-nanoparticles were incorporated into the polyurea matrix in different ratios via in situ polymerization, resulting in the formation of organic/inorganic nanocomposites. The nanocomposites were characterized by thermogravimetric analysis (TGA), real-time fourier transform infrared spectra (RTIR), microscale combustion calorimeter (MCC) and tensile testing machine. The TGA results revealed that FRs-nanoparticles could slightly catalyze the thermal degradation of the nanocomposites in nitrogen atmosphere, but significantly improve the thermal stability of the nanocomposites in air atmosphere. The T{sub 0.5} (50wt.% weight loss) of the nanocomposites was delayed by 32 °C in air atmosphere. Moreover, the char yield increased from 2.3wt.% to 8.9 wt.% at 550 °C when the loadings of FRs-nanoparticles was 10wt.%, indicating the catalyzing charring effect of FRs-nanoparticles. The MCC results revealed that all the nanocomposites exhibited much lower flammability compared with virgin polyurea. Furthermore, the tensile test indicated that the FRs-nanoparticles could also improve the mechanical properties of polyurea. - Highlights: ► Novel organophosphorus modified nanoparticles (FRs-nanoparticles) were synthesized. ► FRs-nanoparticles were incorporated into the polyurea. ► Both the thermal stability and mechanical properties of polyurea were improved.

  3. Detection of Organophosphorus Pesticides in Wheat by Ionic Liquid-Based Dispersive Liquid-Liquid Microextraction Combined with HPLC

    Wei Liu

    2018-01-01

    Full Text Available Food safety issues closely related to human health have always received widespread attention from the world society. As a basic food source, wheat is the fundamental support of human survival; therefore, the detection of pesticide residues in wheat is very necessary. In this work, the ultrasonic-assisted ionic liquid-dispersive liquid-liquid microextraction (DLLME method was firstly proposed, and the extraction and analysis of three organophosphorus pesticides were carried out by combining high-performance liquid chromatography (HPLC. The extraction efficiencies of three ionic liquids with bis(trifluoromethylsulfonylimide (Tf2N anion were compared by extracting organophosphorus in wheat samples. It was found that the use of 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonylimide ([OMIM][Tf2N] had both high enrichment efficiency and appropriate extraction recovery. Finally, the method was used for the determination of three wheat samples, and the recoveries of them were 74.8–112.5%, 71.8–104.5%, and 83.8–115.5%, respectively. The results show that the method proposed is simple, fast, and efficient, which can be applied to the extraction of organic matters in wheat samples.

  4. Synthesis of organophosphorus modified nanoparticles and their reinforcements on the fire safety and mechanical properties of polyurea

    Qian, Xiaodong; Song, Lei; Wang, Bibo; Hu, Yuan; Yuen, Richard K.K.

    2013-01-01

    Novel organophosphorus modified nanoparticles (FRs-nanoparticles) were synthesized by the hydrolysis and condensation of both 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide modified vinyl trimethoxy silane (DOPO-VTS) and 3-triethoxysilylpropylamine. FRs-nanoparticles were incorporated into the polyurea matrix in different ratios via in situ polymerization, resulting in the formation of organic/inorganic nanocomposites. The nanocomposites were characterized by thermogravimetric analysis (TGA), real-time fourier transform infrared spectra (RTIR), microscale combustion calorimeter (MCC) and tensile testing machine. The TGA results revealed that FRs-nanoparticles could slightly catalyze the thermal degradation of the nanocomposites in nitrogen atmosphere, but significantly improve the thermal stability of the nanocomposites in air atmosphere. The T 0.5 (50wt.% weight loss) of the nanocomposites was delayed by 32 °C in air atmosphere. Moreover, the char yield increased from 2.3wt.% to 8.9 wt.% at 550 °C when the loadings of FRs-nanoparticles was 10wt.%, indicating the catalyzing charring effect of FRs-nanoparticles. The MCC results revealed that all the nanocomposites exhibited much lower flammability compared with virgin polyurea. Furthermore, the tensile test indicated that the FRs-nanoparticles could also improve the mechanical properties of polyurea. - Highlights: ► Novel organophosphorus modified nanoparticles (FRs-nanoparticles) were synthesized. ► FRs-nanoparticles were incorporated into the polyurea. ► Both the thermal stability and mechanical properties of polyurea were improved

  5. Organophosphorus flame retardants and heavy metals in municipal landfill leachate treatment system in Guangzhou, China.

    Deng, Mingjun; Kuo, Dave T F; Wu, Qihang; Zhang, Ying; Liu, Xinyu; Liu, Shengyu; Hu, Xiaodong; Mai, Bixian; Liu, Zhineng; Zhang, Haozhi

    2018-05-01

    The occurrence, distribution and removal efficiencies of organophosphorus flame retardants (OPFRs) and metals were examined in a municipal landfill leachate treatment system in Guangzhou, China. Five OPFRs and thirty-five metals were detected in wastewater samples collected at different treatment stages. ∑OPFRs was reduced from 4807.02 ng L -1 to 103.91 ng L -1 through the treatment system, with close to 98% removed from the dissolved phase. Tris(clorisopropyl) phosphates (TCPPs) dominated through the treatment process and accounted for over 80% and 50% of ∑OPFRs at the influent and the effluent, respectively. TCPPs were most efficiently removed (98.6%) followed by tris(2-chloroethyl) phosphate (TCEP) (96.6%) and triphenyl phosphate (TPP) (88.5%). For metals, Fe, Cr, and Rb were dominant in the raw leachate, detected at 7.55, 2.82, and 4.50 mg L -1 , respectively. Thirteen regulated heavy metals - including eight major pollutants (i.e., As. Cd, Cr, Cu, Hg, Ni, Pb, and Zn) - have been detected in all wastewater samples at sub-mg L -1 levels. Over 99.5% removal was achieved for Cr, Ni, and Fe, and close to 95% removal efficiency was observed for Rb. For the eight major heavy metals, over 99% removal was observed; the only exception was Cu, which was removed at 89%. It was found that microfiltration/reverse osmosis was critical for the removal of OPFRs and heavy metals while the core biological treatment played a minor role towards their removal. Remobilization of Co, Cu, Fe, Hg, Mn, Ni, Sb, and Sr from the returned sludge occurred during the second denitrification, indicating the need for additional post-biological process for effective removal of both contaminants. This study highlights the critical need to develop cheap, effective treatment technologies for contaminants-laden leachate generated from open dumps and under-designed landfills. Copyright © 2018 Elsevier Ltd. All rights reserved.

  6. Distinct patterns of gene and protein expression elicited by organophosphorus pesticides in Caenorhabditis elegans

    Dennis William E

    2009-04-01

    Full Text Available Abstract Background The wide use of organophosphorus (OP pesticides makes them an important public health concern. Persistent effects of exposure and the mechanism of neuronal degeneration are continuing issues in OP toxicology. To elucidate early steps in the mechanisms of OP toxicity, we studied alterations in global gene and protein expression in Caenorhabditis elegans exposed to OPs using microarrays and mass spectrometry. We tested two structurally distinct OPs (dichlorvos and fenamiphos and employed a mechanistically different third neurotoxicant, mefloquine, as an out-group for analysis. Treatment levels used concentrations of chemical sufficient to prevent the development of 10%, 50% or 90% of mid-vulval L4 larvae into early gravid adults (EGA at 24 h after exposure in a defined, bacteria-free medium. Results After 8 h of exposure, the expression of 87 genes responded specifically to OP treatment. The abundance of 34 proteins also changed in OP-exposed worms. Many of the genes and proteins affected by the OPs are expressed in neuronal and muscle tissues and are involved in lipid metabolism, cell adhesion, apoptosis/cell death, and detoxification. Twenty-two genes were differentially affected by the two OPs; a large proportion of these genes encode cytochrome P450s, UDP-glucuronosyl/UDP-glucosyltransferases, or P-glycoproteins. The abundance of transcripts and the proteins they encode were well correlated. Conclusion Exposure to OPs elicits a pattern of changes in gene expression in exposed worms distinct from that of the unrelated neurotoxicant, mefloquine. The functional roles and the tissue location of the genes and proteins whose expression is modulated in response to exposure is consistent with the known effects of OPs, including damage to muscle due to persistent hypercontraction, neuronal cell death, and phase I and phase II detoxification. Further, the two different OPs evoked distinguishable changes in gene expression; about half

  7. Tracing organophosphorus and brominated flame retardants and plasticizers in an estuarine food web.

    Brandsma, Sicco H; Leonards, Pim E G; Leslie, Heather A; de Boer, Jacob

    2015-02-01

    Nine organophosphorus flame retardants (PFRs) were detected in a pelagic and benthic food web of the Western Scheldt estuary, The Netherlands. Concentrations of several PFRs were an order of magnitude higher than those of the brominated flame retardants (BFRs). However, the detection frequency of the PFRs (6-56%) was lower than that of the BFRs (50-97%). Tris(2-butoxyethyl) phosphate (TBOEP), tris(isobutyl) phosphate (TIBP) and tris(2-chloroisopropyl) phosphate (TCIPP) were the dominant PFRs in sediment with median concentrations of 7.0, 8.1 and 1.8 ng/g dry weight (dw), respectively. PFR levels in the suspended particular matter (SPM) were 2-12 times higher than that in sediment. TBOEP, TCIPP, TIBP, tris(2-chloroethyl) phosphate (TCEP) and tris(phenyl) phosphate (TPHP) were found in organisms higher in the estuarine food web. The highest PFR concentrations in the benthic food web were found in sculpin, goby and lugworm with median concentrations of 17, 7.4, 4.6 and 2.0 ng/g wet weight (ww) for TBOEP, TIBP, TCIPP and TPHP, respectively. Comparable levels were observed in the pelagic food web, BDE209 was the predominant PBDE in sediment and SPM with median concentrations up to 9.7 and 385 ng/g dw, respectively. BDE47 was predominant in the biotic compartment of the food web with highest median levels observed in sculpin and common tern eggs of 79 ng/g lipid weight (lw) (2.5 ng/g ww) and 80 ng/g lw (11 ng/g ww), respectively. Trophic magnification was observed for all PBDEs with the exception of BDE209. Indications of trophic magnification of PFRs were observed in the benthic food web for TBOEP, TCIPP and TCEP with tentative trophic magnification factors of 3.5, 2.2 and 2.6, respectively (pwebs. The relative high PFR levels in several fish species suggest high emissions and substantial exposure of organisms to PFRs in the Western Scheldt. Copyright © 2014 Elsevier B.V. All rights reserved.

  8. Analysis of monomeric and oligomeric organophosphorus flame retardants in fish muscle tissues using liquid chromatography–electrospray ionization tandem mass spectrometry: Application to Nile tilapia (Oreochromis niloticus) from an e-waste processing area in northern Vietnam

    Matsukami, Hidenori; Suzuki, Go; Tue, Nguyen Minh; Tuyen, Le Huu; Viet, Pham Hung; Takahashi, Shin; Tanabe, Shinsuke; Takigami, Hidetaka

    2016-01-01

    Using electrospray ionization tandem mass spectrometry combined with liquid chromatography (LC), a novel analytical method was developed to quantify eight monomeric organophosphorus flame retardants (m-PFRs) and three oligomeric organophosphorus flame retardants (o-PFRs) in fish muscle samples. The optimization and validation experiments indicate that the developed method can determine accurately the concentrations of analytes in fish muscle samples. The recoveries of analytes in fish muscle ...

  9. Compostos organofosforados pentavalentes: histórico, métodos sintéticos de preparação e aplicações como inseticidas e agentes antitumorais Organophosphorus pentavalent compounds: history, synthetic methods of preparation and application as insecticides and antitumor agents

    Viviane Martins Rebello dos Santos

    2007-02-01

    Full Text Available This paper is a review of the history, synthesis and application of organophosphorus compounds, especially of those of pentavalent phosphorus, such as phosphoramidates, phosphorothioates, phosphonates and phosphonic acids with insecticide and anticancer activities. The organophosphorus compounds with agrochemical applications show great structural variety, They include not only insecticides, but also fungicides, herbicides, and others. The large variety of commercially available organophosphorus pesticides is remarkable. Even more interesting is the high efficiency of some organophosphorus compounds as anticancer agents such as cyclophosphamide and its derivatives.

  10. Degradation of Organophosphorus Pesticides in Water during UV/H2O2 Treatment: Role of Sulphate and Bicarbonate Ions

    Am Fadaei

    2012-01-01

    Full Text Available The photodegradation of two organophosphorus pesticides, malathian and diazinon, by sulfate radicals and bicarbonate radicals in aqueous solution were studied. The effect of the operational parameters such as pH, salt concentration, water type, H2O2 concentration and initial concentration of pesticides was studied. Gas chromatography mass spectroscopy (GC–MS was used for analyses of pesticides. When salt effect was studied, it was found that sodium bicarbonate was the most powerful inhibitor used, while sodium sulfate was the weakest one. The highest degradation in UV/H2O2 process for malathion was found in alkaline condition and for diazinon in acidic condition. The photodegradation in all waters used in this work exhibited first order kinetics. Photodegradation rate in distilled water was higher than real water. The degradation of pesticides increased with increasing of H2O2 concentration.

  11. Effect of two organophosphorus insecticides on the growth, respiration and (/sup 14/C)-glucose metabolism of Azobacter chroococcum Beij

    Balasubramanian, A; Narayanan, R [Tamil Nadu Agricultural Univ., Coimbatore (India)

    1980-01-01

    The two organophosphorus insecticides, commonly applied to soil, viz., disulfoton (0,0-diethyl S-2-ethyl thio ethyl phosphorodithioate) and fensulfothion (0,0-diethyl 0-4-methyl sulphinyl phenyl phosphorothioate) did not affect the in vitro growth of Azotobacter chroococcum Beij., the free-living, nitrogen fixing soil bacterium, at 2 ppm (lower level), while the normal dose (5 ppm) and the higher level (10 ppm) suppressed the growth. Respiration of the organism (glucose oxidation) was adversely affected by the insecticides in the growth medium and the inhibition increased with the concentration of the chemical. Both the insecticides suppressed the assimilation of (/sup 14/C)-glucose in the cold-TCA soluble, hot-TCA soluble fractions and insoluble residue of the cells whereas the /sup 14/C-incorporation in the alcohol soluble and alcohol-ether soluble fractions was enhanced indicating that the insecticides considerably altered the glucose metabolism of the bacterium.

  12. [How aliphatic alcohols and ph affect reactional capability of the horse blood serum cholinesterase at its interaction with organophosphorus inhibitors].

    Basova, N E; Kormilitsin, B N; Perchenok, A Iu; Rozengart, E V; Saakov, V S; Suvorov, A A

    2013-01-01

    There was studied action of aliphatic alcohols (ethanol, propanol, isopropanol, n-butanol, isobutanol, secbutanol, tretbetanol) and pH on various kinds of reactional capability the serum cholinesterase. At the alcohols-affected inhibition of the cholinesterase hydrolytic activity, the determining role was played not the total number carbon atoms in the alcohol molecule, but by the "effective length" of the carbohydrate chain. The fact that the presence of alcohols did not affect parameters of the reverse cholinesterase inhibition with onium ions tetramethylammonium and choline allows suggesting the absence of effect solvents on specific acetylcholine sorption in the enzyme active center. With aid of two rows of hydrophobic organophosphorus inhibitors (OPI), we have managed to estimate both the degree and the character itself of the modifying action of alcohols and pH on the process of irreversible inhibition of serum cholinesterase.

  13. [Comparative analysis of sensitivity of proteases (chymotrypsin and trypsin) and cholinesterases of different origin to some organophosphorus inhibitors].

    Rozengart, E V

    2009-01-01

    The antichymotrypsin, antitrypsin, and anticholinesterase efficiencies of four homologous series of organophosphorus inhibitors are compared: O-ethyl-S-(n-alkyl)methylthiophosphonates, O-(n-alkyl)-S-(n-butyl)methylthiophosphonates, O-(n-alkyl)-S-beta-(ethylmercaptoethylene)methylthiophosphonates, and their methylsulfomethylates. As sources of a-chymotrypsin and trypsin, commercial compounds of Worthington Biochemical Corporation and Leningrad Myasokombinat were tested. Bimolecular constant of the reaction rate was used as the measure of antienzyme efficiency. In all cases, the antichymotrypsin efficiency was lower, while the antitrypsin--essentially higher than the anticholinesterase activity of the studied inhibitors. These differences were found to much depend both on the inhibitor structure and on nature of the cholinesterase compounds.

  14. Towards a Capacitive Enzyme Sensor for Direct Determination of Organophosphorus Pesticides: Fundamental Studies and Aspects of Development

    Ashok Mulchandani

    2003-06-01

    Full Text Available The realisation of a miniaturised potentiometric enzyme biosensor is presented. The biosensor chip utilises the enzyme organophosphorus hydrolase (OPH for the direct determination of pesticides. The transducer structure of the sensors chip consists of a pH-sensitive capacitive electrolyte-insulator-semiconductor (EIS structure that reacts towards pH changes caused by the OPH-catalised hydrolysis of the organophosphate compounds. The biosensor is operated versus a conventional Ag/AgCl reference electrode. Measurements were performed in the capacitance/voltage (C/V and the constant capacitance (ConCap mode for the two different pesticides paraoxon and parathion. For the development of this new type of biosensor, different immobilisation strategies, influence of buffer composition and concentration, transducer material, detection limit, long-term stability and selectivity have been studied.

  15. Effect of two organophosphorus insecticides on the growth, respiration and (14C)-glucose metabolism of Azobacter chroococcum Beij

    Balasubramanian, A.; Narayanan, R.

    1980-01-01

    The two organophosphorus insecticides, commonly applied to soil, viz., disulfoton (0,0-diethyl S-2-ethyl thio ethyl phosphorodithioate) and fensulfothion (0,0-diethyl 0-4-methyl sulphinyl phenyl phosphorothioate) did not affect the in vitro growth of Azotobacter chroococcum Beij., the free-living, nitrogen fixing soil bacterium, at 2 ppm (lower level), while the normal dose (5 ppm) and the higher level (10 ppm) suppressed the growth. Respiration of the organism (glucose oxidation) was adversely affected by the insecticides in the growth medium and the inhibition increased with the concentration of the chemical. Both the insecticides suppressed the assimilation of ( 14 C)-glucose in the cold-TCA soluble, hot-TCA soluble fractions and insoluble residue of the cells whereas the 14 C-incorporation in the alcohol soluble and alcohol-ether soluble fractions was enhanced indicating that the insecticides considerably altered the glucose metabolism of the bacterium. (author)

  16. Electrophysiologic changes following treatment with organophosphorus-induced delayed neuropathy-producing agents in the adult hen.

    Robertson, D G; Schwab, B W; Sills, R D; Richardson, R J; Anderson, R J

    1987-03-15

    Although clinical, pathological, and biochemical effects of organophosphorus-induced delayed neuropathy (OPIDN) have been intensively investigated in the adult hen, detailed electrophysiological studies are lacking. Adult white leghorn hens were treated with a single oral dose of either 30 mg/kg tri-2-cresyl phosphate (TOCP), 750 mg/kg TOCP, 4 mg/kg di-n-butyl-2,2-dichlorovinyl phosphate (DBCV), or 30 mg/kg di-n-butyl-2,2-dichlorovinyl phosphinate (DBCV-P). The 750 mg/kg TOCP and DBCV, but not the 30 mg/kg TOCP and DBCV-P, treatments resulted in clinical signs of OPIDN and mild to marked damage of the tibial nerve 21 days after dose. Twenty-four hr lymphocyte neurotoxic esterase (NTE) inhibition was used as an index of brain NTE inhibition for the various organophosphorus compound (OP) treatment. Twenty-four hr lymphocyte NTE inhibition for 30 mg/kg TOCP, 750 mg/kg TOCP, DBCV, and DBCV-P was 54.1, 87.1, 84.8, and 68.3%, respectively. Twenty-one days after dose, the TOCP-treated hens exhibited some abnormalities in conduction velocity and action potential duration in the tibial or sciatic nerves. No abnormalities were observed in action potential parameters of either the DBCV or DBCV-P treatments. Neurotoxic OP (TOCP and DBCV) treatment resulted in decreased refractoriness in the tibial nerve, increased refractoriness in the sciatic nerve, and elevated strength duration threshold for both nerves. These changes were not present in nerves from DBCV-P (a non-neurotoxic NTE inhibitor)-treated hens. These results suggest that refractory period and strength duration abnormalities in peripheral nerve correlate well with the production of OPIDN and are evident without coincident clinical signs or histopathology.

  17. Determination of no-observed effect level (NOEL-biomarker equivalents to interpret biomonitoring data for organophosphorus pesticides in children

    Bouchard Michèle

    2009-02-01

    Full Text Available Abstract Background Environmental exposure to organophosphorus pesticides has been characterized in various populations, but interpretation of these data from a health risk perspective remains an issue. The current paper proposes biological reference values to help interpret biomonitoring data related to an exposure to organophosphorus pesticides in children for which measurements of alkylphosphate metabolites are available. Methods Published models describing the kinetics of malathion and chlorpyrifos in humans were used to determine no-observed effect level – biomarker equivalents for methylphosphates and ethylphosphates, respectively. These were expressed in the form of cumulative urinary amounts of alkylphosphates over specified time periods corresponding to an absorbed no-observed effect level dose (derived from a published human exposure dose and assuming various plausible exposure scenarios. Cumulative amounts of methylphosphate and ethylphosphate metabolites measured in the urine of a group of Quebec children were then compared to the proposed biological reference values. Results From a published no-observed effect level dose for malathion and chlorpyrifos, the model predicts corresponding oral biological reference values for methylphosphate and ethylphosphate derivatives of 106 and 52 nmol/kg of body weight, respectively, in 12-h nighttime urine collections, and dermal biological reference values of 40 and 32 nmol/kg of body weight. Out of the 442 available urine samples, only one presented a methylphosphate excretion exceeding the biological reference value established on the basis of a dermal exposure scenario and none of the methylphosphate and ethylphosphate excretion values were above the obtained oral biological reference values, which reflect the main exposure route in children. Conclusion This study is a first step towards the development of biological guidelines for organophophorus pesticides using a toxicokinetic modeling

  18. Determination of some organophosphorus pesticides in water and watermelon samples by microextraction prior to high-performance liquid chromatography.

    Wang, Chun; Wu, Qiuhua; Wu, Chunxia; Wang, Zhi

    2011-11-01

    A novel method based on simultaneous liquid-liquid microextraction and carbon nanotube reinforced hollow fiber microporous membrane solid-liquid phase microextraction has been developed for the determination of six organophosphorus pesticides, i.e. isocarbophos, phosmet, parathion-methyl, triazophos, fonofos and phoxim, in water and watermelon samples prior to high-performance liquid chromatography (HPLC). Under the optimum conditions, the method shows a good linearity within a range of 1-200 ng/mL for water samples and 5-200 ng/g for watermelon samples, with the correlation coefficients (r) varying from 0.9990 to 0.9997 and 0.9986 to 0.9995, respectively. The limits of detection (LODs) were in the range between 0.1 and 0.3 ng/mL for water samples and between 1.0 and 1.5 ng/g for watermelon samples. The recoveries of the method at spiking levels of 5.0 and 50.0 ng/mL for water samples were between 85.4 and 100.8%, and at spiking levels of 5.0 and 50.0 ng/g for watermelon samples, they were between 82.6 and 92.4%, with the relative standard deviations (RSDs) varying from 4.5-6.9% and 5.2-7.4%, respectively. The results suggested that the developed method represents a simple, low-cost, high analytes preconcentration and excellent sample cleanup procedure for the determination of organophosphorus pesticides in water and watermelon samples. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. In vitro study of the neuropathic potential of the organophosphorus compounds fenamiphos and profenofos: Comparison with mipafox and paraoxon.

    Emerick, Guilherme L; Fernandes, Laís S; de Paula, Eloísa Silva; Barbosa, Fernando; dos Santos, Neife Aparecida Guinaim; dos Santos, Antonio Cardozo

    2015-08-01

    Organophosphorus-induced delayed neuropathy (OPIDN) is a central-peripheral distal axonopathy that develops 8-14 days after poisoning by a neuropathic organophosphorus compound (OP). Several OPs that caused OPIDN were withdrawn from the agricultural market due to induction of serious delayed effects. Therefore, the development of in vitro screenings able to differentiate neuropathic from non-neuropathic OPs is of crucial importance. Thus, the aim of this study was to evaluate the differences in the neurotoxic effects of mipafox (neuropathic OP) and paraoxon (non-neuropathic OP) in SH-SY5Y human neuroblastoma cells, using the inhibition and aging of neuropathy target esterase (NTE), inhibition of acetylcholinesterase (AChE), activation of calpain, neurite outgrowth, cytotoxicity and intracellular calcium as indicators. Additionally, the potential of fenamiphos and profenofos to cause acute and/or delayed effects was also evaluated. Mipafox had the lowest IC50 and induced the highest percentage of aging of NTE among the OPs evaluated. Only mipafox was able to cause calpain activation after 24 h of incubation. Concentrations of mipafox and fenamiphos which inhibited at least 70% of NTE were also able to reduce neurite outgrowth. Cytotoxicity was higher in non-neuropathic than in neuropathic OPs while the intracellular calcium levels were higher in neuropathic than in non-neuropathic OPs. In conclusion, the SH-SY5Y cellular model was selective to differentiate neuropathic from non-neuropathic OPs; fenamiphos, but not profenofos presented results compatible with the induction of OPIDN. Copyright © 2015 Elsevier Ltd. All rights reserved.

  20. Rapid simultaneous determination of organophosphorus pesticides in human serum and urine by liquid chromatography-mass spectrometry

    Zlatković Milica

    2010-01-01

    Full Text Available Background/Aim. Analysis of organophosphosphorus compounds and their metabolites in a biological material includes the use of numerous methods, covering both preparation of samples for analysis and their identification that is considered to be very complex. Low concentrations monitoring requires implementation of highly sensitive analytical techniques. The aim of this study was to develop and validate an original and sensitive method for the detection and quantitation of organophosphorus pesticides (dimethoate, diazinon, malathion and malaoxon in human biological matrices (serum, urine. Methods. This method was based on a solid-phase extraction procedure, a chromatographic separation using an ACQUITY UPLC ® HSST3 column and mass spectrometric detection in the positve ion mode. Mobile phase: was consited of Solvent A (5 mM ammonium formate pH 3.0 and Solvent B (0.1% acetic formate in methanol, in a linear gradient (constant flow-rate 0.3 mL/min. Results. The standard curve was linear in the range of 0.05-5.00 mg/L for malathion and malaoxon, 0.10-5.00 mg/L for dimethoate and 0.05-2.50 mg/L for diazinon. The correlation coefficient was r ≥ 0.99. Extraction recoveries were satisfactory and ranged between 90-99%. The limits of detection (LOD was between 0.007- 0.07 mg/L and the limits of quantitation (LOQ ranged between 0.022-0.085 mg/L. Intra- and interassay precision and accuracy were satisfactory for all of the pesticides analyzed. Conclusion. The method of liquid chromatography - mass spectrometry is simple, accurate, and useful for the determination of organophosphorus pesticides in both clinical and forensic toxicology.

  1. Sol-gel niobia sorbent with a positively charged octadecyl ligand providing enhanced enrichment of nucleotides and organophosphorus pesticides in capillary microextraction for online HPLC analysis.

    Kesani, Sheshanka; Malik, Abdul

    2018-04-01

    A niobia-based sol-gel organic-inorganic hybrid sorbent carrying a positively charged C 18 ligand (Nb 2 O 5 -C 18 (+ve)) was synthesized to achieve enhanced enrichment capability in capillary microextraction of organophosphorus compounds (which include organophosphorus pesticides and nucleotides) before their online analysis by high-performance liquid chromatography. The sorbent was designed to simultaneously provide three different types of molecular level interactions: electrostatic, Lewis acid-base, and van der Waals interactions. To understand relative contributions of various molecular level analyte-sorbent interactions in the extraction process, two other sol-gel niobia sorbents were also created: (a) a purely inorganic sol-gel niobia sorbent (Nb 2 O 5 ) and (b) an organic-inorganic hybrid sol-gel niobia sorbent carrying an electrically neutral-bonded octadecyl ligand (Nb 2 O 5 -C 18 ). The extraction efficiency of the created sol-gel niobia sorbent (Nb 2 O 5 -C 18 (+ve)) was compared with that of analogously designed and synthesized titania-based sol-gel sorbent (TiO 2 -C 18 (+ve)), taking into consideration that titania-based sorbents present state-of-the-art extraction media for organophosphorus compounds. In capillary microextraction with high-performance liquid chromatography analysis, Nb 2 O 5 -C 18 (+ve) had shown 40-50% higher specific extraction values (a measure of extraction efficiency) over that of TiO 2 -C 18 (+ve). Compared to TiO 2 -C 18 (+ve), Nb 2 O 5 -C 18 (+ve) also provided superior analyte desorption efficiency (96 vs. 90%) during the online release of the extracted organophosphorus pesticides from the sorbent coating in the capillary microextraction capillary to the chromatographic column using reversed-phase high-performance liquid chromatography mobile phase. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. A SAW-Based Chemical Sensor for Detecting Sulfur-Containing Organophosphorus Compounds Using a Two-Step Self-Assembly and Molecular Imprinting Technology

    Yong Pan

    2014-05-01

    Full Text Available This paper presents a new effective approach for the sensitive film deposition of surface acoustic wave (SAW chemical sensors for detecting organophosphorus compounds such as O-ethyl-S-2-diisopropylaminoethyl methylphosphonothiolate (VX containing sulfur at extremely low concentrations. To improve the adsorptive efficiency, a two-step technology is proposed for the sensitive film preparation on the SAW delay line utilizing gold electrodes. First, mono[6-deoxy-6-[(mercaptodecamethylenethio

  3. Actinide immobilization in the subsurface environment by in-situ treatment with a hydrolytically unstable organophosphorus complexant: Uranyl uptake by calcium phytate

    Nash, K.L.; Jensen, M.P.; Schmidt, M.A.

    1997-01-01

    In addition to naturally occurring uranium and thorium, actinide ions exist in the subsurface environment as a result of accidental releases and intentional disposal practices associated with nuclear weapons production. These species present a significant challenge to cost-effective remediation of contaminated environments. An attractive approach to decreasing the probability of actinide migration in the subsurface is to transform the ions into a less mobile form by remote treatment. We have under development a process which relies on a polyfunctional organophosphorus complexant to sequester the mobile metal ions by complexation/cation exchange in the near term, and to subsequently decompose, transforming the actinides into insoluble phosphate mineral forms in the long term. Studies to date include identification of a suitable organophosphorus reagent, profiling of its decomposition kinetics, verification of the formation of phosphate mineral phases upon decomposition of the reagent, and extensive comparison of the actinide uptake ability of the calcium salt of the reagent as compared with hydroxyapatite. In this report, we briefly describe the process with focus on the cation exchange behavior of the calcium salt of the organophosphorus sequestrant

  4. [Feasibility investigation of hydrogen instead of helium as carrier gas in the determination of five organophosphorus pesticides by gas chromatography-mass spectrometry].

    Liu, Zhenxue; Zhou, Shixue

    2015-01-01

    Helium is almost the only choosable carrier gas used in gas chromatography-mass spectrometry (GC-MS). A mixed standard solution of five organophosphorus pesticides was analyzed by using GC-MS, and hydrogen or helium as carrier gas, so as to study the feasibility of hydrogen instead of helium as carrier gas for the determination of organophosphorus pesticides. Combining a mass spectrum database built by ourselves, the results were deconvolved and identified by Automated Mass Spectral Deconvolution & Identification System (AMDIS32), a software belonging to the workstation of the instrument. Then, the statistical software, IBM SPSS Statistics 19.0 was used for the clustering analysis of the data. The results indicated that when hydrogen was used as carrier gas, the peaks of the pesticides detected were slightly earlier than those when helium used as carrier gas, but the resolutions of the chromatographic peaks were lower, and the fraction good indices (Frac. Good) were lower, too. When hydrogen was used as carrier gas, the signals of the pesticides were unstable, the measuring accuracies of the pesticides were reduced too, and even more, some compounds were undetectable. Therefore, considering the measuring accuracy, the signal stability, and the safety, etc., hydrogen should be cautiously used as carrier gas in the determination of organophosphorus pesticides by GC-MS.

  5. Comparison of the Efficiency of Simultaneous Application of UV/O3 for the Removal of Organophosphorus and Carbamat Pesticides in Aqueous Solutions

    Mohammad Taghi Samadi

    2010-03-01

    Full Text Available A vast variety of pesticides are used for agricultural pests in Iran. The release of these persistent organic pollutants. into water supplies leaves adverse effects on both the environment and public health. Advanced oxidation processes have been used recently for pesticide removal. In this research, the combined UV/O3 process has been investigated for the removal of organophosphorus pesticides (Diazinon, Chlorpyrifos, Carbamate pesticides (carbaryl. In this survey, samples have been prepared by adding given concentration (1, 5, 10, 15, 20 mg/L of the pesticides to deionized water. The samples at separation periods were exposed to the combined UV/O3 (UV=50-200 Wm-2 and O3 = 1g hr-1in a bath  reactor at different pH levels (6, 7, 9 and for different contact times (0.5,1,1.5,2 hr and the removal efficiencies were determined. Residual concentrations were determined using GC/MS/MS and HPLC.  Based on the results, increasing pH reduced pesticide concentration and increased contact time had a direct effect on enhancing removal efficiency. The combined UV/O3 process was found to have a high efficiency (>80% in degrading both halogenated Organophosphorus(Chlorpyrifos and non- halogenated Organophosphorus (Diazinon pesticides. Its removal efficiency for degrading carbamate pesticide (Carbari was found to be >90%. Based on our results, this method may be suggested for the removal of pesticides from aqueous solutions.

  6. Determination of organophosphorus pesticides in water samples by using a new sensitive luminescent probe of Eu (III) complex

    Azab, Hassan A., E-mail: azab2@yahoo.com; Anwar, Z.M.; Rizk, M.A.; Khairy, Gasser M.; El-Asfoury, M.H.

    2015-01-15

    This work describes the application of fluorescence for investigating the interactions of Eu(III)-TAN-1,10 phenanthroline (where TAN=4,4,4-Trifluoro-1-(2-naphthyl)-1,3-butanedione) with pesticides Chlorpyrifos, Malathion, Endosulfan, Heptachlor. The complex was synthesized and characterized by elemental analysis, FTIR, x-ray spectroscopy, solid fluorescence and thermal analysis. The results indicated that the composition of this complex is [Eu(TAN){sub 2}(Phen)(H{sub 2}O){sub 2}]Cl. The luminescence properties of the complex in different solvents and at different pH values have been investigated. The results show that the complex exhibits more efficient luminescence at pH=7.5. The interactions of Eu-complex with different pesticides (Chlorpyrifos, Malathion, Endosulfan, and Heptachlor) in aqueous medium have been investigated by fluorescence measurements. The luminescence intensity of the probe is quenched by Malathion and enhanced by (Endosulfan, Heptachlor, and Chlorpyrifos). Direct methods for the determination of the pesticides under investigation have been developed using the luminescence variations of the probe in solution. The detection limits are 0.47, 1.02, 0.66, 0.64 µmol/L for Chlorpyrifos, Endosulfan, Heptachlor, and Malathion, respectively. The binding constants and thermodynamic parameters of the pesticides with probe were evaluated. The emission quantum yield (QY=0.71) of Eu(III)-complex was determined using tris (2,2'-bipyridyl) dichlororuthenium(II) hexahydrate. A thermodynamic analysis showed that the reaction is spontaneous with negative ΔG. Effect of some relevant interferents on the detection of pesticides has been investigated. The new method was applied to the determination of the pesticides in different types of water samples (tap, river, and waste water). - Highlights: • A new luminescent probe of Eu (III) complex has been developed for sensing some organophosphorus pesticides. • Four guest pesticides Chlorpyrifos, Malathion

  7. Determination of organophosphorus pesticides in water samples by using a new sensitive luminescent probe of Eu (III) complex

    Azab, Hassan A.; Anwar, Z.M.; Rizk, M.A.; Khairy, Gasser M.; El-Asfoury, M.H.

    2015-01-01

    This work describes the application of fluorescence for investigating the interactions of Eu(III)-TAN-1,10 phenanthroline (where TAN=4,4,4-Trifluoro-1-(2-naphthyl)-1,3-butanedione) with pesticides Chlorpyrifos, Malathion, Endosulfan, Heptachlor. The complex was synthesized and characterized by elemental analysis, FTIR, x-ray spectroscopy, solid fluorescence and thermal analysis. The results indicated that the composition of this complex is [Eu(TAN) 2 (Phen)(H 2 O) 2 ]Cl. The luminescence properties of the complex in different solvents and at different pH values have been investigated. The results show that the complex exhibits more efficient luminescence at pH=7.5. The interactions of Eu-complex with different pesticides (Chlorpyrifos, Malathion, Endosulfan, and Heptachlor) in aqueous medium have been investigated by fluorescence measurements. The luminescence intensity of the probe is quenched by Malathion and enhanced by (Endosulfan, Heptachlor, and Chlorpyrifos). Direct methods for the determination of the pesticides under investigation have been developed using the luminescence variations of the probe in solution. The detection limits are 0.47, 1.02, 0.66, 0.64 µmol/L for Chlorpyrifos, Endosulfan, Heptachlor, and Malathion, respectively. The binding constants and thermodynamic parameters of the pesticides with probe were evaluated. The emission quantum yield (QY=0.71) of Eu(III)-complex was determined using tris (2,2'-bipyridyl) dichlororuthenium(II) hexahydrate. A thermodynamic analysis showed that the reaction is spontaneous with negative ΔG. Effect of some relevant interferents on the detection of pesticides has been investigated. The new method was applied to the determination of the pesticides in different types of water samples (tap, river, and waste water). - Highlights: • A new luminescent probe of Eu (III) complex has been developed for sensing some organophosphorus pesticides. • Four guest pesticides Chlorpyrifos, Malathion, Endosulfan, and

  8. Effect of Intensive Atropine Doses (Rapid Incremental Loading and Titration for Management of Organophosphorus Pesticide Poisoning: a Case Series

    Abu Saleh Ahmed

    2014-03-01

    Full Text Available Background:Acute poisoning with organophosphorus (OP pesticides is a common method of suicide and entails considerable mortality in Bangladesh. The objective of this study was to evaluate the effects and outcomes of a protocol for treatment of OP poisoning that included titrated incremental atropine as loading dose and slow infusion for maintenance.  Methods:In this prospective descriptive case series, definitive OP poisoned patients were enrolled in an adult medicine unit of Dhaka Medical College Hospital from April 2006 to April 2007. Clinical examinations were done as soon as the patient entered the ward. Patient’s demographics, comorbid conditions and the occurrence of specific clinical outcomes including death, need for assisted ventilation and clinical complications were recorded. The patients were treated according to the protocol. Results: A total of 56 patients were enrolled over the study period. The median age of the study population was 22.5 years. Most patients were men (67.8%. The most common clinical presentation was miosis (58.9%. In total, 11 patients died (19.6%. Intermediate syndrome developed in 12 patients (21.4% and 6 of them died. Assisted ventilation was required in 16 cases (28.5. Patients with diastolic blood pressure ≤ 70 mmHg and/or GCS ≤ 10 were significantly less likely to survive (P = 0.02, 0.006, respectively. Moreover, early respiratory failure (P < 0.001 and the need for assisted ventilation (P < 0.001 were significantly higher among deceased cases. The mortality rate in this study was similar to previous studies. The frequency of atropine toxicity in the present study (1.8% was considerably lower than conventional regimen used in previous studies. Conclusion:Using the new protocol, lower rate of atropine toxicity developed in victims. Hence, the new protocol appears to be safer and its effectiveness should be further evaluated in case control studies in Bangladesh.    How to cite this article: Ahmed AS

  9. Poisoning of raptors with organophosphorus and carbamate pesticides with emphasis on Canada, U.S. and U.K.

    Mineau, P.; Fletcher, M.R.; Glaser, L.C.; Thomas, N.J.; Brassard, C.; Wilson, L.K.; Elliott, J.E.; Lyon, L.A.; Henny, C.J.; Bollinger, T.; Porter, S.L.

    1999-01-01

    We reviewed cases of raptor mortality resulting from cholinesterase-inhibiting pesticides. We compiled records from the U.S., U.K. and Canada for the period 1985-95 (520 incidents) and surveyed the relevant literature to identify the main routes of exposure and those products that led to the greatest number of poisoning cases. A high proportion of cases in the U.K. resulted from abusive uses of pesticides (willful poisoning). The proportion was smaller in North America where problems with labeled uses of pesticides were as frequent as abuse cases. Poisoning resulting from labeled use was possible with a large number of granular pesticides and some seed treatments through secondary poisoning or through the ingestion of contaminated invertebrates, notably earthworms. With the more toxic products, residue levels in freshly-sprayed insects were high enough to cause mortality. The use of organophosphorus products as avicides and for the topical treatment of livestock appeared to be common routes of intoxication. The use of insecticides in dormant oils also gave rise to exposure that can be lethal or which can debilitate birds and increase their vulnerability. A few pesticides of high toxicity were responsible for the bulk of poisoning cases. Based on limited information, raptors appeared to be more sensitive than other bird species to organophosphorus and carbamate pesticides. Some of the more significant risk factors that resulted in raptor poisonings were: insectivory and vermivory; opportunistic taking of debilitated prey; scavenging, especially if the gastrointestinal tracts are consumed; presence in agricultural areas; perceived status as pest species; and flocking or other gregarious behavior at some part of their life cycle. Lethal or sublethal poisoning should always be considered in the diagnosis of dead or debilitated raptors even when another diagnosis (e.g., electrocution, car or building strike) is apparent. Many cases of poisoning are not currently

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

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

    2013-01-01

    Highlights: ► Europium (III) luminescence quenching has been used for sensing organophosphorous pesticides. ► Four guest pesticides chlorfenvinphos, malathion, azinphos, and paraxon ethyl were used. ► A sensitive rapid, cheap direct method for the determination of the pesticides has been developed. ► The method was applied to the determination of the OPs in tap, river, mineral, and waste waters. - Abstract: 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.

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

    Azab, Hassan A., E-mail: azab2@yahoo.com [Chemistry Department, Faculty of Science, Suez Canal University, Ismailia 41522 (Egypt); Duerkop, Axel [Institute of Analytical Chemistry, Chemo and Biosensors, Regensburg University, D-93040 Regensburg (Germany); Anwar, Z.M.; Hussein, Belal H.M.; Rizk, Moustafa A.; Amin, Tarek [Chemistry Department, Faculty of Science, Suez Canal University, Ismailia 41522 (Egypt)

    2013-01-08

    Highlights: Black-Right-Pointing-Pointer Europium (III) luminescence quenching has been used for sensing organophosphorous pesticides. Black-Right-Pointing-Pointer Four guest pesticides chlorfenvinphos, malathion, azinphos, and paraxon ethyl were used. Black-Right-Pointing-Pointer A sensitive rapid, cheap direct method for the determination of the pesticides has been developed. Black-Right-Pointing-Pointer The method was applied to the determination of the OPs in tap, river, mineral, and waste waters. - Abstract: 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){sub 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 {mu}M. The detection limits were 0.24-0.55 {mu}M for P3, P4, and P1 and 2.5 {mu}M for P2, respectively. The binding constants (K), and thermodynamic parameters of the OPs with Eu(III)-(PDCA){sub 2} were evaluated. Positive and negative values of entropy ({Delta}S) and enthalpy ({Delta}H) changes for Eu(III)-(PDCA){sub 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.

  12. Simultaneous detection of dual biomarkers from humans exposed to organophosphorus pesticides by combination of immunochromatographic test strip and ellman assay.

    Yang, Mingming; Zhao, Yuting; Wang, Limin; Paulsen, Michael; Simpson, Christopher D; Liu, Fengquan; Du, Dan; Lin, Yuehe

    2018-05-01

    A novel sandwich immunoassay based immunochromatographic test strip (ICTS) has been developed for simultaneously measuring both butyrylcholinesterase (BChE) activity and the total amount of BChE (including inhibited and active enzyme) from 70 μLpost-exposure human plasma sample. The principle of this method is based on the BChE monoclonal antibody (MAb) capable of acting as both capture antibody and detection antibody. The BChE MAb which was immobilized on the test line was able to recognize both organophosphorus BChE adducts (OP-BChE) and BChE and provided equal binding affinity, permitting detection of the total enzyme amount in post-exposure human plasma samples. The formed immunocomplexes on the test line can further be excised from the test-strip for subsequent off-line measurement of BChE activity using the Ellman assay. Therefore, dual biomarkers of BChE activity and phosphorylation (OP-BChE) will be obtained simultaneously. The whole sandwich-immunoassay was performed on one ICTS, greatly reducing analytical time. The ICTS sensor showed excellent linear responses for assaying total amount of BChE and active BChE ranging from 0.22 to 3.58nM and 0.22-7.17nM, respectively. Both the signal detection limits are 0.10nM. We validated the practical application of the proposed method to measure 124 human plasma samples from orchard workers and cotton farmers with long-term exposure to organophosphorus pesticides (OPs). The results were in highly agreement with LC/MS/MS which verified our method is extremely accurate. Combining the portability and rapidity of test strip and the compatibility of BChE MAb as both capture antibody and detection antibody, the developed method provides a baseline-free, low-cost and rapid tool for in-field monitoring of OP exposures. Copyright © 2018 Elsevier B.V. All rights reserved.

  13. Optical Detection of Paraoxon Using Single-Walled Carbon Nanotube Films with Attached Organophosphorus Hydrolase-Expressed Escherichia coli

    Intae Kim

    2015-05-01

    Full Text Available In whole-cell based biosensors, spectrophotometry is one of the most commonly used methods for detecting organophosphates due to its simplicity and reliability. The sensor performance is directly affected by the cell immobilization method because it determines the amount of cells, the mass transfer rate, and the stability. In this study, we demonstrated that our previously-reported microbe immobilization method, a microbe-attached single-walled carbon nanotube film, can be applied to whole-cell-based organophosphate sensors. This method has many advantages over other whole-cell organophosphate sensors, including high specific activity, quick cell immobilization, and excellent stability. A device with circular electrodes was fabricated for an enlarged cell-immobilization area. Escherichia coli expressing organophosphorus hydrolase in the periplasmic space and single-walled carbon nanotubes were attached to the device by our method. Paraoxon was hydrolyzed using this device, and detected by measuring the concentration of the enzymatic reaction product, p-nitrophenol. The specific activity of our device was calculated, and was shown to be over 2.5 times that reported previously for other whole-cell organophosphate sensors. Thus, this method for generation of whole-cell-based OP biosensors might be optimal, as it overcomes many of the caveats that prevent the widespread use of other such devices.

  14. Heat Release Property and Fire Performance of the Nomex/Cotton Blend Fabric Treated with a Nonformaldehyde Organophosphorus System

    Charles Q. Yang

    2016-09-01

    Full Text Available Blending Nomex® with cotton improves its affordability and serviceability. Because cotton is a highly flammable fiber, Nomex®/cotton blend fabrics containing more than 20% cotton require flame-retardant treatment. In this research, combination of a hydroxyl functional organophosphorus oligmer (HFPO and 1,2,3,4-butanetetracarboxylic acid (BTCA was used for flame retardant finishing of the 65/35 Nomex®/cotton blend woven fabric. The system contains HFPO as a flame retardant, BTCA as a bonding agent, and triethenolamine (TEA as a reactive additive used to enhance the performance of HFPO/BTCA. Addition of TEA improves the hydrolysis resistance of the HFPO/BTCA crosslinked polymeric network on the blend fabric. Additionally, TEA enhances HFPO’s flame retardant performance by reducing formation of calcium salts and also by providing synergistic nitrogen to the treated blend fabric. The Nomex®/cotton blend fabric treated with the HFPO/BTCA/TEA system shows high flame resistance and high laundering durability at a relatively low HFPO concentration of 8% (w/w. The heat release properties of the treated Nomex®/cotton blend fabric were measured using microscale combustion calorimetry. The functions of BTCA; HFPO and TEA on the Nomex®/cotton blend fabric were elucidated based on the heat release properties, char formation, and fire performance of the treated blend fabric.

  15. Cytoplasmic vacuolation in cultured rat astrocytes induced by an organophosphorus agent requires extracellular signal-regulated kinase activation

    Isobe, Ichiro; Maeno, Yoshitaka; Nagao, Masataka; Iwasa, Mineo; Koyama, Hiroyoshi; Seko-Nakamura, Yoshimi; Monma-Ohtaki, Jun

    2003-01-01

    There are various toxic chemicals that cause cell death. However, in certain cases deleterious agents elicit various cellular responses prior to cell death. To determine the cellular mechanisms by which such cellular responses are induced is important, but sufficient attention has not been paid to this issue to date. In this study, we showed the characteristic effects of an organophosphorus (OP) agent, bis(pinacolyl methyl)phosphonate (BPMP), which we synthesized for the study of OP nerve agents, on cultured rat astrocytes. Morphologically, BPMP induced cytoplasmic vacuolation and stellation in the rat astrocytes. Cytoplasmic vacuolation is a cell pathological change observed, for example, in vacuolar degeneration, and stellation has been reported in astrocytic reactions against various stimuli. By pretreatment with cycloheximide, a protein synthesis inhibitor, stellation was inhibited, although vacuolation was not. Cell staining with a mitochondrion-selective dye indicated that the vacuolation probably occurs in the mitochondria that are swollen and vacuolatred in the center. Interestingly, the extracellular signal-regulated kinase (ERK) cascade inhibitor inhibited vacuolation and, to some extent, stellation. These results suggest that the ERK signaling cascade is important for the induction of mitochondrial vacuolation. We expect that a detailed study of these astrocytic reactions will provide us new perspectives regarding the variation and pathological significance of cell morphological changes, such as vacuolar degeneration, and also the mechanisms underlying various neurological disorders

  16. Determination of Carbamate and Organophosphorus Pesticides in Vegetable Samples and the Efficiency of Gamma-Radiation in Their Removal

    Muhammed Alamgir Zaman Chowdhury

    2014-01-01

    Full Text Available In the present study, the residual pesticide levels were determined in eggplants (Solanum melongena (n=16, purchased from four different markets in Dhaka, Bangladesh. The carbamate and organophosphorus pesticide residual levels were determined by high performance liquid chromatography (HPLC, and the efficiency of gamma radiation on pesticide removal in three different types of vegetables was also studied. Many (50% of the samples contained pesticides, and three samples had residual levels above the maximum residue levels determined by the World Health Organisation. Three carbamates (carbaryl, carbofuran, and pirimicarb and six organophosphates (phenthoate, diazinon, parathion, dimethoate, phosphamidon, and pirimiphos-methyl were detected in eggplant samples; the highest carbofuran level detected was 1.86 mg/kg, while phenthoate was detected at 0.311 mg/kg. Gamma radiation decreased pesticide levels proportionately with increasing radiation doses. Diazinon, chlorpyrifos, and phosphamidon were reduced by 40–48%, 35–43%, and 30–45%, respectively, when a radiation strength of 0.5 kGy was utilized. However, when the radiation dose was increased to 1.0 kGy, the levels of the pesticides were reduced to 85–90%, 80–91%, and 90–95%, respectively. In summary, our study revealed that pesticide residues are present at high amounts in vegetable samples and that gamma radiation at 1.0 kGy can remove 80–95% of some pesticides.

  17. A novel fluorimetric sensing platform for highly sensitive detection of organophosphorus pesticides by using egg white-encapsulated gold nanoclusters.

    Yan, Xu; Li, Hongxia; Hu, Tianyu; Su, Xingguang

    2017-05-15

    Assays for organophosphorus pesticides (OPs) with high sensitivity as well as on-site screening have been urgently required to protect ecosystem and prevent disease. Herein, a novel fluorimetric sensing platform was constructed for quantitative detection of OPs via tyrosinase (TYR) enzyme-controlled quenching of gold nanoclusters (AuNCs). One-step green synthetic approach was developed for the synthesis of AuNCs by using chicken egg white (CEW) as template and stabilizer. Initially, TYR can catalyze the oxidation of dopamine to dopaminechrome, which can efficiently quench the fluorescence intensity of AuNCs at 630nm based on dynamic quenching process. However, with the presence of OPs, the activity of TYR was inhibited, resulting in the fluorescence recovery of AuNCs. This proposed fluorescence platform was demonstrated to enable rapid detection for OPs (paraoxon as model) and to provide excellent sensitivity with a detection limit of 0.1ngmL -1 . Significantly, the fluorescence probe was used to prepare paper-based test strips for visual detection of OPs, which validated the excellent potential for real-time and on-site application. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. Optical detection of organophosphorus compounds based on Mn-doped ZnSe d-dot enzymatic catalytic sensor.

    Gao, Xue; Tang, Guangchao; Su, Xingguang

    2012-01-01

    In this paper, we report a sensitive and selective method for detection of organophosphorus compounds (OPs) based on Mn:ZnSe d-dots-enzyme-hydrogen peroxide (H(2)O(2)) fluorescence quenching system. Acetylcholine esterase (AChE) can hydrolyze acetylcholine (ACh) to choline. Subsequently, choline oxidase (ChOx) oxidizes choline to generate H(2)O(2). The enzyme-generated H(2)O(2) can quench the fluorescence of Mn:ZnSe d-dots. When paraoxon are introduced in solution, it can interact with the active centers of AChE and decrease the enzyme activity. This leads to the decrease of the H(2)O(2) production and then the fluorescence quenching rate of Mn:ZnSe d-dots. Experimental results showed that the enzyme inhibition percentage of Mn:ZnSe d-dots-ChOx-AChE-ACh system was proportional to the logarithm of paraoxon in the range 4.84×10(-11) to 4.84×10(-6) mol/L with the detection limit (S/N=3) of 1.31×10(-11) mol/L. The proposed biosensor has been employed for quick determination of paraoxon in tap water and milk samples with satisfactory reproducibility and accuracy. This nano-biosensor was proved to be sensitive, rapid, simple and tolerance of most interfering substances. Copyright © 2012 Elsevier B.V. All rights reserved.

  19. Detection of residual organochlorine and organophosphorus pesticides in agricultural soil in Rio Verde region of San Luis Potosi, Mexico.

    Velasco, Antonio; Hernández, Sergio; Ramírez, Martha; Ortíz, Irmene

    2014-01-01

    Organochlorine pesticides were intensively used in Mexico from 1950 until their ban and restriction in 1991. However, the presence of these compounds is commonly reported in many regions of the country. The aim of the present study was to identify and quantify residual organochlorine and organophosphorus pesticides in agricultural soil in Rio Verde region, San Luis Potosi state, which has been identified as possibly polluted by pesticides. Composed samples from 24 zones covering an area of approximately 5,440 ha were analyzed. The most frequently found pesticides were p,p'-DDT followed by ,p,p'-DDE, heptachlor, endosulfan and γ-HCH whose frequency rates were 100, 91, 83 and 54%, respectively. The concentration of p,p'-DDT in the crops grown in these soils was in the following order: chili > maize > tomato > alfalfa. The results obtained in this study show that p,p'-DDT values are lower or similar to those found in other agricultural regions of Mexico. Methyl and ethyl parathion were the most frequent organophosphate pesticide detected in 100% and 62.5% of the samples with average concentrations of 25.20 and 47.48 μg kg(-1), respectively. More research is needed to establish the background levels of pesticides in agricultural soils and their potential ecological and human health effects in this region.

  20. Matrix solid-phase dispersion extraction of organophosphorus pesticide using SiO2-poly(N-vinylimidazole)

    Gutiérrez-Solís, M C; Muñoz-Rodríguez, D; Carrera-Figueiras, C; Ávila-Ortega, A; Medina-Peralta, S

    2013-01-01

    A sorbent material based on silica particles modified with poly(N-vinylimidazole) (SiO 2 -PVI) has been evaluated for the treatment of samples by matrix solid-phase dispersion (MSPD). The extraction of four organophosphorus pesticides was done from a spiked tomato and the extracts were analyzed by gas chromatography coupled to mass spectrometry. Six elution solvents were evaluated and acetone was selected due to better recovery of the four pesticides and low background signal in the chromatograms. A factorial design 2 4 was used for selection of extraction conditions. The factors were contact time, acetone volume, treatment (with or without freeze-drying) and adsorbent (SiO 2 or SiO 2 -PVI). The best recoveries were obtained using 15 minutes of contact, 2 mL of solvent and sorbent without freeze-drying. The recoveries were between 60 and 83% for SiO 2 -PVI in spiked tomato with 0.2 and 0.8μg/g.

  1. De novo amplification within a silent human cholinesterase gene in a family subjected to prolonged exposure to organophosphorus insecticides

    Prody, C.A.; Dreyfus, P.; Soreq, H.; Zamir, R.; Zakut, H.

    1989-01-01

    A 100-fold DNA amplification in the CHE gene, coding for serum butyrylcholinesterase (BtChoEase), was found in a farmer expressing silent CHE phenotype. Individuals homozygous for this gene display a defective serum BtChoEase and are particularly vulnerable to poisoning by agricultural organophosphorus insecticides, to which all members of this family had long been exposed. DNA blot hybridization with regional BtChoEase cDNA probes suggested that the amplification was most intense in regions encoding central sequences within BtChoEase cDNA, whereas distal sequences were amplified to a much lower extent. This is in agreement with the onion skin model, based on amplification of genes in cultured cells and primary tumors. The amplification was absent in the grandparents but present at the same extent in one of their sons and in a grandson, with similar DNA blot hybridization patterns. In situ hybridization experiments localized the amplified sequences to the long arm of chromosome 3, close to the site where the authors previously mapped the CHE gene. Altogether, these observations suggest that the initial amplification event occurred early in embryogenesis, spermatogenesis, or oogenesis, where the CHE gene is intensely active and where cholinergic functioning was indicated to be physiologically necessary. These findings demonstrate a de novo amplification in apparently healthy individuals within an autosomal gene producing a target protein to an inhibitor

  2. Molecular characterization of the amplified carboxylesterase gene associated with organophosphorus insecticide resistance in the brown planthopper, Nilaparvata lugens.

    Small, G J; Hemingway, J

    2000-12-01

    Widespread resistance to organophosphorus insecticides (OPs) in Nilaparvata lugens is associated with elevation of carboxylesterase activity. A cDNA encoding a carboxylesterase, Nl-EST1, has been isolated from an OP-resistant Sri Lankan strain of N. lugens. The full-length cDNA codes for a 547-amino acid protein with high homology to other esterases/lipases. Nl-EST1 has an N-terminal hydrophobic signal peptide sequence of 24 amino acids which suggests that the mature protein is secreted from cells expressing it. The nucleotide sequence of the homologue of Nl-EST1 in an OP-susceptible, low esterase Sri Lankan strain of N. lugens is identical to Nl-EST1. Southern analysis of genomic DNA from the Sri Lankan OP-resistant and susceptible strains suggests that Nl-EST1 is amplified in the resistant strain. Therefore, resistance to OPs in the Sri Lankan strain is through amplification of a gene identical to that found in the susceptible strain.

  3. Development of a passive air sampler to measure airborne organophosphorus pesticides and oxygen analogs in an agricultural community.

    Armstrong, Jenna L; Yost, Michael G; Fenske, Richard A

    2014-09-01

    Organophosphorus pesticides are some of the most widely used insecticides in the US, and spray drift may result in human exposures. We investigate sampling methodologies using the polyurethane foam passive air sampling device to measure cumulative monthly airborne concentrations of OP pesticides chlorpyrifos, azinphos-methyl, and oxygen analogs. Passive sampling rates (m(3)d(-1)) were determined using calculations using chemical properties, loss of depuration compounds, and calibration with side-by-side active air sampling in a dynamic laboratory exposure chamber and in the field. The effects of temperature, relative humidity, and wind velocity on outdoor sampling rates were examined at 23 sites in Yakima Valley, Washington. Indoor sampling rates were significantly lower than outdoors. Outdoor rates significantly increased with average wind velocity, with high rates (>4m(3)d(-1)) observed above 8ms(-1). In exposure chamber studies, very little oxygen analog was observed on the PUF-PAS, yet substantial amounts chlorpyrifos-oxon and azinphos methyl oxon were measured in outdoor samples. PUF-PAS is a practical and useful alternative to AAS because it results in little artificial transformation to the oxygen analog during sampling, it provides cumulative exposure estimates, and the measured sampling rates were comparable to rates for other SVOCs. It is ideal for community based participatory research due to low subject burden and simple deployment in remote areas. Copyright © 2014 Elsevier Ltd. All rights reserved.

  4. The structural requirements of organophosphorus insecticides (OPI) for reducing chicken embryo NAD(+) content in OPI-induced teratogenesis in chickens.

    Seifert, Josef

    2016-05-01

    The objective of this study was to determine the structural requirements of organophosphorus insecticides (OPI) for reducing chicken embryo nicotinamide adenine dinucleotide (NAD(+)) content in OPI-induced teratogenesis and compare them with those needed for OPI inhibition of yolk sac membrane kynurenine formamidase (KFase), the proposed primary target for OPI teratogens in chicken embryos. The comparative molecular field analysis (COMFA) of three-dimensional quantitative structure-activity relationship (3D QSAR) revealed the electrostatic and steric fields as good predictors of OPI structural requirements to reduce NAD(+) content in chicken embryos. The dominant electrostatic interactions were localized at nitrogen-1, nitrogen-3, nitrogen of 2-amino substituent of the pyrimidinyl of pyrimidinyl phosphorothioates, and at the oxygen of crotonamide carbonyl in crotonamide phosphates. Bulkiness of the substituents at carbon-6 of the pyrimidinyls and/or N-substituents of crotonamides was the steric structural component that contributed to superiority of those OPI for reducing embryonic NAD(+) levels. Both electrostatic and steric requirements are similar to those defined in our previous study for OPI inhibition of chicken embryo yolk sac membrane KFase. The findings of this study provide another piece of evidence for the cause-and-effect relationship between yolk sac membrane KFase inhibition and reduced embryo NAD(+) content in NAD-associated OPI-induced teratogenesis in chickens. Copyright © 2015 Elsevier Inc. All rights reserved.

  5. Field studies on health effects from the application of two organophosphorus insecticide formulations by hand-held ULV to cotton.

    Kummer, R; van Sittert, N J

    1986-10-01

    Two field studies to assess the health implications for farmers applying two different formulations containing organophosphorus (OP) pesticides to cotton by hand-held ULV are described. The first study, carried out in the Ivory Coast, involved the application of an endrin/DDT/methylparathion (MEP) formulation in an aromatic hydrocarbon solvent. The second study took place in Indonesia with a 20% monocrotophos formulation in a mixture of a glycol and a glycol ether. Both studies were carried out under actual field conditions. The purpose of the studies was to get a good assessment of the health hazards of the particular formulation, used under the specific circumstances and agronomic requirements of the area of application and taking into account all local, climatic and cultural conditions that could be of possible influence. The results showed that in both studies skin exposures took place during application and especially during handling, filling and cleaning, and that inhalation of spray mist was negligible. Absorption was confirmed by the presence in urine of metabolites of endrin and methylparathion in the Ivory Coast study, and of dimethyl phosphate in the Indonesia study. No clinical signs or symptoms of intoxication were discovered in either study, nor were inhibitions of cholinesterase (ChE) activity of health significance established under the conditions of the studies. In addition, various practical aspects such as choice of apparatus, of formulation, the application procedures etc. are discussed.

  6. Innovative approach for the electrochemical detection of non-electroactive organophosphorus pesticides using oxime as electroactive probe

    Dong, Jing; Hou, Juying; Jiang, Jianxia; Ai, Shiyun

    2015-01-01

    Highlights: • Novel approach for electrochemical detection of non-electroactive OPs was proposed. • PAM was used as electroactive probe for the first time. • The detection system displayed high sensitivity and promptness. • The developed sensor was used in real samples with satisfactory results. - Abstract: An innovative approach for sensitive and simple electrochemical detection of non-electroactive organophosphorus pesticides (OPs) was described in this report. The novel strategy emphasized the fabrication of an oxime-based sensor via attaching pralidoxime (PAM) on graphene quantum dots (GQDs) modified glassy carbon electrode. The introduction of GQDs significantly increased the effective electrode area, and then enlarged the immobilization quantity of PAM. Thus, the oxidation current of PAM was obviously increased. Relying on the nucleophilic substitution reaction between oxime and OPs, fenthion was detected using PAM as the electroactive probe. Under optimum conditions, the difference of oxidation current of PAM was proportional to fenthion concentration over the range from 1.0 × 10 −11 M to 5.0 × 10 −7 M with a detection limit of 6.8 × 10 −12 M (S/N = 3). Moreover, the favorable detection performance in water and soil samples heralded the promising applications in on-site OPs detection

  7. Application of Box-Behnken design for the removal of two organophosphorus pesticides by used Tea leaves

    Albanis, Triantafyllos; Valileios, Sakkas; Islam, Azharul M.

    2016-04-01

    Removal of two organophosphorus pesticides bromophos methyl [BM: O, O- dimethyl - O - (2, 5-dichloro -4 bromophenyl) phosphorothioate] and quinalphos [QP: O, O-diethyl O-2-quinoxalinyl phosphorothioate] on used tea leaves were studied by batch equilibration method. Adsorption isotherms were conformed well to Langmuir for quinalphos and Freundlich equation for bromophos methyl. The kinetic data fitted well by the pseudo second order model for both pesticides. Box-Behnken design was successfully employed for experimental design and analysis of results. The interactions of pH, initial concentration and adsorbent dose on two pesticides adsorption by used tea leaves were investigated by this model. The optimum pH, initial concentration and adsorbent dose with their corresponding removal efficiency were found to be 7.88, 11.94 mg L-1, 0.37g and 100% for bromophos methyl respectively, for quinalphos 8.72, 6.44 mg L-1, 0.39g and 93.98% respectively. Keywords: Box-Behnken; quinalphos; bromophos methyl; Kinetics; used tea leaves

  8. RESEARCH ON ENVIRONMENTAL CONTAMINATION IN RAW MILK IN TURIN DEPARTEMENT : HEAVY METALS, P.C.B, ORGANOCHLORINE AND ORGANOPHOSPHORUS PESTICIDES – YEARS 2005 – 2008

    S. Cavallera

    2013-02-01

    Full Text Available In the period between 2005 and 2008 was carried out a survey on 252 samples of raw bovine milk collected in Turin departement to certain levels of contamination by heavy metals (Cd, Cr, Fe, Hg, Pb, Zn, PCB and organophosphorus and organochlorine pesticides. These results argue that the levels of heavy metals, PCB and pesticides are well below what is expected by the European legislation and that the situation is under control and that raw milk meets the hygiene requirements for human health.

  9. Activity of Ca(2+,Mg(2+-ATPase of sarcoplasmic reticulum and contraction strength of the frog skeletal muscles under the effect of organophosphorus insecticides

    D. M. Nozdrenko

    2015-08-01

    Full Text Available The results of an experimental study of organo­phosphorus insecticides, including pirimiphosmethyl, diazinon and chlorpyrifos caused a decline of the contraction properties in m. tibialis anterior fiber bundles of Rana temporaria, as well as sarcoplasmic reticulum Ca2+,Mg2+-ATPase enzymatic activity reduction are outlined in this paper. Concentration-dependent strengths response diminishing in isolated skeletal muscle fiber bundles as a result of non-cholinergic influence of organophosphorus insecticides were found. A decrease of Ca2+,Mg2+-ATPase enzymatic activity in sarcoplasmic reticulum was observed after administration of each insecticide. The most significant inhibition of this enzyme was observed when using chlorpyrifos.

  10. Recovery evaluation of organophosphorus pesticides from bee pollen by matrix solid-phase dispersion extraction using sorbents based on silica and titania

    Torres-Perea, C; Muñoz-Rodríguez, D; Carrera-Figueiras, C; Medina-Peralta, S; Moguel-Ordóñez, Y B

    2013-01-01

    This work focused on the evaluation of the recovery of organophosphorus pesticides from bee pollen after matrix solid phase-dispersion extraction (MSPD). Materials based on silica, titania and titania modified with polivylnylimidazole or polyestirene were used as adsorbents for the extraction of pesticides. Small amounts of fortified pollen (0.1 g, at 1 micro-g/g of pesticides), adsorbent (0.4 g) and solvent elution (1 mL de acetonitrile – ACN) were used in the extractions. For recovery evaluation, pollen extracts were analyzed by gas chromatography coupled with mass spectrometry.

  11. [COMPARATIVE SENSITIVITY OF CHOLINESTERASES IN VERTEBRATES AND INVERTEBRATES TO HIGHLY SPECIFIC ORGANOPHOSPHORUS INHIBITORS DIISOPROPYL FLUOROPHOSPHATE (DFP) AND (2-ETHOXYMETHYL PHOSPHORYL THIOETHYL) ETHYL (METHYL) SULPHONIUM SULPHOMETHYLAT (GD-42)].

    Basova, N E; Kormilitsyn, B N; Perchenok, A Yu; Rozengart, E V; Saakov, V S; Suvorov, A A

    2015-01-01

    The review presents data on comparative reactivity of 68 cholinesterase preparation from various organs and tissues in a number of vertebrates and invertebrates based on sensitivity to two highly specific and most studied organophosphorus inhibitors--diisopropyl fluorophosphates (DFP) and (2-ethoxymethyl phosphoryl thioethyl) ethyl (methyl) sulphonium sulphomethylat (GD-42). Analysis of these data suggests a great diversity in enzymologic characteristics of cholinesterase preparation in representatives of vertebrates and invertebrates, this variety observed even for closely related enzymes in animals of almost the same level of development.

  12. Probabilistic acute risk assessment of cumulative exposure to organophosphorus and carbamate pesticides from dietary vegetables and fruits in Shanghai populations.

    Li, Fan; Yuan, Yaqun; Meng, Pai; Wu, Min; Li, Shuguang; Chen, Bo

    2017-05-01

    Organophosphorus pesticides (OPs) and carbamate pesticides (CPs) are among the most widely used pesticides in China, playing a major role in protecting agricultural commodities. In this study, we determined the cumulative acute exposure to OPs and CPs of Shanghai residents from vegetables and fruits (VFs). The food consumption data were obtained from the Shanghai Food Consumption Survey (SHFCS) of 2012-14 including a total of 1973 participants aged 2-90 years. The pesticide residue data were obtained from the Shanghai monitoring programme during 2008-11 with 34 organophosphates and 11 carbamates analysed in a total of 5335 samples of VFs. A probabilistic approach was performed as recommended by the EFSA, using the optimistic model with non-detects set as zero and with processing factors (PFs) being used and the pessimistic model with non-detects replaced by limit of detection (LOD) and without PFs. We used the relative potency factor (RPF) method to normalise the various pesticides to the index compound (IC) of methamidophos and chlorpyrifos separately. Only in the pessimistic model using methamidophos as the IC was there was small risk of exposure exceeding the ARfD (3 µg kg - 1 bw day - 1 ) in the populations of preschool children (0.029%), school-age children (0.022%) and adults (0.002%). There were no risk of exposure exceeding the ARfD of methamidophos in the optimistic model and of chlorpyrifos (100 µg kg - 1 bw day - 1 ) in both optimistic and pessimistic models in all three populations. Considering the Chinese habits of overwhelmingly eating processed food (vegetables being cooked, and fruits being washed or peeled), we conclude that little acute risk was found for the exposure to VF-sourced OPs and CPs in Shanghai.

  13. Exposure assessment of organophosphorus and organobromine flame retardants via indoor dust from elementary schools and domestic houses.

    Mizouchi, Shigekazu; Ichiba, Masayoshi; Takigami, Hidetaka; Kajiwara, Natsuko; Takamuku, Toshiyuki; Miyajima, Toru; Kodama, Hiroki; Someya, Takashi; Ueno, Daisuke

    2015-03-01

    To assess the exposure of flame retardants (FRs) for school-children, organophosphorus flame retardants and plasticizers (PFRs) and organobromine flame retardants (BFRs) were determined in the indoor dust samples collected from elementary schools and domestic houses in Japan in 2009 and 2010. PFRs were detected in all the dust samples analyzed and the highest concentration of total PFRs was thousand-fold higher than that of BFRs. Among the PFRs, tris(butoxyethyl)phosphate (TBOEP) showed the highest concentration with a median (med.) of 270,000 ng g(-1) dry weight (3700-5,500,000 ng g(-1) dry weight), followed by tris(methylphenyl)phosphate (TMPPs)>triphenyl phosphate (TPHP)=tris(1,3-dichloro-2-propyl)phosphate (TDCIPP)=tris(2-chloroisopropyl)phosphate (TCIPP)=tris(2chloroethyl)phosphate (TCEP)>ethylhexyl diphenyl phosphate (EHDPP). Significantly higher concentrations of TBOEP, tri-n-butyl phosphate (TNBP), TPHP, TMPPs, and total-PFRs were found in dust samples from elementary schools than from domestic houses. It might be due to that higher concentrations of TBOEP (as leveling agent) were detected from the floor polisher/wax products collected in those elementary schools. On the other hand, significantly higher concentrations of TCEP, TCIPPs, and total chloroalkyl-PFRs were found in domestic houses than in elementary schools. Exposure assessments of PFRs via indoor dust from elementary schools and domestic houses were conducted by calculating the hazard quotient (HQ). Among PFRs, HQs for TBOEP exceeded 1 (higher than reference dose: RfD) and its highest value was 1.9. To reduce the intake of TBOEP by school-children, it is recommended that the use of floor polisher/wax containing TBOEP be reduced in schools. Copyright © 2014 Elsevier Ltd. All rights reserved.

  14. Determination of organophosphorus pesticides by dispersive liquid-liquid micro extraction coupled with gas chromatography-electron capture detection

    Mohd Marsin Sanagi; Siti Umairah Mokhtar; Mazidatul Akmam Miskam; Wan Aini Wan Ibrahim

    2011-01-01

    A simple, rapid and sensitive method termed as dispersive liquid-liquid micro extraction (DLLME) combined with gas chromatography-electron capture detector (GC-ECD) was developed for the determination of selected organophosphorus pesticides (OPPs) namely chloropyrifos, dimethoate and diazinon in water sample. In this method, a mixture of carbon disulfide, CS 2 (extraction solvent) and methanol (disperser solvent) was rapidly injected using syringe into the 5.00 mL water sample to form a cloudy solution where the OPPs were extracted into the fine droplets of extraction solvent. Upon centrifugation for 3 min at 3500 rpm, the fine droplets were sedimented at the bottom of the centrifuge tube. Sedimented phase (1 μL) was injected into the GC-ECD for separation and determination of OPPs. Important extraction parameters, such as type of disperser solvent, volume of extraction solvent and volume of disperser solvent were investigated. The optimized conditions for DLLME of the selected OPPs were methanol as disperser solvent, 30 μL of extraction solvent (CS 2 ) and 1.0 mL of disperser solvent (methanol). Under the optimum extraction conditions, the method showed good linearity in the range of 0.1 to 1.0 μg/ mL with correlation coefficient (r 2 ), in the range of 0.9976 to 0.9994 and low limits of detection (LOD) between 0.047 and 0.201 μg/ mL. The proposed method provided acceptable recoveries (72.67- 144 %) with good RSDs ranging from 2.74 % to 7.48 %. This method was successfully applied to the determination of OPPs in water samples obtained from a golf course and chloropyrifos and diazinon were detected at concentration 0.18 μg/ mL and 0.07 μg/ mL, respectively. (author)

  15. Galantamine counteracts development of learning impairment in guinea pigs exposed to the organophosphorus poison soman: Clinical significance

    Mamczarz, Jacek; Kulkarni, Girish S.; Pereira, Edna F. R.; Albuquerque, Edson X.

    2017-01-01

    Galantamine, a drug used to treat Alzheimer’s disease, protects guinea pigs against the acute toxicity and lethality of organophosphorus (OP) compounds, including soman. Here, we tested the hypothesis that a single exposure of guinea pigs to 1xLD50 soman triggers cognitive impairments that can be counteracted by galantamine. Thus, animals were injected intramuscularly with saline (0.5 ml/kg) or galantamine (8 mg/kg) and 30 min later injected subcutaneously with soman (26.3 µg/kg) or saline. Cognitive performance was analyzed in the Morris water maze (MWM) four days or three months after the soman challenge. Fifty percent of the saline-injected animals that were challenged with soman survived with mild-to-moderate signs of acute toxicity that subsided within a few hours. These animals showed no learning impairment and no memory retention deficit, when training in the MWM started four days post-soman challenge. In contrast, animals presented significant learning impairment when testing started three months post-challenge. Though the magnitude of the impairment correlated with the severity of the acute toxicity, animals that presented no or only mild signs of toxicity were also learning impaired. All guinea pigs that were treated with galantamine survived the soman challenge with no signs of acute toxicity and learned the MWM task as control animals, regardless of when testing began. Galantamine also prevented memory extinction in both saline-and soman-challenged animals. In conclusion, learning impairment develops months after a single exposure to 1xLD50 soman, and galantamine prevents both the acute toxicity and the delayed cognitive deficits triggered by this OP poison. PMID:21784098

  16. Selectivity improvement of positive photoionization ion mobility spectrometry for rapid detection of organophosphorus pesticides by switching dopant concentration.

    Zhou, Qinghua; Li, Jia; Wang, Bin; Wang, Shuang; Li, Haiyang; Chen, Jinyuan

    2018-01-01

    Ion mobility spectrometry (IMS) opened a potential avenue for the rapid detection of organophosphorus pesticides (OPPs), though an improved selectivity of stand-alone IMS was still in high demand. In this study, a stand-alone positive photoionization ion mobility spectrometry (PP-IMS) apparatus was constructed for the rapid detection of OPPs with acetone as dopant. The photoionization of acetone molecules was induced by the ultraviolet irradiation to produce the reactant ions (Ac) 2 H + , which were employed to ionize the OPPs including fenthion, imidan, phosphamidon, dursban, dimethoate and isocarbophos via the proton transfer reaction. Due to the difference in proton affinity, the tested OPPs exhibited the different dopant-dependent manners. Based on this observation, the switching of dopant concentration was implemented to improve the selectivity of PP-IMS for OPPs detection. For instance, a mixture of fenthion, dursban and dimethoate was tested. By switching the concentration of doped acetone from 0.07 to 2.33 to 19.94mgL -1 , the ion peaks of fenthion and dursban were inhibited in succession, achieving the selective detection of dimethoate at last. In addition, another mixture of imidan and phosphamidon was initially detected by PP-IMS with a dose of 0.07mgL -1 acetone, indicating that their ion peaks were severely overlapped; when the concentration of doped acetone was switched to 19.94mgL -1 , the inhibition of imidan signals promised the accurate identification of phosphamidon in mixture. Finally, the PP-IMS in combination of switching dopant concentration was applied to detect the mixed fenthion, dursban and dimethoate in Chinese cabbage, demonstrating the applicability of proposed method to real samples. Copyright © 2017. Published by Elsevier B.V.

  17. An Innovative Rapid Method for Analysis of 10 Organophosphorus Pesticide Residues in Wheat by HS-SPME-GC-FPD/MSD.

    Du, Xin; Ren, YongLin; Beckett, Stephen J

    2016-01-01

    The rapid detection of pesticide residues in wheat has become a top food security priority. A solvent-free headspace solid-phase microextraction (HS-SPME) has been evaluated for rapid screening of organophosphorus pesticide (OPP) residues in wheat with high sensitivity. Individual wheat samples (1.7 g), spiked with 10 OPPs, were placed in a 4 mL sealed amber glass vial and heated at 60°C for 45 min. During this time, the OPP residues were extracted with a 50 μm/30 μm divinylbenzene (DVB)/carboxen (CAR)/plasma desorption mass spectroscopy polydimethylsiloxane (PDMS) fiber from the headspace above the sample. The fiber was then removed and injected into the GC injection port at 250°C for desorption of the extracted chemicals. The multiple residues were identified by a GC mass spectrometer detector (GC-MSD) and quantified with a GC flame photometric detector (GC-FPD). Seven spiked levels of 10 OPPs on wheat were analyzed. The GC responses for a 50 μm/30 μm DVB/CAR/PDMS fiber increased with increasing spiking levels, yielding significant (R(2) > 0.98) linear regressions. The lowest LODs of the multiple pesticide standards were evaluated under the conditions of the validation study in a range of levels from 0 (control) to 100 ng of pesticide residue per g of wheat that separated on a low-polar GC capillary column (Agilent DB-35UI). The results of the HS-SPME method were compared with the QuEChERS AOAC 2007.01 method and they showed several advantages over the latter. These included improved sensitivity, selectivity, and simplicity.

  18. Method development and validation for the simultaneous determination of organochlorine and organophosphorus pesticides in a complex sediment matrix.

    Alcántara-Concepción, Victor; Cram, Silke; Gibson, Richard; Ponce de León, Claudia; Mazari-Hiriart, Marisa

    2013-01-01

    The Xochimilco area in the southeastern part of Mexico City has a variety of socioeconomic activities, such as periurban agriculture, which is of great importance in the Mexico City metropolitan area. Pesticides are used extensively, some being legal, mostly chlorpyrifos and malathion, and some illegal, mostly DDT. Sediments are a common sink for pesticides in aquatic systems near agricultural areas, and Xochimilco sediments have a complex composition with high contents of organic matter and clay that are ideal adsorption sites for organochlorine (OC) and organophosphorus (OP) pesticides. Therefore, it is important to have a quick, affordable, and reliable method to determine these pesticides. Conventional methods for the determination of OC and OP pesticides are long, laborious, and costly owing to the high volume of solvents and adsorbents. The present study developed and validated a method for determining 18 OC and five OP pesticides in sediments with high organic and clay contents. In contrast with other methods described in the literature, this method allows isolation of the 23 pesticides with a 12 min microwave-assisted extraction (MAE) and one-step cleanup of pesticides. The method developed is a simpler, time-saving procedure that uses only 3.5 g of dry sediment. The use of MAE eliminates excessive handling and the possible loss of analytes. It was shown that the use of LC-Si cartridges with hexane-ethyl acetate (75+25, v/v) in the cleanup procedure recovered all pesticides with rates between 70 and 120%. The validation parameters demonstrated good performance of the method, with intermediate precision ranging from 7.3 to 17.0%, HorRat indexes all below 0.5, and tests of accuracy with the 23 pesticides at three concentration levels demonstrating recoveries ranging from 74 to 114% and RSDs from 3.3 to 12.7%.

  19. Planarian cholinesterase: in vitro characterization of an evolutionarily ancient enzyme to study organophosphorus pesticide toxicity and reactivation.

    Hagstrom, Danielle; Hirokawa, Hideto; Zhang, Limin; Radic, Zoran; Taylor, Palmer; Collins, Eva-Maria S

    2017-08-01

    The freshwater planarian Dugesia japonica has recently emerged as an animal model for developmental neurotoxicology and found to be sensitive to organophosphorus (OP) pesticides. While previous activity staining of D. japonica, which possess a discrete cholinergic nervous system, has shown acylthiocholine catalysis, it is unknown whether this is accomplished through an acetylcholinesterase (AChE), butyrylcholinesterase (BChE), or a hybrid esterase and how OP exposure affects esterase activity. Here, we show that the majority of D. japonica cholinesterase (DjChE) activity departs from conventional AChE and BChE classifications. Inhibition by classic protonable amine and quaternary reversible inhibitors (ethopropazine, donepezil, tacrine, edrophonium, BW284c51, propidium) shows that DjChE is far less sensitive to these inhibitors than human AChE, suggesting discrete differences in active center and peripheral site recognition and structures. Additionally, we find that different OPs (chlorpyrifos oxon, paraoxon, dichlorvos, diazinon oxon, malaoxon) and carbamylating agents (carbaryl, neostigmine, physostigmine, pyridostigmine) differentially inhibit DjChE activity in vitro. DjChE was most sensitive to diazinon oxon and neostigmine and least sensitive to malaoxon and carbaryl. Diazinon oxon-inhibited DjChE could be reactivated by the quaternary oxime, pralidoxime (2-PAM), and the zwitterionic oxime, RS194B, with RS194B being significantly more potent. Sodium fluoride (NaF) reactivates OP-DjChE faster than 2-PAM. As one of the most ancient true cholinesterases, DjChE provides insight into the evolution of a hybrid enzyme before the separation into distinct AChE and BChE enzymes found in higher vertebrates. The sensitivity of DjChE to OPs and capacity for reactivation validate the use of planarians for OP toxicology studies.

  20. A sensitive LC-MS/MS method for measurement of organophosphorus pesticides and their oxygen analogs in air sampling matrices.

    Armstrong, Jenna L; Dills, Russell L; Yu, Jianbo; Yost, Michael G; Fenske, Richard A

    2014-01-01

    A rapid liquid chromatography tandem mass spectrometry (LC-MS/MS) method has been developed for determination of levels of the organophosphorus (OP) pesticides chlorpyrifos (CPF), azinphos methyl (AZM), and their oxygen analogs chlorpyrifos-oxon (CPF-O) and azinphos methyl-oxon (AZM-O) on common active air sampling matrices. XAD-2 resin and polyurethane foam (PUF) matrices were extracted with acetonitrile containing stable-isotope labeled internal standards (ISTD). Analysis was accomplished in Multiple Reaction Monitoring (MRM) mode, and analytes in unknown samples were identified by retention time (±0.1 min) and qualifier ratio (±30% absolute) as compared to the mean of calibrants. For all compounds, calibration linearity correlation coefficients were ≥0.996. Limits of detection (LOD) ranged from 0.15-1.1 ng/sample for CPF, CPF-O, AZM, and AZM-O on active sampling matrices. Spiked fortification recoveries were 78-113% from XAD-2 active air sampling tubes and 71-108% from PUF active air sampling tubes. Storage stability tests also yielded recoveries ranging from 74-94% after time periods ranging from 2-10 months. The results demonstrate that LC-MS/MS is a sensitive method for determining these compounds from two different matrices at the low concentrations that can result from spray drift and long range transport in non-target areas following agricultural applications. In an inter-laboratory comparison, the limit of quantification (LOQ) for LC-MS/MS was 100 times lower than a typical gas chromatography-mass spectrometry (GC-MS) method.

  1. A Disposable Organophosphorus Pesticides Enzyme Biosensor Based on Magnetic Composite Nano-Particles Modified Screen Printed Carbon Electrode

    Weigang Wen

    2010-01-01

    Full Text Available A disposable organophosphorus pesticides (OPs enzyme biosensor based on magnetic composite nanoparticle-modified screen printed carbon electrodes (SPCE has been developed. Firstly, an acetylcholinesterase (AChE-coated Fe3O4/Au (GMP magnetic nanoparticulate (GMP-AChE was synthesized. Then, GMP-AChE was absorbed on the surface of a SPCE modified by carbon nanotubes (CNTs/nano-ZrO2/prussian blue (PB/Nafion (Nf composite membrane by an external magnetic field. Thus, the biosensor (SPCE|CNTs/ZrO2/PB/Nf|GMP-AChE for OPs was fabricated. The surface of the biosensor was characterized by scanning electron micrography (SEM and X-ray fluorescence spectrometery (XRFS and its electrochemical properties were studied by cyclic voltammetry (CV and differential pulse voltammetry (DPV. The degree of inhibition (A% of the AChE by OPs was determined by measuring the reduction current of the PB generated by the AChE-catalyzed hydrolysis of acetylthiocholine (ATCh. In pH = 7.5 KNO3 solution, the A was related linearly to the concentration of dimethoate in the range from 1.0 × 10-3–10 ng•mL-1 with a detection limit of 5.6 × 10-4 ng•mL-1. The recovery rates in Chinese cabbage exhibited a range of 88%–105%. The results were consistent with the standard gas chromatography (GC method. Compared with other enzyme biosensors the proposed biosensor exhibited high sensitivity, good selectivity with disposable, low consumption of sample. In particular its surface can be easily renewed by removal of the magnet. The convenient, fast and sensitive voltammetric measurement opens new opportunities for OPs analysis.

  2. Organophosphorus pesticide and ester analysis by using comprehensive two-dimensional gas chromatography with flame photometric detection.

    Liu, Xiangping; Li, Dengkun; Li, Jiequan; Rose, Gavin; Marriott, Philip J

    2013-12-15

    Thirty-seven phosphorus (P)-containing compounds comprising organophosphorus pesticides and organophosphate esters were analyzed by using comprehensive two-dimensional gas chromatography with flame photometric detection in P mode (GC × GC-FPD(P)), with a non-polar/moderately polar column set. A suitable modulation temperature and period was chosen based on experimental observation. A number of co-eluting peak pairs on the (1)D column were well separated in 2D space. Excellent FPD(P) detection selectivity, responding to compounds containing the P atom, produces clear 2D GC × GC plots with little interference from complex hydrocarbon matrices. Limits of detection (LOD) were within the range of 0.0021-0.048 μmol L(-1), and linear calibration correlation coefficients (R(2)) for all 37 P-compounds were at least 0.998. The P-compounds were spiked in 2% diesel and good reproducibility for their response areas and retention times was obtained. Spiked recoveries were 88%-157% for 5 μg L(-1) and 80%-138% for 10 μg L(-1) spiked levels. Both (1)tR and (2)tR shifts were noted when the content of diesel was in excess of 5% in the matrix. Soil samples were analyzed by using the developed method; some P-compounds were positively detected. In general, this study shows that GC × GC-FPD(P) is an accurate, sensitive and simple method for P-compound analysis in complicated environmental samples. Copyright © 2013 Elsevier B.V. All rights reserved.

  3. Synthesis and application of molecularly imprinted polymers for the selective extraction of organophosphorus pesticides from vegetable oils.

    Boulanouar, Sara; Combès, Audrey; Mezzache, Sakina; Pichon, Valérie

    2017-09-01

    The increasing use of pesticides in agriculture causes environmental issues and possible serious health risks to humans and animals. Their determination at trace concentrations in vegetable oils constitutes a significant analytical challenge. Therefore, their analysis often requires both an extraction and a purification step prior to separation with liquid chromatography (LC) and mass spectrometry (MS) detection. This work aimed at developing sorbents that are able to selectively extract from vegetable oil samples several organophosphorus (OPs) pesticides presenting a wide range of physico-chemical properties. Therefore, different conditions were screened to prepare molecularly imprinted polymers (MIPs) by a non-covalent approach. The selectivity of the resulting polymers was evaluated by studying the OPs retention in pure media on both MIPs and non-imprinted polymers (NIP) used as control. The most promising MIP sorbent was obtained using monocrotophos (MCP) as the template, methacrylic acid (MAA) as the monomer and ethylene glycol dimethacrylate (EGDMA) as the cross-linker with a molar ratio of 1/4/20 respectively. The repeatability of the extraction procedure and of the synthesis procedure was demonstrated in pure media. The capacity of this MIP was 1mg/g for malathion. This MIP was also able to selectively extract three OPs from almond oil by applying the optimized SPE procedure. Recoveries were between 73 and 99% with SD values between 4 and 6% in this oil sample. The calculated LOQs (between 0.3 and 2μg/kg) in almond seeds with a SD between 0.1 and 0.4μg/kg were lower than the Maximum Residue Levels (MRLs) established for the corresponding compounds in almond seed. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Multiwalled carbon nanotubes as solid-phase extraction materials for the gas chromatographic determination of organophosphorus pesticides in waters.

    Ravelo-Pérez, Lidia M; Hernández-Borges, Javier; Angel Rodríguez-Delgado, Miguel

    2008-10-01

    In the present work, a GC method with nitrogen-phosphorus detection (NPD) was developed for the simultaneous determination of eight organophosphorus pesticide (OPP) residues (i.e., ethoprofos, diazinon, chlorpyrifos-methyl, fenitrothion, malathion, chlorpyrifos, fenamiphos, and buprofezin) in water samples. Preconcentration of the water samples was carried out using an SPE procedure with multiwalled carbon nanotubes (MWCNTs) of 10-15 nm od, 2-6 nm id, and 0.1-10 microm length as stationary phase. Extraction parameters, such as the amount of MWCNTs, sample volume, pH, and type and amount of the eluent were optimized. The most favorable conditions were as follows: 40 mg MWCNTs, 800 mL water, pH 6.0, and 20 mL dichloromethane, respectively. The MWCNTs-SPE-GC-NPD method was applied to the determination of these pesticides in real water samples: mineral and ground water as well as run-off water from an agricultural area collected shortly before opening out onto the sea. A recovery study was developed with five consecutive extractions of the three types of water spiked at three concentration levels (n = 15). Mean recovery values were in the range of 75-116% for mineral water (RSD water (RSD waters (RSDs waters, RSDs waters). The proposed method was also applied to the analysis of six water samples (two of each type: mineral, ground, and run-off waters) in which no residues of the selected pesticides were found. Results show that the MWCNTs used in this work have a high adsorbability of the pesticides under study. The main advantage of the use of these MWCNTs is their low cost when compared with those MWCNTs previously used in the literature and with conventional SPE cartridges.

  5. Organophosphorus insecticides chlorpyrifos and diazinon and oxidative stress in neuronal cells in a genetic model of glutathione deficiency

    Giordano, Gennaro; Afsharinejad, Zhara; Guizzetti, Marina; Vitalone, Annabella; Kavanagh, Terrance J.; Costa, Lucio G.

    2007-01-01

    Over the past several years evidence has been accumulating from in vivo animal studies, observations in humans, and in vitro studies, that organophosphorus (OP) insecticides may induce oxidative stress. Such effects may contribute to some of the toxic manifestations of OPs, particularly upon chronic or developmental exposures. The aim of this study was to investigate the role of oxidative stress in the neurotoxicity of two commonly used OPs, chlorpyrifos (CPF) and diazinon (DZ), their oxygen analogs (CPO and DZO), and their 'inactive' metabolites (TCP and IMP), in neuronal cells from a genetic model of glutathione deficiency. Cerebellar granule neurons from wild type mice (Gclm +/+) and mice lacking the modifier subunit of glutamate cysteine ligase (Gclm -/-), the first and limiting step in the synthesis of glutathione (GSH), were utilized. The latter display very low levels of GSH and are more susceptible to the toxicity of agents that increase oxidative stress. CPO and DZO were the most cytotoxic compounds, followed by CPF and DZ, while TCP and IMP displayed lower toxicity. Toxicity was significantly higher (10- to 25-fold) in neurons from Gclm (-/-) mice, and was antagonized by various antioxidants. Depletion of GSH from Gclm (+/+) neurons significantly increased their sensitivity to OP toxicity. OPs increased intracellular levels of reactive oxygen species and lipid peroxidation and in both cases the effects were greater in neurons from Gclm (-/-) mice. OPs did not alter intracellular levels of GSH, but significantly increased those of oxidized glutathione (GSSG). Cytotoxicity was not antagonized by cholinergic antagonists, but was decreased by the calcium chelator BAPTA-AM. These studies indicate that cytotoxicity of OPs involves generation of reactive oxygen species and is modulated by intracellular GSH, and suggest that it may involve disturbances in intracellular homeostasis of calcium

  6. Plasma esterases in the tegu lizard Tupinambis merianae (Reptilia, Teiidae): impact of developmental stage, sex, and organophosphorus in vitro exposure.

    Basso, Agustín; Attademo, Andrés M; Lajmanovich, Rafael C; Peltzer, Paola M; Junges, Celina; Cabagna, Mariana C; Fiorenza, Gabriela S; Sanchez-Hernandez, Juan Carlos

    2012-01-01

    In this study, we determined normal serum butyrylcholinesterase (BChE) and carboxylesterase (CbE) activities in Tupinambis merianae in order to obtain reference values for organophosphorus pesticide monitoring. Forty-two T. merianae individuals were grouped by sex and size to identify potential differences in their enzyme levels to allow for proper representation of normal values for females, males, juveniles, and hatchlings. Mean CbE was determined using two model substrates: alpha-naphtylacetate (α-NA) and p-nitrophenyl valerate (4-NPV). BChE and CbE sensitivity to malaoxon (Mx) was also evaluated as well as the possibility of BChE reactivation with pyridine-2-aldoxime methochloride (2-PAM). Mean adult females' BChE was significantly higher than adult males, juveniles, and hatchlings. No significant differences were found between groups regarding CbE. CbE (4-NPV) activity showed slightly negative correlation with lizard snout-vent length, while BChE and CbE (α-NA) showed no correlation with body size. Apparent IC(50) values for BChE and CbE (α-NA) suggested different sensitivities among groups. CbE (4-NPV) could not be inhibited. All Mx-inhibited groups treated with 2-PAM in a final concentration of 2.8 mM showed clear signs of reactivation. In conclusion, the results demonstrate that (1) plasma esterase activity did not vary with age and sex, except for BChE activity, and (2) because biological and environmental variables could be confounding factors in the response of plasma cholinesterases, complementary biomarkers like CbE inhibition and oxime-induced reactivation of esterases are strongly recommended.

  7. Organophosphorus pesticide residues in vegetables from farms, markets, and a supermarket around Kwan Phayao Lake of Northern Thailand.

    Sapbamrer, Ratana; Hongsibsong, Surat

    2014-07-01

    This study investigated organophosphorus (OP) residues in vegetables from 27 farms, 106 markets, and 1 supermarket around Kwan Phayao Lake, Northern Thailand, between August and September 2013. Types of vegetables sampled were all vegetables cultivated or sold around the study site. The most common OP pesticides detected in farm samples were chlorpyrifos (50 %), malathion (31.8 %), monocrotophos (31.8 %), diazinon (13.6 %), omethoate (13.6 %), and dicrotophos (9.1 %). The most common OP pesticides detected in market samples were chlorpyrifos (33.9 %), diazinon (18.6 %), parathion-methyl (3.4 %), profenofos (3.4 %), primiphos-ethyl (3.4 %), and fenitrothion (1.7 %). The OP pesticides detected in supermarket samples were chlorpyrifos (33.3 %), and diazinon (66.7 %). Among the compounds detected, chlorpyrifos was detected in most of the vegetable samples from all sources. The highest chlorpyrifos level in farm samples were found in lemon balm (2.423 mg/kg) followed by Vietnamese coriander (0.835 mg/kg), and cowpea (0.027 mg/kg). The highest level in markets samples were found in garlic (7.785 mg/kg) followed by Chinese cabbage (2.864 mg/kg) and Vietnamese coriander (1.308 mg/kg). Residues from supermarket samples were found only in parsley (0.027 mg/kg). The findings showed that 16 samples (59.3 %) from farms and 14 samples (13.2 %) from markets contained OP residues at or above the maximum residue limits established by the European Union. It is concluded that awareness, safety education, and strict regulation of pesticide use are necessary.

  8. Proton conducting membranes prepared by incorporation of organophosphorus acids into alcohol barrier polymers for direct methanol fuel cells

    Jiang, Zhongyi; Zheng, Xiaohong; Wu, Hong; Pan, Fusheng

    A novel type of DMFC membrane was developed via incorporation of organophosphorus acids (OPAs) into alcohol barrier materials (polyvinyl alcohol/chitosan, PVA/CS) to simultaneously acquire high proton conductivity and low methanol permeability. Three kinds of OPAs including amino trimethylene phosphonic acid (ATMP), ethylene diamine tetra(methylene phosphonic acid) (EDTMP) and hexamethylene diamine tetra(methylene phosphonic acid) (HDTMP), with different molecular structure and phosphonic acid groups content were added into PVA/CS blends and served the dual functions as proton conductor as well as crosslinker. The as-prepared OPA-doped PVA/CS membranes exhibited remarkably enhanced proton conducting ability, 2-4 times higher than that of the pristine PVA/CS membrane, comparable with that for Nafion ®117 membrane (5.04 × 10 -2 S cm -1). The highest proton conductivities 3.58 × 10 -2, 3.51 × 10 -2 and 2.61 × 10 -2 S cm -1 for ATMP-, EDTMP- and HDTMP-doped membranes, respectively were all achieved at highest initial OPA doping content (23.1 wt.%) at room temperature. The EDTMP-doped PVA/CS membrane with an acid content of 13.9 wt.% showed the lowest methanol permeability of 2.32 × 10 -7 cm 2 s -1 which was 16 times lower than that of Nafion ®117 membrane. In addition, the thermal stability and oxidative durability were both significantly improved by the incorporation of OPAs in comparison with pristine PVA/CS membranes.

  9. Proton conducting membranes prepared by incorporation of organophosphorus acids into alcohol barrier polymers for direct methanol fuel cells

    Jiang, Zhongyi; Zheng, Xiaohong; Wu, Hong; Pan, Fusheng [Key Laboratory for Green Chemical Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China)

    2008-10-15

    A novel type of DMFC membrane was developed via incorporation of organophosphorus acids (OPAs) into alcohol barrier materials (polyvinyl alcohol/chitosan, PVA/CS) to simultaneously acquire high proton conductivity and low methanol permeability. Three kinds of OPAs including amino trimethylene phosphonic acid (ATMP), ethylene diamine tetra(methylene phosphonic acid) (EDTMP) and hexamethylene diamine tetra(methylene phosphonic acid) (HDTMP), with different molecular structure and phosphonic acid groups content were added into PVA/CS blends and served the dual functions as proton conductor as well as crosslinker. The as-prepared OPA-doped PVA/CS membranes exhibited remarkably enhanced proton conducting ability, 2-4 times higher than that of the pristine PVA/CS membrane, comparable with that for Nafion {sup registered} 117 membrane (5.04 x 10{sup -2} S cm{sup -1}). The highest proton conductivities 3.58 x 10{sup -2}, 3.51 x 10{sup -2} and 2.61 x 10{sup -2} S cm{sup -1} for ATMP-, EDTMP- and HDTMP-doped membranes, respectively were all achieved at highest initial OPA doping content (23.1 wt.%) at room temperature. The EDTMP-doped PVA/CS membrane with an acid content of 13.9 wt.% showed the lowest methanol permeability of 2.32 x 10{sup -7} cm{sup 2} s{sup -1} which was 16 times lower than that of Nafion {sup registered} 117 membrane. In addition, the thermal stability and oxidative durability were both significantly improved by the incorporation of OPAs in comparison with pristine PVA/CS membranes. (author)

  10. Resistance to organophosphorus agent toxicity in transgenic mice expressing the G117H mutant of human butyrylcholinesterase

    Wang Yuxia; Ticu Boeck, Andreea; Duysen, Ellen G.; Van Keuren, Margaret; Saunders, Thomas L.; Lockridge, Oksana

    2004-01-01

    Organophosphorus toxicants (OP) include chemical nerve agents and pesticides. The goal of this work was to find out whether an animal could be made resistant to OP toxicity by genetic engineering. The human butyrylcholinesterase (BChE) mutant G117H was chosen for study because it has the unusual ability to hydrolyze OP as well as acetylcholine, and it is resistant to inhibition by OP. Human G117H BChE, under the control of the ROSA26 promoter, was expressed in all tissues of transgenic mice. A stable transgenic mouse line expressed 0.5 μg/ml of human G117H BChE in plasma as well as 2 μg/ml of wild-type mouse BChE. Intestine, kidneys, stomach, lungs, heart, spleen, liver, brain, and muscle expressed 0.6-0.15 μg/g of G117H BChE. Transgenic mice were normal in behavior and fertility. The LD50 dose of echothiophate for wild-type mice was 0.1 mg/kg sc. This dose caused severe cholinergic signs of toxicity and lethality in wild-type mice, but caused no deaths and only mild toxicity in transgenic animals. The mechanism of protection was investigated by measuring acetylcholinesterase (AChE) and BChE activity. It was found that AChE and endogenous BChE were inhibited to the same extent in echothiophate-treated wild type and transgenic mice. This led to the hypothesis that protection against echothiophate toxicity was not explained by hydrolysis of echothiophate. In conclusion, the transgenic G117H BChE mouse demonstrates the factors required to achieve protection from OP toxicity in a vertebrate animal

  11. Polyacrylic acid-coated cerium oxide nanoparticles: An oxidase mimic applied for colorimetric assay to organophosphorus pesticides.

    Zhang, Shi-Xiang; Xue, Shi-Fan; Deng, Jingjing; Zhang, Min; Shi, Guoyue; Zhou, Tianshu

    2016-11-15

    It is important and urgent to develop reliable and highly sensitive methods that can provide on-site and rapid detection of extensively used organophosphorus pesticides (OPs) for their neurotoxicity. In this study, we developed a novel colorimetric assay for the detection of OPs based on polyacrylic acid-coated cerium oxide nanoparticles (PAA-CeO2) as an oxidase mimic and OPs as inhibitors to suppress the activity of acetylcholinesterase (AChE). Firstly, highly dispersed PAA-CeO2 was prepared in aqueous solution, which could catalyze the oxidation of TMB to produce a color reaction from colorless to blue. And the enzyme of AChE was used to catalyze the substrate of acetylthiocholine (ATCh) to produce thiocholine (TCh). As a thiol-containing compound with reducibility, TCh can decrease the oxidation of TMB catalyzed by PAA-CeO2. Upon incubated with OPs, the enzymatic activity of AChE was inhibited to produce less TCh, resulting in more TMB catalytically oxidized by PAA-CeO2 to show an increasing blue color. The two representative OPs, dichlorvos and methyl-paraoxon, were tested using our proposed assay. The novel assay showed notable color change in a concentration-dependent manner, and as low as 8.62 ppb dichlorvos and 26.73 ppb methyl-paraoxon can be readily detected. Therefore, taking advantage of such oxidase-like activity of PAA-CeO2, our proposed colorimetric assay can potentially be a screening tool for the precise and rapid evaluation of the neurotoxicity of a wealth of OPs. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Biodegradation and bioremediation potential of diazinon-degrading Serratia marcescens to remove other organophosphorus pesticides from soils.

    Cycoń, Mariusz; Żmijowska, Agnieszka; Wójcik, Marcin; Piotrowska-Seget, Zofia

    2013-03-15

    The ability of diazinon-degrading Serratia marcescens to remove organophosphorus pesticides (OPPs), i.e. chlorpyrifos (CP), fenitrothion (FT), and parathion (PT) was studied in a mineral salt medium (MSM) and in three soils of different characteristics. This strain was capable of using all insecticides at concentration of 50 mg/l as the only carbon source when grown in MSM, and 58.9%, 70.5%, and 82.5% of the initial dosage of CP, FT, and PT, respectively was degraded within 14 days. The biodegradation experiment showed that autochthonous microflora in all soils was characterized by a degradation potential of all tested OPPs; however, the initial lag phases for degradation of CP and FT, especially in sandy soil, were observed. During the 42-day experiment, 45.3%, 61.4% and 72.5% of the initial dose of CP, FT, and PT, respectively, was removed in sandy soil whereas the degradation of CP, FT, and PT in the same period, in sandy loam and silty soils reached 61.4%, 79.7% and 64.2%, and 68.9%, 81.0% and 63.6%, respectively. S. marcescens introduced into sterile soils showed a higher degradation potential (5-13%) for OPPs removal than those observed in non-sterile soil with naturally occurring attenuation. Inoculation of non-sterile soils with S. marcescens enhanced the disappearance rates of all insecticides, and DT50 for CP, FT, and PT was reduced by 20.7, 11.3 and 13.0 days, and 11.9, 7.0 and 8.1 days, and 9.7, 14.5 and 12.6 days in sandy, sandy loam, and silty soils, respectively, in comparison with non-sterile soils with only indigenous microflora. This ability of S. marcescens makes it a suitable strain for bioremediation of soils contaminated with OPPs. Copyright © 2013 Elsevier Ltd. All rights reserved.

  13. Lysophosphatidylcholine hydrolases of human erythrocytes, lymphocytes, and brain: Sensitive targets of conserved specificity for organophosphorus delayed neurotoxicants

    Vose, Sarah C.; Holland, Nina T.; Eskenazi, Brenda; Casida, John E.

    2007-01-01

    Brain neuropathy target esterase (NTE), associated with organophosphorus (OP)-induced delayed neuropathy, has the same OP inhibitor sensitivity and specificity profiles assayed in the classical way (paraoxon-resistant, mipafox-sensitive hydrolysis of phenyl valerate) or with lysophosphatidylcholine (LysoPC) as the substrate. Extending our earlier observation with mice, we now examine human erythrocyte, lymphocyte, and brain LysoPC hydrolases as possible sensitive targets for OP delayed neurotoxicants and insecticides. Inhibitor profiling of human erythrocytes and lymphocytes gave the surprising result of essentially the same pattern as with brain. Human erythrocyte LysoPC hydrolases are highly sensitive to OP delayed neurotoxicants, with in vitro IC 50 values of 0.13-85 nM for longer alkyl analogs, and poorly sensitive to the current OP insecticides. In agricultural workers, erythrocyte LysoPC hydrolyzing activities are similar for newborn children and their mothers and do not vary with paraoxonase status but have high intersample variation that limits their use as a biomarker. Mouse erythrocyte LysoPC hydrolase activity is also of low sensitivity in vitro and in vivo to the OP insecticides whereas the delayed neurotoxicant ethyl n-octylphosphonyl fluoride inhibits activity in vivo at 1-3 mg/kg. Overall, inhibition of blood LysoPC hydrolases is as good as inhibition of brain NTE as a predictor of OP inducers of delayed neuropathy. NTE and lysophospholipases (LysoPLAs) both hydrolyze LysoPC, yet they are in distinct enzyme families with no sequence homology and very different catalytic sites. The relative contributions of NTE and LysoPLAs to LysoPC hydrolysis and clearance from erythrocytes, lymphocytes, and brain remain to be defined

  14. Integrated Lateral Flow Test Strip with Electrochemical Sensor for Quantification of Phosphorylated Cholinesterase: Biomarker of Exposure to Organophosphorus Agents

    Du, Dan; Wang, Jun; Wang, Limin; Lu, Donglai; Lin, Yuehe

    2012-02-08

    An integrated lateral flow test strip with electrochemical sensor (LFTSES) device with rapid, selective and sensitive response for quantification of exposure to organophosphorus (OP) pesticides and nerve agents has been developed. The principle of this approach is based on parallel measurements of post-exposure and baseline acetylcholinesterase (AChE) enzyme activity, where reactivation of the phosphorylated AChE is exploited to enable measurement of total amount of AChE (including inhibited and active) which is used as a baseline for calculation of AChE inhibition. Quantitative measurement of phosphorylated adduct (OP-AChE) was realized by subtracting the active AChE from the total amount of AChE. The proposed LFTSES device integrates immunochromatographic test strip technology with electrochemical measurement using a disposable screen printed electrode which is located under the test zone. It shows linear response between AChE enzyme activity and enzyme concentration from 0.05 to 10 nM, with detection limit of 0.02 nM. Based on this reactivation approach, the LFTSES device has been successfully applied for in vitro red blood cells inhibition studies using chlorpyrifos oxon as a model OP agent. This approach not only eliminates the difficulty in screening of low-dose OP exposure because of individual variation of normal AChE values, but also avoids the problem in overlapping substrate specificity with cholinesterases and avoids potential interference from other electroactive species in biological samples. It is baseline free and thus provides a rapid, sensitive, selective and inexpensive tool for in-field and point-of-care assessment of exposures to OP pesticides and nerve agents.

  15. An Age-Dependent Physiologically-Based Pharmacokinetic/Pharmacodynamic Model for the Organophosphorus Insecticide Chlorpyrifos in the Preweanling Rat

    Timchalk, Chuck; Kousba, Ahmed A.; Poet, Torka S.

    2007-08-01

    Juvenile rats are more susceptible than adults to the acute toxicity of organophosphorus insecticides like chlorpyrifos (CPF). Age- and dose-dependent differences in metabolism may be responsible. Of importance is CYP450 activation and detoxification of CPF to chlorpyrifos-oxon (CPF-oxon) and trichloropyridinol (TCP), as well as B-esterase (cholinesterase; ChE) and A-esterase (PON-1) detoxification of CPF-oxon to TCP. In the current study, a modified physiologically based pharmacokinetic/pharmacodynamic (PBPK/PD) model incorporating age-dependent changes in CYP450, PON-1, and tissue ChE levels for rats was developed. In this model, age was used as a dependent function to estimate body weight which was then used to allometrically scale both metabolism and tissue ChE levels. Model simulations suggest that preweanling rats are particularly sensitive to CPF toxicity, with levels of CPF-oxon in blood and brain disproportionately increasing, relative to the response in adult rats. This age-dependent non-linear increase in CPF-oxon concentration may potentially result from the depletion of non-target B-esterases, and a lower PON-1 metabolic capacity in younger animals. These results indicate that the PBPK/PD model behaves consistently with the general understanding of CPF toxicity, pharmacokinetics and tissue ChE inhibition in neonatal and adult rats. Hence, this model represents an important starting point for developing a computational model to assess the neurotoxic potential of environmentally relevant organophosphate exposures in infants and children.

  16. Consumption of fruits and vegetables and probabilistic assessment of the cumulative acute exposure to organophosphorus and carbamate pesticides of schoolchildren in Slovenia.

    Blaznik, Urška; Yngve, Agneta; Eržen, Ivan; Hlastan Ribič, Cirila

    2016-02-01

    Adequate consumption of fruits and vegetables is a part of recommendations for a healthy diet. The aim of the present study was to assess acute cumulative dietary exposure to organophosphorus and carbamate pesticides via fruit and vegetable consumption by the population of schoolchildren aged 11-12 years and the level of risk for their health. Cumulative probabilistic risk assessment methodology with the index compound approach was applied. Slovenia, primary schools. Schoolchildren (n 1145) from thirty-one primary schools in Slovenia. Children were part of the PRO GREENS study 2009/10 which assessed 11-year-olds' consumption of fruit and vegetables in ten European countries. The cumulative acute exposure amounted to 8.3 (95% CI 7.7, 10.6) % of the acute reference dose (ARfD) for acephate as index compound (100 µg/kg body weight per d) at the 99.9th percentile for daily intake and to 4.5 (95% CI 3.5, 4.7) % of the ARfD at the 99.9th percentile for intakes during school time and at lunch. Apples, bananas, oranges and lettuce contributed most to the total acute pesticides intake. The estimations showed that acute dietary exposure to organophosphorus and carbamate pesticides is not a health concern for schoolchildren with the assessed dietary patterns of fruit and vegetable consumption.

  17. Isolation of the opdE gene that encodes for a new hydrolase of Enterobacter sp. capable of degrading organophosphorus pesticides.

    Chino-Flores, Concepción; Dantán-González, Edgar; Vázquez-Ramos, Alejandra; Tinoco-Valencia, Raunel; Díaz-Méndez, Rafael; Sánchez-Salinas, Enrique; Castrejón-Godínez, Maria Luisa; Ramos-Quintana, Fernando; Ortiz-Hernández, Maria Laura

    2012-06-01

    Microbial enzymes that can hydrolyze organophosphorus compounds have been isolated, identified and characterized from different microbial species in order to use them in biodegradation of organophosphorus compounds. We isolated a bacterial strain Cons002 from an agricultural soil bacterial consortium, which can hydrolyze methyl-parathion (MP) and other organophosphate pesticides. HPLC analysis showed that strain Cons002 is capable of degrading pesticides MP, parathion and phorate. Pulsed-field gel electrophoresis and 16S rRNA amplification were performed for strain characterization and identification, respectively, showing that the strain Cons002 is related to the genus Enterobacter sp. which has a single chromosome of 4.6 Mb and has no plasmids. Genomic library was constructed from DNA of Enterobacter sp. Cons002. A gene called opdE (Organophosphate Degradation from Enterobacter) consists of 753 bp and encodes a protein of 25 kDa, which was isolated using activity methods. This gene opdE had no similarity to any genes reported to degrade organophosphates. When kanamycin-resistance cassette was placed in the gene opdE, hydrolase activity was suppressed and Enterobacter sp. Cons002 had no growth with MP as a nutrients source.

  18. Simultaneous determination of organophosphorus pesticides in fruits and vegetables using atmospheric pressure gas chromatography quadrupole-time-of-flight mass spectrometry.

    Cheng, Zhipeng; Dong, Fengshou; Xu, Jun; Liu, Xingang; Wu, Xiaohu; Chen, Zenglong; Pan, Xinglu; Gan, Jay; Zheng, Yongquan

    2017-09-15

    This paper describes the application of atmospheric pressure gas chromatography quadrupole-time-of-flight mass spectrometry for the simultaneous determination of organophosphorus pesticides in apple, pear, tomato, cucumber and cabbage. Soft ionization with atmospheric pressure ionization source was compared with traditional electron impact ionization (EI). The sensitivity of GC coupled to atmospheric pressure ionization (APGC) for all the analytes was enhanced by 1.0-8.2 times. The ionization modes with atmospheric pressure ionization source was studied by comparing the charge-transfer and proton-transfer conditions. The optimized QuEChERs method was used to pretreat the samples. The calibration curves were found linear from 10 to 1000μg/L, obtaining correlation coefficients higher than 0.9845. Satisfactory mean recovery values, in the range of 70.0-115.9%, and satisfactory precision, with all RSD r <19.7% and all RSD R values <19.5% at the three fortified concentration levels for all the fifteen OPPs. The results demonstrate the potential of APGC-QTOF-MS for routine quantitative analysis of organophosphorus pesticide in fruits and vegetables. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. [High throuput analysis of organophosphorus pesticide residues and their metabolites in animal original foods by dual gas chromatography-dual pulse flame photometric detection].

    Yang, Lixin; Li, Heli; Miao, Hong; Zeng, Fangang; Li, Ruifeng; Chen, Huijing; Zhao, Yunfeng; Wu, Yongning

    2011-10-01

    A method was established for the quantitative determination of 54 organophosphorus pesticide residues and their metabolites in foods of animal origin by dual gas chromatography-dual pulse flame photometric detection. Homogenized samples were extracted with acetone and methylene chloride, and cleaned-up by gel permeation chromatography (GPC). The response of each analyte showed a good linearity with a correlation coefficient not less than 0. 99. The recovery experiments were performed by a blank sample spiked at low, medium and high fortification levels. The recoveries for beef, mutton, pork, chicken were in the range of 50. 5% -128. 1% with the relative standard deviations (n = 6) of 1. 1% -25. 5%, which demonstrated the good precision and accuracy of the present method. The limits of detection for the analytes were in the range of 0. 001 -0. 170 mg/kg, and the limits of quantification were in the range of 0. 002 -0. 455 mg/kg. Animal food samples collected from markets such as meat, liver and kidney were analyzed, and the residues of dichlorovos and disulfoton-sulfoxide were found in the some samples. The established method is sensitive and selective enough to detect organophosphorus pesticide residues in animal foods.

  20. Developmental exposure to terbutaline alters cell signaling in mature rat brain regions and augments the effects of subsequent neonatal exposure to the organophosphorus insecticide chlorpyrifos

    Meyer, Armando; Seidler, Frederic J.; Aldridge, Justin E.; Slotkin, Theodore A.

    2005-01-01

    Exposure to apparently unrelated neurotoxicants can nevertheless converge on common neurodevelopmental events. We examined the long-term effects of developmental exposure of rats to terbutaline, a β-adrenoceptor agonist used to arrest preterm labor, and the organophosphorus insecticide chlorpyrifos (CPF) separately and together. Treatments mimicked the appropriate neurodevelopmental stages for human exposures: terbutaline on postnatal days (PN) 2-5 and CPF on PN11-14, with assessments conducted on PN45. Although neither treatment affected growth or viability, each elicited alterations in CNS cell signaling mediated by adenylyl cyclase (AC), a transduction pathway shared by numerous neuronal and hormonal signals. Terbutaline altered signaling in the brainstem and cerebellum, with gender differences particularly notable in the cerebellum (enhanced AC in males, suppressed in females). By itself, CPF exposure elicited deficits in AC signaling in the midbrain, brainstem, and striatum. However, sequential exposure to terbutaline followed by CPF produced larger alterations and involved a wider spectrum of brain regions than were obtained with either agent alone. In the cerebral cortex, adverse effects of the combined treatment intensified between PN45 and PN60, suggesting that exposures alter the long-term program for development of synaptic communication, leading to alterations in AC signaling that emerge even after adolescence. These findings indicate that terbutaline, like CPF, is a developmental neurotoxicant, and reinforce the idea that its use in preterm labor may create a subpopulation that is sensitized to long-term CNS effects of organophosphorus insecticides

  1. Establishment of Exposure to Organophosphorus Warfare Agents by Means of SPME-GSMS Analysis of Bodily Fluids

    Saveleva, E. I.; Koryagina, N. L.; Radilov, A. S.; Khlebnikova, N. S.; Khrustaleva, V. S.; Feld, V. E.

    2007-01-01

    Reliable chemical analytical procedures for revealing an exposure to toxic chemicals, identifying the active substance, and assessing the degree of exposure are necessary as a component of medical and forensic activities in cases of the possible use of highly toxic chemicals in war conflicts and terrorism acts, as well as emergency situations in chemical industry, specifically at chemical weapons storage and destruction facilities. According to Chemical Weapons Convention, Part XI, Appendix 4, e-17, 'samples of importance in the investigation of alleged use include biomedical samples from human or animal sources (blood, urine, excreta, tissue etc.)'. Urinary metabolites, O-alkyl esters of methylphosphic acid, offer one of the simplest means of confirming an exposure to organophosphorus warfare agents (OPWA). Urine, unlike blood or tissues, does not require invasive collection demanding in terms of sterility. Excretion with urine is the major route of elimination of OPWA from an organism. According to published data, 90% of OPWA metabolites are excreted within 48-72 h after intoxication. We developed an SPME-GCMS procedure for the determination of O-alkyl esters methylphosphonic acid in urine, with the following detection limits,: isopropyl and isobutyl esters 5 ng/ml and pinacolyl ester 1 ng/ml. The procedure involves derivatization of the target compounds directly on the microfiber. The total analysis time is 1-1.5 h. In animal experiments in vivo we could establish the exposure to OPWA at a half-LD50 level within no less than 48 h after intoxication. In principle, OPWA metabolites could be detected in urine within two weeks after intoxication but at higher doses. Retrospective analysis of urinary metabolites in cases of the exposure to low doses of OPWA requires lower detection limits (0.1-1 ng/ml). Optimal objects for the retrospective analysis of OPWA in an organism are long-lived blood protein adducts. We developed a procedure for revealing an exposure to

  2. Organophosphorus pesticide and ester analysis by using comprehensive two-dimensional gas chromatography with flame photometric detection

    Liu, Xiangping; Li, Dengkun; Li, Jiequan [Nanjing Centre for Disease Control and Prevention, Zizhulin Street, Gulou 210003, Nanjing (China); Rose, Gavin [Department of Environment and Primary Industries, Macleod Centre, Ernest Jones Drive, Macleod, Vic 3085 (Australia); Marriott, Philip J., E-mail: philip.marriott@monash.edu [Australian Centre for Research on Separation Science, School of Chemistry, Monash University, Wellington Road, Clayton 3800 (Australia)

    2013-12-15

    Highlights: • GC × GC-FPD(P-mode) was applied to detection of 37 phosphorus (P)-containing compounds. • The method improves resolution of P-compounds that coelute in the first dimension. • P-compounds are analyzed with excellent sensitivity supported by cryogenic modulation. • The FPD(P-mode) selectivity allows analysis in high hydrocarbon (H/C) matrix. • Soil samples and spiked chemical weapon compounds in H/C matrix are readily screened. -- Abstract: Thirty-seven phosphorus (P)-containing compounds comprising organophosphorus pesticides and organophosphate esters were analyzed by using comprehensive two-dimensional gas chromatography with flame photometric detection in P mode (GC × GC-FPD(P)), with a non-polar/moderately polar column set. A suitable modulation temperature and period was chosen based on experimental observation. A number of co-eluting peak pairs on the {sup 1}D column were well separated in 2D space. Excellent FPD(P) detection selectivity, responding to compounds containing the P atom, produces clear 2D GC × GC plots with little interference from complex hydrocarbon matrices. Limits of detection (LOD) were within the range of 0.0021–0.048 μmol L{sup −1}, and linear calibration correlation coefficients (R{sup 2}) for all 37 P-compounds were at least 0.998. The P-compounds were spiked in 2% diesel and good reproducibility for their response areas and retention times was obtained. Spiked recoveries were 88%–157% for 5 μg L{sup −1} and 80%–138% for 10 μg L{sup −1} spiked levels. Both {sup 1}t{sub R} and {sup 2}t{sub R} shifts were noted when the content of diesel was in excess of 5% in the matrix. Soil samples were analyzed by using the developed method; some P-compounds were positively detected. In general, this study shows that GC × GC-FPD(P) is an accurate, sensitive and simple method for P-compound analysis in complicated environmental samples.

  3. A set of triple-resonance nuclear magnetic resonance experiments for structural characterization of organophosphorus compounds in mixture samples

    Koskela, Harri, E-mail: Harri.T.Koskela@helsinki.fi [VERIFIN, University of Helsinki, P.O. Box 55, FIN-00014 Helsinki (Finland)

    2012-11-02

    Highlights: Black-Right-Pointing-Pointer New {sup 1}H, {sup 13}C, {sup 31}P triple-resonance NMR pulse experiments. Black-Right-Pointing-Pointer Analysis of organophosphorus (OP) compounds in complex matrix. Black-Right-Pointing-Pointer Selective extraction of {sup 1}H, {sup 31}P, and {sup 13}C chemical shifts and connectivities. Black-Right-Pointing-Pointer More precise NMR identification of OP nerve agents and their degradation products. - Abstract: The {sup 1}H, {sup 13}C correlation NMR spectroscopy utilizes J{sub CH} couplings in molecules, and provides important structural information from small organic molecules in the form of carbon chemical shifts and carbon-proton connectivities. The full potential of the {sup 1}H, {sup 13}C correlation NMR spectroscopy has not been realized in the Chemical Weapons Convention (CWC) related verification analyses due to the sample matrix, which usually contains a high amount of non-related compounds obscuring the correlations of the relevant compounds. Here, the results of the application of {sup 1}H, {sup 13}C, {sup 31}P triple-resonance NMR spectroscopy in characterization of OP compounds related to the CWC are presented. With a set of two-dimensional triple-resonance experiments the J{sub HP}, J{sub CH} and J{sub PC} couplings are utilized to map the connectivities of the atoms in OP compounds and to extract the carbon chemical shift information. With the use of the proposed pulse sequences the correlations from the OP compounds can be recorded without significant artifacts from the non-OP compound impurities in the sample. Further selectivity of the observed correlations is achieved with the application of phosphorus band-selective pulse in the pulse sequences to assist the analysis of multiple OP compounds in mixture samples. The use of the triple-resonance experiments in the analysis of a complex sample is shown with a test mixture containing typical scheduled OP compounds, including the characteristic degradation

  4. Are organohalogen contaminants a bears (Ursus maritimus)?

    Sonne, Christian; Dietz, Rune; Leifsson, PS

    2006-01-01

    PBDE, polychlorinated biphenyl, and hexachlorocyclohexane concentrations. The lesions were consistent with those reported previously in highly OHC-contaminated Baltic seal populations and exposed laboratory animals. The renal lesions were a result of aging. However, based on the above statistical findings as well......, whereas none was associated with the sex of the animals. In an age-controlled statistical analysis of covariance, increases in glomerular mesangial deposits and interstitial fibrosis were significantly (p

  5. Simultaneous determination of organophosphorus pesticides and phthalates in baby food samples by ultrasound-vortex-assisted liquid-liquid microextraction and GC-IT/MS.

    Notardonato, Ivan; Salimei, Elisabetta; Russo, Mario Vincenzo; Avino, Pasquale

    2018-05-01

    Baby foods are either a soft, liquid paste or an easily chewed food since babies lack developed muscles and teeth to chew effectively. Babies typically move to consuming baby food once nursing or formula is not sufficient for the child's appetite. Some commercial baby foods have been criticized for their contents. This article focuses on the simultaneous determination of organophosphorus pesticides and phthalates by means of a method based on ultrasound-vortex-assisted liquid-liquid microextraction coupled with gas chromatography-ion trap mass spectrometry (GC-IT/MS). The protocol developed allowed the determination of six phthalates [dimethyl phthalate, diethyl phthalate, dibutyl phthalate, isobutyl cyclohexyl phthalate, benzyl butyl phthalate, bis(2-ethylhexyl) phthalate] and 19 organophosphorus pesticides. Freeze-dried product samples (0.1-0.2 g) were dissolved in 10 mL of warm distilled water along with 5 μL of an internal standard (anthracene at 10 mg mL -1 in acetone): the choice of extraction solvent was studied, with the most suitable being n-heptane, which is used for phthalate determination in similar matrices. The solution, held for 5 min in a vortex mixer and for 6 min in a 100-W ultrasonic bath to favor solvent dispersion and consequently analyte extraction, was centrifuged at 4000 rpm for 30 min. Then 1 μL was injected into the GC-IT/MS system (SE-54 capillary column; length 30 m, inner diameter 250 μm, film thickness 0.25 μm). All analytical parameters investigated are discussed in depth. The method was applied to real commercial freeze-dried samples: significant contaminant concentrations were not found. Graphical abstract Simultaneous and sensitive determination of organophosphorus pesticides and phthalates in baby foods by the ultrasound-vortex-assisted liquid-liquid microextraction ֪gas chromatography-ion trap mass spectrometry procedure. 1 methacrifos, 2 pirofos, 3 phorate, 4 seraphos, 5 diazinon, 6 etrimphos, 7 dichlofenthion, 8

  6. High-performance liquid chromatography using reversed-phase stationary phases dynamically modified with organophosphorus compound for the separation and determination of lanthanoid elements

    Tsuyoshi, Akira; Akiba, Kenichi

    2000-01-01

    An acidic organophosphorus compound, 2-ethylhexylphosphonic acid mono-2-ethlhexyl ester (EHPA), has been applied to reversed-phase high-performance liquid chromatography (RP-HPLC). The reversed-phase stationary phase was dynamically modified with EHPA by flowing the mobile phase of an acetone-water mixture containing the extracting regent. The retention of lanthanoid elements was widely varied by changing the conditions of the mobile phase, i.e., the pH, the EHPA concentration and the acetone content. The selectivity of EHPA is well reflected to the chromatographic systems, and a precise separation of lanthanoid elements was achieved with sufficient resolution. The determination of Sm was examined in the presence of a large amount of Nd. A linear calibration graph was obtained for Sm at the level of 10 -7 mol dm -3 , in the presence of 1x10 -4 mol dm -3 of Nd. (author)

  7. Acute effects of a sarin-like organophosphorus agent, bis(isopropyl methyl)phosphonate, on cardiovascular parameters in anaesthetized, artificially ventilated rats

    Watanabe, Yoshimasa [Department of Pharmacology, Graduate School of Medical Sciences, Nagoya City University, Nagoya (Japan); Itoh, Takeo, E-mail: titoh@med.nagoya-cu.ac.jp [Department of Pharmacology, Graduate School of Medical Sciences, Nagoya City University, Nagoya (Japan); Shiraishi, Hiroaki [Department of Forensic Medicine, Institute of Biomedical and Health Sciences, Hiroshima University, Hiroshima (Japan); Maeno, Yoshitaka [Department of Forensic Medical Science, Graduate School of Medical Sciences, Nagoya City University, Nagoya (Japan); Arima, Yosuke; Torikoshi, Aiko; Namera, Akira [Department of Forensic Medicine, Institute of Biomedical and Health Sciences, Hiroshima University, Hiroshima (Japan); Makita, Ryosuke [Department of Nursing, Faculty of Health Sciences, Hiroshima Cosmopolitan University, Hiroshima (Japan); Yoshizumi, Masao [Department of Cardiovascular Physiology and Medicine, Institute of Biomedical and Health Sciences, Hiroshima University, Hiroshima (Japan); Nagao, Masataka [Department of Forensic Medicine, Institute of Biomedical and Health Sciences, Hiroshima University, Hiroshima (Japan)

    2013-10-01

    The organophosphorus compound sarin irreversibly inhibits acetylcholinesterase. We examined the acute cardiovascular effects of a sarin-like organophosphorus agent, bis(isopropyl methyl)phosphonate (BIMP), in anaesthetized, artificially ventilated rats. Intravenous administration of BIMP (0.8 mg/kg; the LD50 value) induced a long-lasting increase in blood pressure and tended to increase heart rate. In rats pretreated with the non-selective muscarinic-receptor antagonist atropine, BIMP significantly increased both heart rate and blood pressure. In atropine-treated rats, hexamethonium (antagonist of ganglionic nicotinic receptors) greatly attenuated the BIMP-induced increase in blood pressure without changing the BIMP-induced increase in heart rate. In rats treated with atropine plus hexamethonium, intravenous phentolamine (non-selective α-adrenergic receptor antagonist) plus propranolol (non-selective β-adrenergic receptor antagonist) completely blocked the BIMP-induced increases in blood pressure and heart rate. In atropine-treated rats, the reversible acetylcholinesterase inhibitor neostigmine (1 mg/kg) induced a transient increase in blood pressure, but had no effect on heart rate. These results suggest that in anaesthetized rats, BIMP induces powerful stimulation of sympathetic as well as parasympathetic nerves and thereby modulates heart rate and blood pressure. They may also indicate that an action independent of acetylcholinesterase inhibition contributes to the acute cardiovascular responses induced by BIMP. - Highlights: • A sarin-like agent BIMP markedly increased blood pressure in anaesthetized rats. • Muscarinic receptor blockade enhanced the BIMP-induced increase in blood pressure. • Ganglionic nicotinic receptor blockade attenuated the BIMP-induced response. • Blockade of α- as well as β-receptors attenuated the BIMP-induced response.

  8. Quantitative structure-activity analysis of acetylcholinesterase inhibition by oxono and thiono analogues of organophosphorus compounds. (Reannouncement with new availability information)

    Maxwell, D.M.; Brecht, K.M.

    1992-02-01

    A comparison of the bimolecular rate constants (ki) for inhibition of electric eel acetylcholinesterase (AChE) by the oxono (i.e., P=O) and thiono (i.e., P=S) analogues of parathion, methylparathion, leptophos, fonofos, sarin, and soman revealed that the oxono/thiono ratios of ki values varied from 14 for soman to 1240 for parathion. Analysis of the relative importance of the dissociation equilibrium constant and the phosphorylation rate constant in producing this variation in ki values indicated that the oxono analogues had phosphorylation rate constant values that varied in a narrow range from 8- to 14-fold greater than their thiono counterparts, while the oxono/thiono ratios for dissociation constants varied widely from 1 for soman to 82 for fonofos. The lower affinities of thiono analogues for AChE probably resulted from differences in the hydrophobic binding of oxono and thiono analogues to the active site of AChE, inasmuch as the hydrophobicities (i.e., octanol/water partition coefficients) of thiono organophosphorus compounds were much greater than the hydrophobicities of their oxono analogues. Quantitative structure-activity analysis indicated that the hydrophobic effects of oxono and thiono moieties correlated with log ki for AChE inhibition to a greater extent (r2 = 0.79) than their electronic effects (r2 equal to or less than 0.48). These observations suggest that the differences in hydrophobicity of oxono and thiono analogues of organophosphorus compounds may be as important as their electronic differences in determining their effectiveness as AChE inhibitors. Acetylcholinesterase, soman (GD), structure-activity analysis inhibition, oxono analogues, thiono analogues.

  9. Acute effects of a sarin-like organophosphorus agent, bis(isopropyl methyl)phosphonate, on cardiovascular parameters in anaesthetized, artificially ventilated rats

    Watanabe, Yoshimasa; Itoh, Takeo; Shiraishi, Hiroaki; Maeno, Yoshitaka; Arima, Yosuke; Torikoshi, Aiko; Namera, Akira; Makita, Ryosuke; Yoshizumi, Masao; Nagao, Masataka

    2013-01-01

    The organophosphorus compound sarin irreversibly inhibits acetylcholinesterase. We examined the acute cardiovascular effects of a sarin-like organophosphorus agent, bis(isopropyl methyl)phosphonate (BIMP), in anaesthetized, artificially ventilated rats. Intravenous administration of BIMP (0.8 mg/kg; the LD50 value) induced a long-lasting increase in blood pressure and tended to increase heart rate. In rats pretreated with the non-selective muscarinic-receptor antagonist atropine, BIMP significantly increased both heart rate and blood pressure. In atropine-treated rats, hexamethonium (antagonist of ganglionic nicotinic receptors) greatly attenuated the BIMP-induced increase in blood pressure without changing the BIMP-induced increase in heart rate. In rats treated with atropine plus hexamethonium, intravenous phentolamine (non-selective α-adrenergic receptor antagonist) plus propranolol (non-selective β-adrenergic receptor antagonist) completely blocked the BIMP-induced increases in blood pressure and heart rate. In atropine-treated rats, the reversible acetylcholinesterase inhibitor neostigmine (1 mg/kg) induced a transient increase in blood pressure, but had no effect on heart rate. These results suggest that in anaesthetized rats, BIMP induces powerful stimulation of sympathetic as well as parasympathetic nerves and thereby modulates heart rate and blood pressure. They may also indicate that an action independent of acetylcholinesterase inhibition contributes to the acute cardiovascular responses induced by BIMP. - Highlights: • A sarin-like agent BIMP markedly increased blood pressure in anaesthetized rats. • Muscarinic receptor blockade enhanced the BIMP-induced increase in blood pressure. • Ganglionic nicotinic receptor blockade attenuated the BIMP-induced response. • Blockade of α- as well as β-receptors attenuated the BIMP-induced response

  10. Synergistic solvent extraction investigation of Am (III), Eu (III), Zn(II), and Cs(I), using 2-heptyl-2-methyl-nonanoic acid mixed with different organophosphorus compounds from nitrate media. Vol. 3

    El-Naggar, H.A.; Ramadan, A.; Abdel-Fattah, A.

    1996-01-01

    Extraction studies for investigating the effect of mixing 2-heptyl-2-methyl nonanoic acid (HA) with a number of organophosphorus compounds; namely tributyl phosphate (TBP), terphenyl phosphate oxide (TPPO); tri octyl phosphine oxide (TOPO) or bis-2-(ethyl hexyl) phosphoric acid (HDEHP) in benzene on the extraction of trace elements Am(III), Eu(III), Zn(II), and Cs(I) from nitrate media of ionic strength, I=0.1 M were carried out. The effect of adding different organophosphorus compounds to HA was tested to account for the presence or absence of the phenomenon of synergism. It was found that TBP, TPPO, and TOPO causing some antagonistic effects for the elements studied. Extraction enhancement was only observed with bis- (2-ethyl-hexyl) -phosphoric acid (HDEHP) for all the elements investigated. The extraction mechanisms as well as the thermodynamic parameters for the mixed extracted species are discussed. 19 figs

  11. Synergistic solvent extraction investigation of Am (III), Eu (III), Zn(II), and Cs(I), using 2-heptyl-2-methyl-nonanoic acid mixed with different organophosphorus compounds from nitrate media. Vol. 3

    El-Naggar, H A; Ramadan, A; Abdel-Fattah, A [Nuclear Chemistry Department, Hot Laboratories Center, Atomic Energy Authority, Cairo (Egypt)

    1996-03-01

    Extraction studies for investigating the effect of mixing 2-heptyl-2-methyl nonanoic acid (HA) with a number of organophosphorus compounds; namely tributyl phosphate (TBP), terphenyl phosphate oxide (TPPO); tri octyl phosphine oxide (TOPO) or bis-2-(ethyl hexyl) phosphoric acid (HDEHP) in benzene on the extraction of trace elements Am(III), Eu(III), Zn(II), and Cs(I) from nitrate media of ionic strength, I=0.1 M were carried out. The effect of adding different organophosphorus compounds to HA was tested to account for the presence or absence of the phenomenon of synergism. It was found that TBP, TPPO, and TOPO causing some antagonistic effects for the elements studied. Extraction enhancement was only observed with bis- (2-ethyl-hexyl) -phosphoric acid (HDEHP) for all the elements investigated. The extraction mechanisms as well as the thermodynamic parameters for the mixed extracted species are discussed. 19 figs.

  12. Zero valent Fe-reduced graphene oxide quantum dots as a novel magnetic dispersive solid phase microextraction sorbent for extraction of organophosphorus pesticides in real water and fruit juice samples prior to analysis by gas chromatography-mass spectrometry.

    Akbarzade, Samaneh; Chamsaz, Mahmoud; Rounaghi, Gholam Hossein; Ghorbani, Mahdi

    2018-01-01

    A selective and sensitive magnetic dispersive solid-phase microextraction (MDSPME) coupled with gas chromatography-mass spectrometry was developed for extraction and determination of organophosphorus pesticides (Sevin, Fenitrothion, Malathion, Parathion, and Diazinon) in fruit juice and real water samples. Zero valent Fe-reduced graphene oxide quantum dots (rGOQDs@ Fe) as a new and effective sorbent were prepared and applied for extraction of organophosphorus pesticides using MDSPME method. In order to study the performance of this new sorbent, the ability of rGOQDs@ Fe was compared with graphene oxide and magnetic graphene oxide nanocomposite by recovery experiments of the organophosphorus pesticides. Several affecting parameters in the microextraction procedure, including pH of donor phase, donor phase volume, stirring rate, extraction time, and desorption conditions such as the type and volume of solvents and desorption time were thoroughly investigated and optimized. Under the optimal conditions, the method showed a wide linear dynamic range with R-square between 0.9959 and 0.9991. The limit of detections, the intraday and interday relative standard deviations (n = 5) were less than 0.07 ngmL -1 , 4.7, and 8.6%, respectively. The method was successfully applied for extraction and determination of organophosphorus pesticides in real water samples (well, river and tap water) and fruit juice samples (apple and grape juice). The obtained relative recoveries were in the range of 82.9%-113.2% with RSD percentages of less than 5.8% for all the real samples.

  13. 31P-edited diffusion-ordered 1H NMR spectroscopy for the spectral isolation and identification of organophosphorus compounds related to chemical weapons agents and their degradation products.

    Mayer, Brian P; Valdez, Carlos A; Hok, Saphon; Chinn, Sarah C; Hart, Bradley R

    2012-12-04

    Organophosphorus compounds represent a large class of molecules that include pesticides, flame-retardants, biologically relevant molecules, and chemical weapons agents (CWAs). The detection and identification of organophosphorus molecules, particularly in the cases of pesticides and CWAs, are paramount to the verification of international treaties by various organizations. To that end, novel analytical methodologies that can provide additional support to traditional analyses are important for unambiguous identification of these compounds. We have developed an NMR method that selectively edits for organophosphorus compounds via (31)P-(1)H heteronuclear single quantum correlation (HSQC) and provides an additional chromatographic-like separation based on self-diffusivities of the individual species via (1)H diffusion-ordered spectroscopy (DOSY): (1)H-(31)P HSQC-DOSY. The technique is first validated using the CWA VX (O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate) by traditional two-dimensional DOSY spectra. We then extend this technique to a complex mixture of VX degradation products and identify all the main phosphorus-containing byproducts generated after exposure to a zinc-cyclen organometallic homogeneous catalyst.

  14. Pilot-scale incineration of wastes with high content of chlorinated and non-halogenated organophosphorus flame retardants used as alternatives for PBDEs

    Matsukami, Hidenori; Kose, Tomohiro; Watanabe, Mafumi; Takigami, Hidetaka

    2014-01-01

    Chlorinated and non-halogenated organophosphorus flame retardants (OPFRs) including tris(2-chloroisopropyl) phosphate (TCIPP), diethylene glycol bis(di(2-chloroisopropyl) phosphate) (DEG-BDCIPP), triphenyl phosphate (TPHP), and bisphenol A bis(diphenyl phosphate) (BPA-BDPP) have been used increasingly as alternatives to polybrominated diphenyl ethers and other brominated flame retardants. For this study, five batches of incineration experiments of wastes containing approximately 1% of TCIPP, DEG-BDCIPP, TPHP, and BPA-BDPP were conducted using a pilot-scale incinerator. Destruction and emission behaviors of OPFRs were investigated along with the effects on behaviors of unintentional persistent organic pollutants (POPs) such as polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (dl-PCBs), hexachlorobenzene (HCB), pentachlorobenzene (PeCB), and pentachlorophenol (PCP). Incineration conditions were chosen according to current regulations for waste incinerators in Japan and UNEP. The OPFRs in the input materials were mainly destroyed in the primary combustion with destruction efficiencies greater than 99.999%. Concentrations of the OPFRs in the exhaust gases and ash were, respectively, < 0.01–0.048 μg m −3 and < 0.5–68 μg kg −1 . Almost all of the total phosphorus in the input materials was partitioned into the ash, but less into final exit gases, indicating negligible emissions of volatile phosphorus compounds during incineration. Inputs of chlorinated OPFRs did not affect the formation markedly. Destruction and emission behaviors of unintentional POPs were investigated. Emissions of such POPs in exhaust gases and the ash were lower than the Japanese and international standards. Results show that even in wastes with high contents of chlorinated and non-halogenated OPFRs, waste incineration by the current regulations for the waste incinerators can control environmental emissions of OPFRs and

  15. Pilot-scale incineration of wastes with high content of chlorinated and non-halogenated organophosphorus flame retardants used as alternatives for PBDEs

    Matsukami, Hidenori, E-mail: matsukami.hidenori@nies.go.jp [Center for Material Cycles and Waste Management Research, National Institute for Environmental Studies (NIES), 16-2 Onogawa, Tsukuba 305-8506 (Japan); Graduate School of Frontier Sciences, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa 277-8563 (Japan); Kose, Tomohiro [Faculty of Applied Life Sciences, Niigata University of Pharmacy and Applied Life Sciences, 265-1, Higashijima, Akiha-ku, Niigata 956-8603 (Japan); Watanabe, Mafumi [Center for Material Cycles and Waste Management Research, National Institute for Environmental Studies (NIES), 16-2 Onogawa, Tsukuba 305-8506 (Japan); Takigami, Hidetaka [Center for Material Cycles and Waste Management Research, National Institute for Environmental Studies (NIES), 16-2 Onogawa, Tsukuba 305-8506 (Japan); Graduate School of Frontier Sciences, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa 277-8563 (Japan)

    2014-09-15

    Chlorinated and non-halogenated organophosphorus flame retardants (OPFRs) including tris(2-chloroisopropyl) phosphate (TCIPP), diethylene glycol bis(di(2-chloroisopropyl) phosphate) (DEG-BDCIPP), triphenyl phosphate (TPHP), and bisphenol A bis(diphenyl phosphate) (BPA-BDPP) have been used increasingly as alternatives to polybrominated diphenyl ethers and other brominated flame retardants. For this study, five batches of incineration experiments of wastes containing approximately 1% of TCIPP, DEG-BDCIPP, TPHP, and BPA-BDPP were conducted using a pilot-scale incinerator. Destruction and emission behaviors of OPFRs were investigated along with the effects on behaviors of unintentional persistent organic pollutants (POPs) such as polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (dl-PCBs), hexachlorobenzene (HCB), pentachlorobenzene (PeCB), and pentachlorophenol (PCP). Incineration conditions were chosen according to current regulations for waste incinerators in Japan and UNEP. The OPFRs in the input materials were mainly destroyed in the primary combustion with destruction efficiencies greater than 99.999%. Concentrations of the OPFRs in the exhaust gases and ash were, respectively, < 0.01–0.048 μg m{sup −3} and < 0.5–68 μg kg{sup −1}. Almost all of the total phosphorus in the input materials was partitioned into the ash, but less into final exit gases, indicating negligible emissions of volatile phosphorus compounds during incineration. Inputs of chlorinated OPFRs did not affect the formation markedly. Destruction and emission behaviors of unintentional POPs were investigated. Emissions of such POPs in exhaust gases and the ash were lower than the Japanese and international standards. Results show that even in wastes with high contents of chlorinated and non-halogenated OPFRs, waste incineration by the current regulations for the waste incinerators can control environmental emissions of

  16. Kinetic Spectrophotometric Method for the 1,4-Diionic Organophosphorus Formation in the Presence of Meldrum′s Acid: Stopped-Flow Approach

    Fatemeh Ghodsi

    2016-11-01

    Full Text Available The kinetics of the reaction between triphenylphosphine (TPP and dimethyl acetylenedicarboxylate (DMAD in the presence of Meldrum’s acid (MA for the generation of the 1,4-diionic organophosphorus compound has been investigated using the stopped-flow and UV-VIS spectrophotometry techniques. The first step of the reaction between TPP and DMAD for the generation of (I1 in ethanol was followed by the stopped-flow apparatus. This step was recognized as a fast step. The reaction between the intermediate (I1 and MA showed first-order kinetics, and it was followed by the UV-VIS spectrophotometry technique. The activation parameters for the slow step of the proposed mechanism were determined using two linearized forms of the Eyring equation. From the temperature, concentration and solvent studies, the activation energy (Ea = 20.16 kJ·mol−1 and the related activation parameters (ΔG‡ = 71.17 ± 0.015 kJ·mol−1, ΔS‡ = −185.49 ± 0.026 J·mol−1 and ΔH‡ =17.72 ± 0.007 kJ·mol−1 were calculated. The experimental data indicated that the reaction was zero-order in MA and second-order overall. The proposed mechanism was confirmed with the observed kinetic data obtained from the UV-VIS and stopped-flow techniques.

  17. A novel amperometric biosensor based on covalently attached multilayer assemblies of gold nanoparticles, diazo-resins and acetylcholinesterase for the detection of organophosphorus pesticides.

    Jiang, Bin; Dong, Pei; Zheng, Jianbin

    2018-06-01

    Using an ionic layer-by-layer self-assembly technique, colloidal gold nanoparticles (AuNPs) and diazo-resins (DAR) were immobilised on the surface of a p-aminobenzenesulfonic acid-modified glassy carbon electrode to form a matrix composite membrane for acetylcholinesterase (AChE) immobilisation. Photo-sensitive DAR was used as the assembly interlayer to convert the ionic bond into a covalent bond to improve the biosensor stability. These fabrication processes were followed by electrochemical impedance spectroscopy and cyclic voltammetry to verify the membrane formation. Because of the introduction of AuNPs/DAR/AChE biofilms, the modified electrode exhibited excellent electron transfer mediation and electrical conductivity. In addition, it exhibited high sensitivity in the range of linear concentration from 1.0 × 10 -8 to 1.0 × 10 -12 g L -1 with the detection limit of 5.12 × 10 -13 and 5.85 × 10 -13 g L -1 for malathion and methyl parathion, respectively. More importantly, the presented biosensor considerably improved stability because the electrostatic interaction was converted into covalent bonds by UV irradiation. It is a simple, cheap and stable method for quantitative detection of organophosphorus pesticides, and this method may pave a way for the sensitive, simple detection of different analytes without the need of expensive instrumentation. Copyright © 2018 Elsevier B.V. All rights reserved.

  18. Isolation and characterization of bacteria capable of degrading polycyclic aromatic hydrocarbons (PAHs) and organophosphorus pesticides from PAH-contaminated soil in Hilo, Hawaii.

    Seo, Jong-Su; Keum, Young-Soo; Harada, Renee M; Li, Qing X

    2007-07-11

    Nineteen bacterial strains were isolated from petroleum-contaminated soil in Hilo, HI, and characterized by two different spray-plated methods, turbidity test in liquid medium, and 16S rRNA gene sequence analysis. Analysis of the soil showed 13 polycyclic aromatic hydrocarbons (PAHs) in a range from 0.6 to 30 mg/kg of dry weight each and 12 PAH metabolites. Five distinct bacterial strains (C3, C4, P1-1, JS14, and JS19b1) selected from preliminary plating and turbidity tests were further tested for PAH degradation through single PAH degradation assay. Strains C3, C4, and P1-1 degraded phenanthrene (40 mg/L) completely during 7 days of incubation. Strain JS14 degraded fluoranthene (40 mg/L) completely during 10 days of incubation. Strain JS19b1 degraded 100% of phenanthrene (40 mg/L) in 7 days, 77% of fluorene (40 mg/L) in 14 days, 97% of fluoranthene (40 mg/L) in 10 days, and 100% of pyrene (40 mg/L) in 14 days. Turbidity tests showed that strains P1-1, JS14, and JS19b1 utilized several organophosphorus pesticides as growth substrate. P1-1 can degrade carbofenothion, chlorfenvinphos, diazinon, fonofos, and pirimiphos-methyl. JS14 can transform chlorfenvinphos and diazinon. JS19b1 can break down diazinon, pirimiphos-methyl, and temephos.

  19. Fluorometric determination of paraoxon in human serum using a gold nanoparticle-immobilized organophosphorus hydrolase and coumarin 1 as a competitive inhibitor

    Kamelipour, Nahid; Mohsenifar, Afshin; Rahmani-Cherati, Tavoos; Tabatabaei, Meisam; Khoshnevisan, Kamyar; Allameh, Abdolamir; Milani, Majid M.; Etemadikia, Batool; Najavand, Saeid

    2014-01-01

    A dimeric organophosphorus hydrolase (OPH; EC 3.1.8.1; 72 kDa) was isolated from wild-type bacteria, analyzed for its 16s rRNA sequence, purified, and immobilized on gold nanoparticles (AuNPs) to form the transducer part of a biosensor. The isolated strain was identified as Pseudomonas aeruginosa. The AuNPs were characterized by transmission electron microscopy and localized surface plasmon resonance. Covalent binding of OPH to the AuNPs was confirmed by spectrophotometry, enzymatic activity assays, and FTIR spectroscopy. Coumarin 1, a competitive inhibitor of OPH, was used as a fluorogenic probe. The bioconjugates quench the emission of coumarin 1 upon binding, but the addition of paraoxon results in an enhancement of fluorescence that is directly proportional to the concentration of paraoxon. The gold-OPH conjugates were then used to determine paraoxon in serum samples spiked with varying levels of paraoxon. The method works in the 50 to 1,050 nM concentration range, has a low standard deviation (with a CV of 5.7–11 %), and a detection limit as low as 5 × 10 −11 M. (author)

  20. One-step electrochemical deposition of a graphene-ZrO2 nanocomposite: Preparation, characterization and application for detection of organophosphorus agents

    Du, Dan; Liu, Juan; Zhang, Xiao-Yan; Cui, Xiao-Li; Lin, Yuehe

    2011-04-27

    This paper described the preparation, characterization, and electrochemical properties of a graphene-ZrO2 nanocomposite (GZN) and its application for both the enrichment and detection of methyl parathion (MP). GZN was fabricated using electrochemical deposition and characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), which showed the successful formation of nanocomposites. Due to the strong affinity to the phosphoric group and the fast electron-transfer kinetics of GZN, both the extraction and electrochemical detection of organophosphorus (OP) agents at the same GZN modified electrochemical sensor was possible. The combination of solid-phase extraction and stripping voltammetric analysis allowed fast, sensitive, and selective determination of MP in garlic samples. The stripping response was highly linear over the MP concentrations ranging from 0.5 ng mL-1 to 100 ng mL-1, with a detection limit of 0.1 ng mL-1. This new nanocomposite-based electrochemical sensor provides an opportunity to develop a field-deployable, sensitive, and quantitative method for monitoring exposure to OPs.

  1. Sensitive Detection of Organophosphorus Pesticides in Medicinal Plants Using Ultrasound-Assisted Dispersive Liquid-Liquid Microextraction Combined with Sweeping Micellar Electrokinetic Chromatography.

    Wei, Jin-Chao; Hu, Ji; Cao, Ji-Liang; Wan, Jian-Bo; He, Cheng-Wei; Hu, Yuan-Jia; Hu, Hao; Li, Peng

    2016-02-03

    A simple, rapid, and sensitive method using ultrasound-assisted dispersive liquid-liquid microextraction (UA-DLLME) combined with sweeping micellar electrokinetic chromatography (sweeping-MEKC) has been developed for the determination of nine organophosphorus pesticides (chlorfenvinphos, parathion, quinalphos, fenitrothion, azinphos-ethyl, parathion-methyl, fensulfothion, methidathion, and paraoxon). The important parameters that affect the UA-DLLME and sweeping efficiency were investigated. Under the optimized conditions, the proposed method provided 779.0-6203.5-fold enrichment of the nine pesticides compared to the normal MEKC method. The limits of detection ranged from 0.002 to 0.008 mg kg(-1). The relative standard deviations of the peak area ranged from 1.2 to 6.5%, indicating the good repeatability of the method. Finally, the developed UA-DLLME-sweeping-MEKC method has been successfully applied to the analysis of the investigated pesticides in several medicinal plants, including Lycium chinense, Dioscorea opposite, Codonopsis pilosula, and Panax ginseng, indicating that this method is suitable for the determination of trace pesticide residues in real samples with complex matrices.

  2. An absorbing microwave micro-solid-phase extraction device used in non-polar solvent microwave-assisted extraction for the determination of organophosphorus pesticides.

    Wang, Ziming; Zhao, Xin; Xu, Xu; Wu, Lijie; Su, Rui; Zhao, Yajing; Jiang, Chengfei; Zhang, Hanqi; Ma, Qiang; Lu, Chunmei; Dong, Deming

    2013-01-14

    A single-step extraction-cleanup method, including microwave-assisted extraction (MAE) and micro-solid-phase extraction (μ-SPE), was developed for the extraction of ten organophosphorus pesticides in vegetable and fruit samples. Without adding any polar solvent, only one kind of non-polar solvent (hexane) was used as extraction solvent in the whole extraction step. Absorbing microwave μ-SPE device, was prepared by packing activated carbon with microporous polypropylene membrane envelope, and used as not only the sorbent in μ-SPE, but also the microwave absorption medium. Some experimental parameters effecting on extraction efficiency was investigated and optimized. 1.0 g of sample, 8 mL of hexane and three absorbing microwave μ-SPE devices were added in the microwave extraction vessel, the extraction was carried out under 400 W irradiation power at 60°C for 10 min. The extracts obtained by MAE-μ-SPE were directly analyzed by GC-MS without any clean-up process. The recoveries were in the range of 93.5-104.6%, and the relative standard deviations were lower than 8.7%. Copyright © 2012 Elsevier B.V. All rights reserved.

  3. Development of square wave voltammetry method for the assessment of organophosphorus compound impact on the cholinesterase of Pheretima with 2,6-dichloroindophenol as a redox indicator.

    Qiu, Jingxia; Chen, Jin; Ma, Qianqian; Miao, Yuqing

    2009-09-01

    A square wave voltammetry method was developed for the assessment of organophosphorus (OPs) compound impact on the cholinesterase of Pheretima with 2,6-dichloroindophenol (2,6-DCIP) as a redox indicator. The substrate of acetylthiocholine is hydrolysed by the cholinesterase (ChE) from soil animal pheretima, and the produced thiocholine reacts with the 2,6-DCIP to give obvious shift of electrochemical signal. The inhibition of ChE was assessed by measuring the enzyme activity before and after incubating with parathion-methyl. The reduction peak current of 2,6-DCIP decreases with the time of enzymatical reaction. The ChE loses almost 32.74% activity after 10 min incubation with 1ng mL(-1) paraoxon and 54.62% with 10 microg mL(-1) paraoxon, while the activity that corresponds to 100 microg mL(-1) paraoxon was nearly completely inhibited. This method can be employed to assess the inhibition of ChE and investigate OPs impact on environmental animals.

  4. A Mobile-Based High Sensitivity On-Field Organophosphorus Compounds Detecting System for IoT-Based Food Safety Tracking

    Han Jin

    2017-01-01

    Full Text Available A mobile-based high sensitivity absorptiometer is presented to detect organophosphorus (OP compounds for Internet-of-Things based food safety tracking. This instrument consists of a customized sensor front-end chip, LED-based light source, low power wireless link, and coin battery, along with a sample holder packaged in a recycled format. The sensor front-end integrates optical sensor, capacitive transimpedance amplifier, and a folded-reference pulse width modulator in a single chip fabricated in a 0.18 μm 1-poly 5-metal CMOS process and has input optical power dynamic range of 71 dB, sensitivity of 3.6 nW/cm2 (0.77 pA, and power consumption of 14.5 μW. Enabled by this high sensitivity sensor front-end chip, the proposed absorptiometer has a small size of 96 cm3, with features including on-field detection and wireless communication with a mobile. OP compound detection experiments of the handheld system demonstrate a limit of detection (LOD of 0.4 μmol/L, comparable to that of a commercial spectrophotometer. Meanwhile, an android-based application (APP is presented which makes the absorptiometer access to the Internet-of-Things (IoT.

  5. Ascorbic acid surface modified TiO₂-thin layers as a fully integrated analysis system for visual simultaneous detection of organophosphorus pesticides.

    Li, Shunxing; Liang, Wenjie; Zheng, Fengying; Lin, Xiaofeng; Cai, Jiabai

    2014-11-06

    TiO₂ photocatalysis and colorimetric detection are coupled with thin layer chromatography (TLC) for the first time to develop a fully integrated analysis system. Titania@polystyrene hybrid microspheres were surface modified with ascorbic acid, denoted AA-TiO₂@PS, and used as the stationary phase for TLC. Because the affinity between AA-TiO₂@PS and organophosphorus pesticides (OPs) was different for different species of OPs (including chlopyrifos, malathion, parathion, parathion-methyl, and methamidophos), OPs could be separated simultaneously by the mobile phase in 12.0 min with different Rf values. After surface modification, the UV-vis wavelength response range of AA-TiO₂@PS was expanded to 650 nm. Under visible-light irradiation, all of the OPs could be photodegraded to PO₄(3-) in 25.0 min. Based on the chromogenic reaction between PO₄(3-) and chromogenic agents (ammonium molybdate and ascorbic acid), OPs were quantified from color intensity images using a scanner in conjunction with image processing software. So, AA-TiO₂@PS was respectively used as the stationary phase of TLC for efficient separation of OPs, as a photocatalyst for species transformation of phosphorus, and as a colorimetric probe for on-field simultaneous visual detection of OPs in natural water. Linear calibration curves for each OP ranged from 19.3 nmol P L(-1) to 2.30 μmol P L(-1). This integrated analysis system was simple, inexpensive, easy to operate, and sensitive.

  6. In vitro skin permeation and decontamination of the organophosphorus pesticide paraoxon under various physical conditions--evidence for a wash-in effect.

    Misik, Jan; Pavlikova, Ruzena; Josse, Denis; Cabal, Jiri; Kuca, Kamil

    2012-09-01

    Misuse of various chemicals, such as chemical warfare agents, industrial chemicals or pesticides during warfare or terrorists attacks requires adequate protection. Thus, development and evaluation of novel decontamination dispositives and techniques are needed. In this study, in vitro permeation and decontamination of a potentially hazardous compound paraoxon, an active metabolite of organophosphorus pesticide parathion, was investigated. Skin permeation and decontamination experiments were carried out in modified Franz diffusion cells. Pig skin was used as a human skin model. Commercially produced detergent-based washing solutions FloraFree(™) and ArgosTM were used as decontamination means. The experiments were done under "warm", "cold", "dry" and "wet" skin conditions in order to determine an effect of various physical conditions on skin permeation of paraoxon and on a subsequent decontamination process. There was no significant difference in skin permeation of paraoxon under warm, cold and dry conditions, whereas wet conditions provided significantly higher permeation rates. In the selected conditions, decontamination treatments performed 1 h after a skin exposure did not decrease the agent volume that permeated through the skin. An exception were wet skin conditions with non-significant decontamination efficacy 18 and 28% for the FloraFree(™) and Argos(™) treatment, respectively. In contrast, the skin permeation of paraoxon under warm, cold and dry conditions increased up to 60-290% following decontamination compared to non-decontaminated controls. This has previously been described as a skin wash-in effect.

  7. Graphene Quantum Dots/Eggshell Membrane Composite as a Nano-sorbent for Preconcentration and Determination of Organophosphorus Pesticides by High-Performance Liquid Chromatography

    Vahideh Abdollahi

    2017-10-01

    Full Text Available In this study graphene quantum dots/eggshell membrane nanocomposite (GQDS/ESM is prepared and used as an efficient solid-phase extraction (SPE sorbent for preconcentration of organophosphorus pesticides (OPPs from aqueous solutions. The retained analytes on the sorbent are stripped by acetonitrile and subsequently are determined by high-performance liquid chromatography. Various parameters affecting the extraction efficiency of OPPs on the GQDS/ESM, such as solution pH, amount of nano-sorbent, sample loading flow rate, elution conditions and sample volume are investigated. The results demonstrated that the proposed method has a wide dynamic linear range (0.05–100 ng mL-1, good linearity (R2>0.997 and low detection limits (0.006-0.32 ng mL-1. High enrichment factors are achieved ranging from 110 to 140. In the optimum experimental conditions, the established method is successfully applied for the determination of OPPs in spiked water samples (well, tap, shaft and canal and apple juice. Satisfactory recovery results show that the sample matrices under consideration do not significantly affect the extraction process.

  8. Efficient Degradation of Malathion in the Presence of Detergents Using an Engineered Organophosphorus Hydrolase Highly Expressed by Pichia pastoris without Methanol Induction.

    Bai, Yun-Peng; Luo, Xiao-Jing; Zhao, Yu-Lian; Li, Chun-Xiu; Xu, Dian-Sheng; Xu, Jian-He

    2017-10-18

    The biodegradation of pesticides by organophosphorus hydrolases (OPHs) requires an efficient enzyme production technology in industry. Herein, a Pichia pastoris strain was constructed for the extracellular expression of PoOPH M9 , an engineered malathion-degrading enzyme. After optimization, the maximum titer and yield of fermentation reached 50.8 kU/L and 4.1 g protein /L after 3 days, with the highest space-time yield (STY) reported so far, 640 U L -1 h -1 . PoOPH M9 displayed its high activity and stability in the presence of 0.1% (w/w) plant-derived detergent. Only 0.04 mg/mL enzyme could completely remove 0.15 mM malathion in aqueous solution within 20 min. Furthermore, 12 μmol malathion on apples and cucumbers surfaces was completely removed by 0.05 mg/mL PoOPH M9 in tap water after 35 min washing. The efficient production of the highly active PoOPH M9 has cleared a major barrier to biodegradation of pesticide residues in food industry.

  9. Determinação de pesticidas organofosforados em água usando microextração em fase sólida e CGAR-EM Determination of organophosphorus pesticides in water using SPME-GC-MS

    Fernando Carvalho Silva

    1999-04-01

    Full Text Available Solid-phase microextraction (SPME has been applied to direct extraction of 11 organophosphorus pesticides in water using a 100 mm fiber polydimethylsiloxane. The method was evaluated with respect time of exposure, detection limits (LODs, linearity and precision. The detection limits (S/N = 3 depend of each pesticide and varie about ng/L levels. The linearity was satisfactory with coefficients of correlation usually greater than 0.993. The precision of the method was determined by extraction from 4.0 mg/L aqueous standard with coefficients of variation between 5.7 to 17.2%.

  10. Ascorbic acid surface modified TiO2-thin layers as a fully integrated analysis system for visual simultaneous detection of organophosphorus pesticides

    Li, Shunxing; Liang, Wenjie; Zheng, Fengying; Lin, Xiaofeng; Cai, Jiabai

    2014-11-01

    TiO2 photocatalysis and colorimetric detection are coupled with thin layer chromatography (TLC) for the first time to develop a fully integrated analysis system. Titania@polystyrene hybrid microspheres were surface modified with ascorbic acid, denoted AA-TiO2@PS, and used as the stationary phase for TLC. Because the affinity between AA-TiO2@PS and organophosphorus pesticides (OPs) was different for different species of OPs (including chlopyrifos, malathion, parathion, parathion-methyl, and methamidophos), OPs could be separated simultaneously by the mobile phase in 12.0 min with different Rf values. After surface modification, the UV-vis wavelength response range of AA-TiO2@PS was expanded to 650 nm. Under visible-light irradiation, all of the OPs could be photodegraded to PO43- in 25.0 min. Based on the chromogenic reaction between PO43- and chromogenic agents (ammonium molybdate and ascorbic acid), OPs were quantified from color intensity images using a scanner in conjunction with image processing software. So, AA-TiO2@PS was respectively used as the stationary phase of TLC for efficient separation of OPs, as a photocatalyst for species transformation of phosphorus, and as a colorimetric probe for on-field simultaneous visual detection of OPs in natural water. Linear calibration curves for each OP ranged from 19.3 nmol P L-1 to 2.30 μmol P L-1. This integrated analysis system was simple, inexpensive, easy to operate, and sensitive.TiO2 photocatalysis and colorimetric detection are coupled with thin layer chromatography (TLC) for the first time to develop a fully integrated analysis system. Titania@polystyrene hybrid microspheres were surface modified with ascorbic acid, denoted AA-TiO2@PS, and used as the stationary phase for TLC. Because the affinity between AA-TiO2@PS and organophosphorus pesticides (OPs) was different for different species of OPs (including chlopyrifos, malathion, parathion, parathion-methyl, and methamidophos), OPs could be separated

  11. Occurrence of Organophosphorus Flame Retardants and Plasticizers (PFRs) in Belgian Foodstuffs and Estimation of the Dietary Exposure of the Adult Population.

    Poma, Giulia; Sales, Carlos; Bruyland, Bram; Christia, Christina; Goscinny, Séverine; Van Loco, Joris; Covaci, Adrian

    2018-02-20

    The occurrence of 14 organophosphorus flame retardants and plasticizers (PFRs) was investigated in 165 composite food samples purchased from the Belgian market and divided into 14 food categories, including fish, crustaceans, mussels, meat, milk, cheese, dessert, food for infants, fats and oils, grains, eggs, potatoes and derived products, other food (stocks), and vegetables. Seven PFRs [namely, tri-n-butyl phosphate (TnBP), tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCIPP), tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), triphenyl phosphate (TPHP), 2-ethylhexyldiphenyl phosphate (EHDPHP), and tris(2-ethylhexyl) phosphate (TEHP)] were detected at concentrations above quantification limits. Fats and oils were the most contaminated category, with a total PFR concentration of 84.4 ng/g of wet weight (ww), followed by grains (36.9 ng/g of ww) and cheese (20.1 ng/g of ww). Our results support the hypothesis that PFR contamination may occur during industrial processing and manipulation of food products (e.g., packaging, canning, drying, etc.). Considering the daily average intake of food for the modal adult Belgian (15-64 years of age), the dietary exposure to sum PFRs was estimated to be ≤7500 ± 1550 ng/day [103 ± 21 ng/kg of body weight (bw)/day]. For individual PFRs, TPHP contributed on average 3400 ng/day (46.6 ng/kg of bw/day), TCIPP 1350 ng/day (18.5 ng/kg of bw/day), and EHDPHP 1090 ng/day (15 ng/kg of bw/day), values that were lower than their corresponding health-based reference doses. The mean dietary exposure mainly originated from grains (39%), followed by fats and oils (21%) and dairy products (20%). No significant differences between the intakes of adult men and women were observed.

  12. Monocrotophos, an organophosphorus insecticide, disrupts the expression of HpNetrin and its receptor neogenin during early development in the sea urchin (Hemicentrotus pulcherrimus).

    Zhang, Xiaona; Xu, Lei; Tian, Hua; Wang, Cuicui; Wang, Wei; Ru, Shaoguo

    2017-09-01

    Netrins, chemotropic guidance cues, can guide the extension of serotonergic axons by binding to netrin receptors during neural development. However, little is known about whether disruption of netrin signaling is involved in the mechanisms by which organophosphorus pesticides affect serotonergic nervous system (SNS) development. In this study, we evaluated the effects of the pesticide monocrotophos (MCP) on the expression patterns of HpNetrin and its receptor neogenin as well as on the intracellular calcium ion (Ca 2+ ) levels in Hemicentrotus pulcherrimus (sea urchin) by exposing fertilized embryos to 0, 0.01, 0.10, and 1.00mg/L MCP. The results showed that MCP disrupted HpNetrin and neogenin expression at different developmental stages in H. pulcherrimus and that Ca 2+ appeared to be involved in the MCP-induced developmental neurotoxicity. Specifically, the lower concentrations of MCP elevated HpNetrin and neogenin transcription, resulting in higher intracellular Ca 2+ levels during the early developmental stages in the sea urchin; this may affect netrin-directed cell migration/axon extension and subsequently disrupt serotonergic axon branching and synapse formation. In contrast, 1.00mg/L MCP exhibited an inhibitory effect on HpNetrin and neogenin transcription. This finding implies that the regulatory roles of these factors may be diminished during early development, thereby causing developmental defects in the sea urchin. Collectively, our results provide a basis for exploring the involvement of netrin and neogenin in the organophosphate-induced disruption of the SNS during development. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Rapid and sensitive suspension array for multiplex detection of organophosphorus pesticides and carbamate pesticides based on silica–hydrogel hybrid microbeads

    Wang, Xuan [Key Laboratory of Environmental Medicine Engineering, Ministry of Education, School of Public Health, Southeast University, Nanjing, Jiangsu (China); Mu, Zhongde; Shangguan, Fengqi [State Key Laboratory of Bioelectronics, School of Biological Science and Medical Engineering, Southeast University, Nanjing, Jiangsu (China); Liu, Ran; Pu, Yuepu [Key Laboratory of Environmental Medicine Engineering, Ministry of Education, School of Public Health, Southeast University, Nanjing, Jiangsu (China); Yin, Lihong, E-mail: lhyin@seu.edu.cn [Key Laboratory of Environmental Medicine Engineering, Ministry of Education, School of Public Health, Southeast University, Nanjing, Jiangsu (China)

    2014-05-01

    Highlights: • Silica–hydrogel hybrid microbeads were used to develop suspension array. • The results in detecting pesticides agree well with those from LC–MS/MS. • The method showed the good capability for multiplex analysis of pesticides residues. - Abstract: A technique for multiplex detection of organophosphorus pesticides and carbamate pesticides has been developed using a suspension array based on silica–hydrogel hybrid microbeads (SHHMs). The main advantage of SHHMs, which consist of both silica and hydrogel materials, is that they not only could be distinguished by their characteristic reflection peak originating from the stop-band of the photonic crystal but also have low non-specific adsorption of proteins. Using fluorescent immunoassay, the LODs for fenitrothion, chlorpyrifos-methyl, fenthion, carbaryl and metolcarb were measured to be 0.02 ng/mL, 0.012 ng/mL, 0.04 ng/mL, 0.05 ng/mL and 0.1 ng/mL, respectively, all of which are much lower than the maximum residue limits, as reported in the European Union pesticides database. All the determination coefficients for these five pesticides were greater than 0.99, demonstrating excellent correlations. The suspension array was specific and had no significant cross-reactivity with other chemicals. The results for the detection of pesticide residues collected from agricultural samples using this method agree well with those from liquid chromatography–tandem mass spectrometry. Our results showed that this simple method is suitable for simultaneous detection of these five pesticides residues in fruits and vegetables.

  14. Rapid and sensitive suspension array for multiplex detection of organophosphorus pesticides and carbamate pesticides based on silica–hydrogel hybrid microbeads

    Wang, Xuan; Mu, Zhongde; Shangguan, Fengqi; Liu, Ran; Pu, Yuepu; Yin, Lihong

    2014-01-01

    Highlights: • Silica–hydrogel hybrid microbeads were used to develop suspension array. • The results in detecting pesticides agree well with those from LC–MS/MS. • The method showed the good capability for multiplex analysis of pesticides residues. - Abstract: A technique for multiplex detection of organophosphorus pesticides and carbamate pesticides has been developed using a suspension array based on silica–hydrogel hybrid microbeads (SHHMs). The main advantage of SHHMs, which consist of both silica and hydrogel materials, is that they not only could be distinguished by their characteristic reflection peak originating from the stop-band of the photonic crystal but also have low non-specific adsorption of proteins. Using fluorescent immunoassay, the LODs for fenitrothion, chlorpyrifos-methyl, fenthion, carbaryl and metolcarb were measured to be 0.02 ng/mL, 0.012 ng/mL, 0.04 ng/mL, 0.05 ng/mL and 0.1 ng/mL, respectively, all of which are much lower than the maximum residue limits, as reported in the European Union pesticides database. All the determination coefficients for these five pesticides were greater than 0.99, demonstrating excellent correlations. The suspension array was specific and had no significant cross-reactivity with other chemicals. The results for the detection of pesticide residues collected from agricultural samples using this method agree well with those from liquid chromatography–tandem mass spectrometry. Our results showed that this simple method is suitable for simultaneous detection of these five pesticides residues in fruits and vegetables

  15. A simple solvothermal process for fabrication of a metal-organic framework with an iron oxide enclosure for the determination of organophosphorus pesticides in biological samples.

    Zhang, Suling; Jiao, Zhe; Yao, Weixuan

    2014-12-05

    An active magnetic metal-organic framework (MOF) hybrid material was prepared using a novel in situ solvothermal method in the presence of magnetite (Fe3O4) particles, that holds much promise for large-scale synthesis. MIL-101(Fe), an iron terephthalate with pore structure and high resistance to water and common solvents, was functionalized as a model with superparamagnetic qualities, using Fe3O4. The electrostatic interaction between Fe3O4 and metal ions was thereby used to chemically stabilize magnetic nanoparticles, and thus MOF crystals were uniformly enclosed by Fe3O4 to form a homogeneous magnetic product identified as a Fe3O4/MIL-101 composite. This hybrid material with magnetic susceptibility but with the lowest possible loading amount of Fe3O4 was examined, and its potential application for magnetic solid-phase extraction of six organophosphorus pesticides (OPPs) from human hair and urine samples, followed by gas chromatography analysis, was assessed. The main effect parameters including solution ionic strength, desorption solvent, extraction time and desorption time were investigated in sequence. Under optimized conditions, this method showed low detection limits (0.21-2.28 ng/mL), wide linearity, and good precision (1.8-8.7% for intra-day, 2.9-9.4% for inter-day). The matrix interference produced by hair or urine could be effectively eliminated using this method, and satisfactory recoveries of the spiked samples were 76.8-94.5% and 74.9-92.1%, respectively, indicating that the Fe3O4/MIL-101 sorbents are feasible for the analysis of trace analytes from biological samples. Copyright © 2014. Published by Elsevier B.V.

  16. An absorbing microwave micro-solid-phase extraction device used in non-polar solvent microwave-assisted extraction for the determination of organophosphorus pesticides

    Wang Ziming; Zhao Xin; Xu Xu; Wu Lijie; Su Rui; Zhao Yajing; Jiang Chengfei; Zhang Hanqi; Ma Qiang; Lu Chunmei; Dong Deming

    2013-01-01

    Highlights: ► An absorbing microwave μ-SPE device packed with activated carbon was used. ► Absorbing microwave μ-SPE device was made and used to enrich the analytes. ► Absorbing microwave μ-SPE device was made and used to heat samples directly. ► MAE-μ-SPE was applied to the extraction of OPPs with non-polar solvent only. - Abstract: A single-step extraction-cleanup method, including microwave-assisted extraction (MAE) and micro-solid-phase extraction (μ-SPE), was developed for the extraction of ten organophosphorus pesticides in vegetable and fruit samples. Without adding any polar solvent, only one kind of non-polar solvent (hexane) was used as extraction solvent in the whole extraction step. Absorbing microwave μ-SPE device, was prepared by packing activated carbon with microporous polypropylene membrane envelope, and used as not only the sorbent in μ-SPE, but also the microwave absorption medium. Some experimental parameters effecting on extraction efficiency was investigated and optimized. 1.0 g of sample, 8 mL of hexane and three absorbing microwave μ-SPE devices were added in the microwave extraction vessel, the extraction was carried out under 400 W irradiation power at 60 °C for 10 min. The extracts obtained by MAE-μ-SPE were directly analyzed by GC–MS without any clean-up process. The recoveries were in the range of 93.5–104.6%, and the relative standard deviations were lower than 8.7%.

  17. Preparation, characterization of Fe3O4 at TiO2 magnetic nanoparticles and their application for immunoassay of biomarker of exposure to organophosphorus pesticides

    Zhang, Xiao; Wang, Hongbo; Yang, Chunming; Du, Dan; Lin, Yuehe

    2013-03-15

    Novel Fe3O4 at TiO2 magnetic nanoparticles were prepared and developed for a new nanoparticle-based immunosensor for electrochemical quantification of organophosphorylated butyrylcholinesterase (BChE) in plasma, a specific biomarker of exposure to organophosphorus (OP) agents. The Fe3O4 at TiO2 nanoparticles were synthesized by hydrolysis of tetrabutyltitanate on the surface of Fe3O4 magnetic nanospheres, and characterized by attenuated total reflection Fourier-transform infrared spectra, transmission electron microscope and X-ray diffraction. The functional Fe3O4 at TiO2 nanoparticles were performed as capture antibody to selectively enrich phosphorylated moiety instead of phosphoserine antibody in the traditional sandwich immunoassays. The secondary recognition was served by quantum dots (QDs)-tagged anti-BChE antibody (QDs-anti-BChE). With the help of a magnet, the resulting sandwich-like complex, Fe3O4 at TiO2/OP-BChE/QDs-anti-BChE, was easily isolated from sample solutions and the released cadmium ions were detected on a disposable screen-printed electrode (SPE). The binding affinities were investigated by both surface plasmon resonance (SPR) and square wave voltammetry (SWV). This method not only avoids the drawback of unavailability of commercial OP-specific antibody but also amplifies detection signal by QDs-tags together with easy separation of samples by magnetic forces. The proposed immunosensor yields a linear response over a broad OP-BChE concentrations range from 0.02 to 10 nM, with detection limit of 0.01 nM. Moreover, the disposable nanoparticle-based immunosensor has been validated with human plasma samples. It offers a new method for rapid, sensitive, selective and inexpensive screening/evaluating exposure to OP pesticides.

  18. Synthesis and Characterization of TiO2 Modified with Polystyrene and Poly(3-chloro-2-hydroxypropyl Methacrylate as Adsorbents for the Solid Phase Extraction of Organophosphorus Pesticides

    Enrique Alejo-Molina

    2016-01-01

    Full Text Available Novel hybrid TiO2 particles were developed and assessed as an adsorbent for solid phase extraction (SPE of organophosphorus pesticides (fensulfothion, parathion methyl, coumaphos, and diazinon from spiked water. The sol-gel method was used to synthesize TiO2 particles, which were coated with free-radical polystyrene (PS and poly(3-chloro-2-hydroxypropyl methacrylate (PClHPMA polymers. Particle structures were determined via Fourier transform infrared spectroscopy to confirm that the polymers were successfully anchored to the TiO2 particles. Thermogravimetric analysis was conducted to determine organic and inorganic matter in TiO2-PS and TiO2-PClHPMA particles showing results of 20 : 80 wt/wt% and 23 : 77 wt/wt%, respectively. SEM-EDS and X-ray diffraction test were conducted to determine the morphology and semielemental composition of the particles showing amorphous characteristics. By observing the contact angle, particles coated with PClHPMA were determined to be more hydrophilic than TiO2-PS particles. The pore size distributions obtained from the N2 adsorption-desorption isotherms were 0.150 and 0.168 cm3g−1. The specific surface area (BET was 239.9 m2g−1 for TiO2-PS and 225.7 m2g−1 for TiO2-PClHPMA. The synthesized particles showed relatively high yields of adsorption in SPE. The pesticide recoveries obtained by high performance liquid chromatography ranged from 6 to 26% for TiO2-PClHPMA and 44 to 92% for TiO2-PS.

  19. Pilot-scale incineration of wastes with high content of chlorinated and non-halogenated organophosphorus flame retardants used as alternatives for PBDEs.

    Matsukami, Hidenori; Kose, Tomohiro; Watanabe, Mafumi; Takigami, Hidetaka

    2014-09-15

    Chlorinated and non-halogenated organophosphorus flame retardants (OPFRs) including tris(2-chloroisopropyl) phosphate (TCIPP), diethylene glycol bis(di(2-chloroisopropyl) phosphate) (DEG-BDCIPP), triphenyl phosphate (TPHP), and bisphenol A bis(diphenyl phosphate) (BPA-BDPP) have been used increasingly as alternatives to polybrominated diphenyl ethers and other brominated flame retardants. For this study, five batches of incineration experiments of wastes containing approximately 1% of TCIPP, DEG-BDCIPP, TPHP, and BPA-BDPP were conducted using a pilot-scale incinerator. Destruction and emission behaviors of OPFRs were investigated along with the effects on behaviors of unintentional persistent organic pollutants (POPs) such as polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (dl-PCBs), hexachlorobenzene (HCB), pentachlorobenzene (PeCB), and pentachlorophenol (PCP). Incineration conditions were chosen according to current regulations for waste incinerators in Japan and UNEP. The OPFRs in the input materials were mainly destroyed in the primary combustion with destruction efficiencies greater than 99.999%. Concentrations of the OPFRs in the exhaust gases and ash were, respectively, incineration. Inputs of chlorinated OPFRs did not affect the formation markedly. Destruction and emission behaviors of unintentional POPs were investigated. Emissions of such POPs in exhaust gases and the ash were lower than the Japanese and international standards. Results show that even in wastes with high contents of chlorinated and non-halogenated OPFRs, waste incineration by the current regulations for the waste incinerators can control environmental emissions of OPFRs and unintentional POPs. Incineration is regarded as a best available technology (BAT) for waste management systems. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. Determination of organophosphorus flame retardants in fish by pressurized liquid extraction using aqueous solutions and solid-phase microextraction coupled with gas chromatography-flame photometric detector.

    Gao, Zhanqi; Deng, Yuehua; Yuan, Wenting; He, Huan; Yang, Shaogui; Sun, Cheng

    2014-10-31

    A novel method was developed for the determination of organophosphorus flame retardants (PFRs) in fish. The method consists of a combination of pressurized liquid extraction (PLE) using aqueous solutions and solid-phase microextraction (SPME), followed by gas chromatography-flame photometric detector (GC-FPD). The experimental parameters that influenced extraction efficiency were systematically evaluated. The optimal responses were observed by extracting 1g of fish meat with the solution of water:acetonitrile (90:10, v/v) at 150°C for 5min and acid-washed silica gel used as lipid sorbent. The obtained extract was then analyzed by SPME coupled with GC-FPD without any additional clean-up steps. Under the optimal conditions, the proposed procedure showed a wide linear range (0.90-5000ngg(-1)) obtained by analyzing the spiked fish samples with increasing concentrations of PFRs and correlation coefficient (R) ranged from 0.9900 to 0.9992. The detection limits (S/N=3) were in the range of 0.010-0.208ngg(-1) with standard deviations (RSDs) ranging from 2.0% to 9.0%. The intra-day and inter-day variations were less than 9.0% and 7.8%, respectively. The proposed method was successfully applied to the determination of PFRs in real fish samples with recoveries varying from 79.8% to 107.3%. The results demonstrate that the proposed method is highly effective for analyzing PFRs in fish samples. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. Rapid gas chromatography with flame photometric detection of multiple organophosphorus pesticides in Salvia miltiorrhizae after ultrasonication assisted one-step extraction.

    Zhang, Shanshan; Liu, Xiaofei; Qin, Jia'an; Yang, Meihua; Zhao, Hongzheng; Wang, Yong; Guo, Weiying; Ma, Zhijie; Kong, Weijun

    2017-11-15

    A simple and rapid gas chromatography-flame photometric detection (GC-FPD) method was developed for the determination of 12 organophosphorus pesticides (OPPs) in Salvia miltiorrhizae by using ultrasonication assisted one-step extraction (USAE) without any clean-up steps. Some crucial parameters such as type of extraction solvent were optimized to improve the method performance for trace analysis. Any clean-up steps were negligent as no interferences were detected in the GC-FPD chromatograms for sensitive detection. Under the optimized conditions, limits of detection (LODs) and quantitation (LOQs) for all pesticides were in the range of 0.001-0.002mg/kg and 0.002-0.01mg/kg and 0.002-0.01mg/kg, respectively, which were all below the regulatory maximum residue limits suggested. RSDs for method precision (intra- and inter-day variations) were lower than 6.8% in approval with international regulations. Average recovery rates for all pesticides at three fortification levels (0.5, 1.0 and 5.0mg/kg) were in the range of 71.2-101.0% with relative standard deviations (RSDs) pesticide (dimethoate) out of the 12 targets was simultaneously detected in four samples at concentrations of 0.016-0.02mg/kg. Dichlorvos and omethoate were found in the same sample from Sichuan province at 0.004 and 0.027mg/kg, respectively. Malathion and monocrotophos were determined in the other two samples at 0.014 and 0.028mg/kg, respectively. All the positive samples were confirmed by LC-MS/MS. The simple, reliable and rapid USAE-GC-FPD method with many advantages over traditional techniques would be preferred for trace analysis of multiple pesticides in more complex matrices. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Organophosphorus and Carbamate Pesticide Residues Detected in Water Samples Collected from Paddy and Vegetable Fields of the Savar and Dhamrai Upazilas in Bangladesh

    Nurul Karim

    2012-09-01

    Full Text Available Several types of organophosphorous and carbamate pesticides have been used extensively by the farmers in Bangladesh during the last few decades. Twenty seven water samples collected from both paddy and vegetable fields in the Savar and Dhamrai Upazilas in Bangladesh were analyzed to determine the occurrence and distribution of organo-phosphorus (chlorpyrifos, malathion and diazinon and carbamate (carbaryl and carbofuran pesticide residues. A high performance liquid chromatograph instrument equipped with a photodiode array detector was used to determine the concentrations of these pesticide residues. Diazinon and carbofuran were detected in water samples collected from Savar Upazila at 0.9 μg/L and 198.7 μg/L, respectively. Malathion was also detected in a single water sample at 105.2 μg/L from Dhamrai Upazila. Carbaryl was the most common pesticide detected in Dhamrai Upazila at 14.1 and 18.1 μg/L, while another water sample from Dhamrai Upazila was contaminated with carbofuran at 105.2 μg/L. Chlorpyrifos was not detected in any sample. Overall, the pesticide residues detected were well above the maximum acceptable levels of total and individual pesticide contamination, at 0.5 and 0.1 μg/L, respectively, in water samples recommended by the European Economic Community (Directive 98/83/EC. The presence of these pesticide residues may be attributed by their intense use by the farmers living in these areas. Proper handling of these pesticides should be ensured to avoid direct or indirect exposure to these pesticides.

  3. Is the World Health Organization-recommended dose of pralidoxime effective in the treatment of organophosphorus poisoning? A randomized, double-blinded and placebo-controlled trial

    Sumaya Syed

    2015-01-01

    Full Text Available Background: Organophosphorus poisoning (OPP is a major global public health problem. Pralidoxime has been used in a complimentary role to atropine for the management of OPP. World Health Organization (WHO recommends use of pralidoxime but studies regarding its role have been inconclusive, ranging from being ineffective to harmful or beneficial. Materials and Methods: The present study was undertaken to evaluate the effectiveness of pralidoxime. Eddleston′s study was the most compelling factor for our study, as he showed worst outcomes using pralidoxime. Our practice of continuous use of pralidoxime was based on the WHO guidelines and the study by Pawar (2006, which showed better outcome with higher doses of pralidoxime. These conflicting results suggested that a re-evaluation of its use in our clinical practice was indicated. Results: There was no difference in mortality rates, hemodynamic parameters and atropine requirements between the AP and A groups. Mean duration of ventilation (3.6 ± 4.6 in AP group vs. 3.6 ± 4.4 in A group and Intensive Care Unit stay (7.1 ± 5.4 in AP group vs. 6.8 ± 4.7 in A group was comparable. Serum sodium concentrations showed a correlation with mortality, with lower concentrations associated with better outcomes. Conclusion: The study suggests that add-on WHO-recommended pralidoxime therapy does not provide any benefit over atropine monotherapy. Adding pralidoxime does not seem to be beneficial and at the same time does not result in increased mortality rates. Our practice changed after completion of this study, and it has proven to be of significant benefit to patients who had to bear the expense of treatment.

  4. An absorbing microwave micro-solid-phase extraction device used in non-polar solvent microwave-assisted extraction for the determination of organophosphorus pesticides

    Wang Ziming, E-mail: wangziming@jlu.edu.cn [College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012 (China); College of Environment and Resources, Jilin University, 2699 Qianjin Street, Changchun 130012 (China); Zhao Xin; Xu Xu; Wu Lijie; Su Rui; Zhao Yajing; Jiang Chengfei; Zhang Hanqi [College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012 (China); Ma Qiang [Chinese Academy of Inspection and Quarantine, Beijing 100123 (China); Lu Chunmei [College of Technology Center, Jilin Entry-Exit Inspection and Quarantine Bureau, Changchun 130062 (China); Dong Deming [College of Environment and Resources, Jilin University, 2699 Qianjin Street, Changchun 130012 (China)

    2013-01-14

    Highlights: Black-Right-Pointing-Pointer An absorbing microwave {mu}-SPE device packed with activated carbon was used. Black-Right-Pointing-Pointer Absorbing microwave {mu}-SPE device was made and used to enrich the analytes. Black-Right-Pointing-Pointer Absorbing microwave {mu}-SPE device was made and used to heat samples directly. Black-Right-Pointing-Pointer MAE-{mu}-SPE was applied to the extraction of OPPs with non-polar solvent only. - Abstract: A single-step extraction-cleanup method, including microwave-assisted extraction (MAE) and micro-solid-phase extraction ({mu}-SPE), was developed for the extraction of ten organophosphorus pesticides in vegetable and fruit samples. Without adding any polar solvent, only one kind of non-polar solvent (hexane) was used as extraction solvent in the whole extraction step. Absorbing microwave {mu}-SPE device, was prepared by packing activated carbon with microporous polypropylene membrane envelope, and used as not only the sorbent in {mu}-SPE, but also the microwave absorption medium. Some experimental parameters effecting on extraction efficiency was investigated and optimized. 1.0 g of sample, 8 mL of hexane and three absorbing microwave {mu}-SPE devices were added in the microwave extraction vessel, the extraction was carried out under 400 W irradiation power at 60 Degree-Sign C for 10 min. The extracts obtained by MAE-{mu}-SPE were directly analyzed by GC-MS without any clean-up process. The recoveries were in the range of 93.5-104.6%, and the relative standard deviations were lower than 8.7%.

  5. Comparative Pharmacokinetics of the Organophosphorus Insecticide Chlorpyrifos and its Major Metabolites Diethylphosphate, Diethylthiophosphate and 3,5,6-Trichloro-2-pyridinol in the Rat

    Timchalk, Chuck; Busby, Andrea L; Campbell, James A; Needham, Larry L; Barr, Dana

    2007-07-31

    Abstract Chlorpyrifos (CPF) is a commonly used diethylphosphorothionate organophosphorus (OP) insecticide. Diethylphosphate (DEP), diethylthiophosphate (DETP) and 3,5,6-trichloro-2-pyridinol (TCPy) are products of metabolism and of environmental degradation of CPF and are routinely measured in urine as biomarkers of exposure. However, because these same chemicals can result from metabolism or by biodegradation, monitoring total urinary metabolite levels may be reflective of not only an individual’s contact with the parent pesticide, but also exposure with the metabolites, which are present in the environment. The objective of the current study was to compare the pharmacokinetics of orally administered DEP, DETP and TCPy with their kinetics following oral dosing with the parent insecticide CPF in the rat. Groups of rats were orally administered CPF, DEP, TCPy or DETP at doses of 140 μmol/kg body weight, and the time-courses of the metabolites were evaluated in blood and urine. Following oral administration, all three metabolites were well absorbed with peak blood concentrations being attained between 1-3 h post-dosing. In the case of DEP and TCPy virtually all the administered dose was recovered in the urine by 72 h post-dosing, suggesting negligible, if any, metabolism; whereas with DETP, ~50% of the orally administered dose was recovered in the urine. The CPF oral dose was likewise rapidly absorbed and metabolized to DEP, TCPy and DETP, with the distribution of metabolites in the urine followed the order: TCPy (22 ± 3 μmol) > DETP (14 ± 2 μmol) > DEP (1.4 ± 0.7 μmol). Based upon the total amount of TCPy detected in the urine a minimum of 63% of the oral CPF dose was absorbed. These studies support the hypotheses that DEP, DETP and TCPy present in the environment can be readily absorbed and eliminated in the urine of rats and potentially humans.

  6. Inhibition of the prostaglandin EP2 receptor is neuroprotective and accelerates functional recovery in a rat model of organophosphorus induced status epilepticus

    Rojas, Asheebo; Ganesh, Thota; Lelutiu, Nadia; Gueorguieva, Paoula; Dingledine, Raymond

    2015-01-01

    Exposure to high levels of organophosphorus compounds (OP) can induce status epilepticus (SE) in humans and rodents via acute cholinergic toxicity, leading to neurodegeneration and brain inflammation. Currently there is no treatment to combat the neuropathologies associated with OP exposure. We recently demonstrated that inhibition of the EP2 receptor for PGE2 reduces neuronal injury in mice following pilocarpine-induced SE. Here, we investigated the therapeutic effects of an EP2 inhibitor (TG6-10-1) in a rat model of SE using diisopropyl fluorophosphate (DFP). We tested the hypothesis that EP2 receptor inhibition initiated well after the onset of DFP-induced SE reduces the associated neuropathologies. Adult male Sprague-Dawley rats were injected with pyridostigmine bromide (0.1 mg/kg, sc) and atropine methylbromide (20 mg/kg, sc) followed by DFP (9.5 mg/kg, ip) to induce SE. DFP administration resulted in prolonged upregulation of COX-2. The rats were administered TG6-10-1 or vehicle (ip) at various time points relative to DFP exposure. Treatment with TG6-10-1 or vehicle did not alter the observed behavioral seizures, however six doses of TG6-10-1 starting 80-150 min after the onset of DFP-induced SE significantly reduced neurodegeneration in the hippocampus, blunted the inflammatory cytokine burst, reduced microglial activation and decreased weight loss in the days after status epilepticus. By contrast, astrogliosis was unaffected by EP2 inhibition 4 d after DFP. Transient treatments with the EP2 antagonist 1 h before DFP, or beginning 4 h after DFP, were ineffective. Delayed mortality, which was low (10%) after DFP, was unaffected by TG6-10-1. Thus, selective inhibition of the EP2 receptor within a time window that coincides with the induction of cyclooxygenase-2 by DFP is neuroprotective and accelerates functional recovery of rats. PMID:25656476

  7. Analysis of monomeric and oligomeric organophosphorus flame retardants in fish muscle tissues using liquid chromatography–electrospray ionization tandem mass spectrometry: Application to Nile tilapia (Oreochromis niloticus from an e-waste processing area in northern Vietnam

    Hidenori Matsukami

    2016-06-01

    Full Text Available Using electrospray ionization tandem mass spectrometry combined with liquid chromatography (LC, a novel analytical method was developed to quantify eight monomeric organophosphorus flame retardants (m-PFRs and three oligomeric organophosphorus flame retardants (o-PFRs in fish muscle samples. The optimization and validation experiments indicate that the developed method can determine accurately the concentrations of analytes in fish muscle samples. The recoveries of analytes in fish muscle samples were in the range of 74–105%. The coefficients of variation of the concentrations of analytes in fish muscle samples were 0.6–8.9%. The concentrations of analytes in procedural blanks were below the limit of quantification (LOQ values. Furthermore, the developed method was applied to the analysis of m-PFRs and o-PFRs in the muscle samples of tilapias collected from an electronic waste (e-waste processing area in northern Vietnam. The concentrations of m-PFRs such as tris(2-chloroethyl phosphate (TCEP, tris(2-chloroisopropyl phosphate (TCIPP, and triphenyl phosphate (TPHP were dominant among the investigated m-PFRs. The respective concentrations of TCEP, TCIPP, and TPHP were up to 160, 300, and 230 ng g−1 lipid weight, respectively, whereas those of o-PFRs were up to 10 ng g−1 lipid weight. The results of this study indicate lower accumulation potential of o-PFRs compared with m-PFRs for the first time.

  8. Simultaneous quantification of the organophosphorus pesticides dimethoate and omethoate in porcine plasma and urine by LC-ESI-MS/MS and flow-injection-ESI-MS/MS.

    John, Harald; Eddleston, Michael; Clutton, R Eddie; Worek, Franz; Thiermann, Horst

    2010-05-15

    Dimethoate is an organophosphorus toxicant used in agri- and horticulture as a systemic broad-spectrum insecticide. It also exhibits toxic activity towards mammalian organism provoked by catalytic desulfuration in the liver producing its oxon-derivative omethoate thus inhibiting acetylcholinesterase, initiating cholinergic crisis and ultimately leading to death by respiratory paralysis and cardiovascular collapse. Pharmaco- and toxicokinetic studies in animal models help to broaden basic understanding of medical intervention by antidotes and supportive care. Therefore, we developed and validated a LC-ESI-MS/MS method suitable for the simultaneous, selective, precise (RSD(intra-day) 1-8%; RSD(inter-day) 5-14%), accurate (intra-day: 95-107%; inter-day: 90-115%), and robust quantification of both pesticides from porcine urine and plasma after deproteinization by precipitation and extensive dilution (1:11,250 for plasma and 1:40,000 for urine). Accordingly, lower limits of quantification (0.24-0.49 microg/ml plasma and 0.78-1.56 microg/ml urine) and lower limits of detection (0.12-0.24 microg/ml plasma and 0.39-0.78 microg/ml urine) were equivalent to quite low absolute on-column amounts (1.1-2.1 pg for plasma and 2.0-3.9 pg for urine). The calibration range (0.24-250 microg/ml plasma and 0.78-200 microg/ml urine) was subdivided into two linear ranges (r(2)>or=0.998) each covering nearly two orders of magnitude. The lack of any interfering peak in 6 individual blank specimens from plasma and urine demonstrated the high selectivity of the method. Furthermore, extensive sample dilution causing lowest concentration of potentially interfering matrix ingredients prompted us to develop and validate an additional flow-injection method (FI-ESI-MS/MS). Validation characteristics were as good as for the chromatographic method but sample throughput was enhanced by a factor of 6. Effects on ionization provoked by plasma and urine matrix from 6 individuals as well as in the

  9. Flame retardant emission from e-waste recycling operation in northern Vietnam: Environmental occurrence of emerging organophosphorus esters used as alternatives for PBDEs

    Matsukami, Hidenori; Tue, Nguyen Minh; Suzuki, Go; Someya, Masayuki; Tuyen, Le Huu; Viet, Pham Hung; Takahashi, Shin; Tanabe, Shinsuke; Takigami, Hidetaka

    2015-01-01

    Three oligomeric organophosphorus flame retardants (o-PFRs), eight monomeric PFRs (m-PFRs), tetrabromobisphenol A (TBBPA), and polybrominated diphenyl ethers (PBDEs) were identified and quantified in surface soils and river sediments around the e-waste recycling area in Bui Dau, northern Vietnam. Around the e-waste recycling workshops, 1,3-phenylene bis(diphenyl phosphate) (PBDPP), bisphenol A bis(diphenyl phosphate) (BPA-BDPP), triphenyl phosphate (TPHP), TBBPA, and PBDEs were dominant among the investigated flame retardants (FRs). The respective concentrations of PBDPP, BPA-BDPP, TPHP, TBBPA and the total PBDEs were 6.6–14000 ng/g-dry, < 2–1500 ng/g-dry, 11–3300 ng/g-dry, < 5–2900 ng/g-dry, and 67–9200 ng/g-dry in surface soils, and 4.4–78 ng/g-dry, < 2–20 ng/g-dry, 7.3–38 ng/g-dry, 6.0–44 ng/g-dry and 100–350 ng/g-dry in river sediments. Near the open burning site of e-waste, tris(methylphenyl) phosphate (TMPP), (2-ethylhexyl)diphenyl phosphate (EHDPP), TPHP, and the total PBDEs were abundantly with respective concentrations of < 2–190 ng/g-dry, < 2–69 ng/g-dry, < 3–51 ng/g-dry and 1.7–67 ng/g-dry in surface soils. Open storage and burning of e-waste have been determined to be important factors contributing to the emissions of FRs. The environmental occurrence of emerging FRs, especially o-PFRs, indicates that the alternation of FRs addition in electronic products is shifting in response to domestic and international regulations of PBDEs. The emissions of alternatives from open storage and burning of e-waste might become greater than those of PBDEs in the following years. The presence and environmental effects of alternatives should be regarded as a risk factor along with e-waste recycling. - Highlights: • Open storage and burning of e-waste contributed to emission of FRs. • Types of FRs currently in emission are shifting in response to regulations of PBDEs. • Emerging PFRs were detected in soils and sediments around e

  10. An amperometric biosensor based on acetylcholinesterase immobilized onto iron oxide nanoparticles/multi-walled carbon nanotubes modified gold electrode for measurement of organophosphorus insecticides

    Chauhan, Nidhi [Department of Biochemistry, M.D. University, Rohtak 124001, Haryana (India); Pundir, Chandra Shekhar, E-mail: pundircs@rediffmail.com [Department of Biochemistry, M.D. University, Rohtak 124001, Haryana (India)

    2011-09-02

    Graphical abstract: The stepwise amperometric biosensor fabrication process and immobilized acetylcholinesterase inhibition in pesticide solution. Highlights: {center_dot} Constructed a novel composite material using Fe{sub 3}O{sub 4}NP and c-MWCNT at Au electrode for electrocatalysis. {center_dot} The properties of nanoparticles modified electrodes were studied by SEM, FTIR, CVs and EIS. {center_dot} The biosensor exhibited good sensitivity (0.475 mA {mu}M{sup -1}) {center_dot} The half life of electrode was 2 months. {center_dot} The sensor was suitable for trace detection of OP pesticide residues in milk and water. - Abstract: An acetylcholinesterase (AChE) purified from maize seedlings was immobilized covalently onto iron oxide nanoparticles (Fe{sub 3}O{sub 4}NP) and carboxylated multi walled carbon nanotubes (c-MWCNT) modified Au electrode. An organophosphorus (OP) biosensor was fabricated using this AChE/Fe{sub 3}O{sub 4}/c-MWCNT/Au electrode as a working electrode, Ag/AgCl as standard and Pt wire as an auxiliary electrode connected through a potentiostat. The biosensor was based on inhibition of AChE by OP compounds/insecticides. The properties of nanoparticles modified electrodes were studied by scanning electron microscopy (SEM), Fourier transform infrared (FTIR), cyclic voltammograms (CVs) and electrochemical impedance spectroscopy (EIS). The synergistic action of Fe{sub 3}O{sub 4}NP and c-MWCNT showed excellent electrocatalytic activity at low potential (+0.4 V). The optimum working conditions for the sensor were pH 7.5, 35 deg. C, 600 {mu}M substrate concentration and 10 min for inhibition by pesticide. Under optimum conditions, the inhibition rates of OP pesticides were proportional to their concentrations in the range of 0.1-40 nM, 0.1-50 nM, 1-50 nM and 10-100 nM for malathion, chlorpyrifos, monocrotophos and endosulfan respectively. The detection limits were 0.1 nM for malathion and chlorpyrifos, 1 nM for monocrotophos and 10 nM for endosulfan. The

  11. Flame retardant emission from e-waste recycling operation in northern Vietnam: Environmental occurrence of emerging organophosphorus esters used as alternatives for PBDEs

    Matsukami, Hidenori, E-mail: matsukami.hidenori@nies.go.jp [Center for Material Cycles and Waste Management Research, National Institute for Environmental Studies (NIES), 16-2 Onogawa, Tsukuba 305-8506 (Japan); Graduate School of Frontier Sciences, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa 277-8563 (Japan); Tue, Nguyen Minh [Center for Marine Environmental Studies (CMES), Ehime University, 2-5 Bunkyo-cho, Matsuyama 790-8577 (Japan); Centre for Environmental Technology and Sustainable Development (CETASD), Hanoi University of Science, 334 Nguyen Trai, Hanoi (Viet Nam); Suzuki, Go [Center for Material Cycles and Waste Management Research, National Institute for Environmental Studies (NIES), 16-2 Onogawa, Tsukuba 305-8506 (Japan); Someya, Masayuki [Tokyo Metropolitan Research Institute for Environmental Protection, 1-7-5 Shinsuna Koto, Tokyo 136-0075 (Japan); Tuyen, Le Huu; Viet, Pham Hung [Centre for Environmental Technology and Sustainable Development (CETASD), Hanoi University of Science, 334 Nguyen Trai, Hanoi (Viet Nam); Takahashi, Shin [Center for Marine Environmental Studies (CMES), Ehime University, 2-5 Bunkyo-cho, Matsuyama 790-8577 (Japan); Center of Advanced Technology for the Environment, Faculty of Agriculture, Ehime University, 3-5-7 Tarumi, Matsuyama 790-8566 (Japan); Tanabe, Shinsuke [Center for Marine Environmental Studies (CMES), Ehime University, 2-5 Bunkyo-cho, Matsuyama 790-8577 (Japan); Takigami, Hidetaka [Center for Material Cycles and Waste Management Research, National Institute for Environmental Studies (NIES), 16-2 Onogawa, Tsukuba 305-8506 (Japan); Graduate School of Frontier Sciences, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa 277-8563 (Japan)

    2015-05-01

    Three oligomeric organophosphorus flame retardants (o-PFRs), eight monomeric PFRs (m-PFRs), tetrabromobisphenol A (TBBPA), and polybrominated diphenyl ethers (PBDEs) were identified and quantified in surface soils and river sediments around the e-waste recycling area in Bui Dau, northern Vietnam. Around the e-waste recycling workshops, 1,3-phenylene bis(diphenyl phosphate) (PBDPP), bisphenol A bis(diphenyl phosphate) (BPA-BDPP), triphenyl phosphate (TPHP), TBBPA, and PBDEs were dominant among the investigated flame retardants (FRs). The respective concentrations of PBDPP, BPA-BDPP, TPHP, TBBPA and the total PBDEs were 6.6–14000 ng/g-dry, < 2–1500 ng/g-dry, 11–3300 ng/g-dry, < 5–2900 ng/g-dry, and 67–9200 ng/g-dry in surface soils, and 4.4–78 ng/g-dry, < 2–20 ng/g-dry, 7.3–38 ng/g-dry, 6.0–44 ng/g-dry and 100–350 ng/g-dry in river sediments. Near the open burning site of e-waste, tris(methylphenyl) phosphate (TMPP), (2-ethylhexyl)diphenyl phosphate (EHDPP), TPHP, and the total PBDEs were abundantly with respective concentrations of < 2–190 ng/g-dry, < 2–69 ng/g-dry, < 3–51 ng/g-dry and 1.7–67 ng/g-dry in surface soils. Open storage and burning of e-waste have been determined to be important factors contributing to the emissions of FRs. The environmental occurrence of emerging FRs, especially o-PFRs, indicates that the alternation of FRs addition in electronic products is shifting in response to domestic and international regulations of PBDEs. The emissions of alternatives from open storage and burning of e-waste might become greater than those of PBDEs in the following years. The presence and environmental effects of alternatives should be regarded as a risk factor along with e-waste recycling. - Highlights: • Open storage and burning of e-waste contributed to emission of FRs. • Types of FRs currently in emission are shifting in response to regulations of PBDEs. • Emerging PFRs were detected in soils and sediments around e

  12. Kinetics of the inhibitory interaction of organophosphorus neuropathy inducers and non-inducers in soluble esterases in the avian nervous system

    Mangas, Iris; Vilanova, Eugenio; Estevez, Jorge, E-mail: jorge.estevez@umh.es

    2011-11-15

    Some published studies suggest that low level exposure to organophosphorus esters (OPs) may cause neurological and neurobehavioral effects at long term exposure. These effects cannot be explained by action on known targets. In this work, the interactions (inhibition, spontaneous reactivation and 'ongoing inhibition') of two model OPs (paraoxon, non neuropathy-inducer, and mipafox, neuropathy-inducer) with the chicken brain soluble esterases were evaluated. The best-fitting kinetic model with both inhibitors was compatible with three enzymatic components. The amplitudes (proportions) of the components detected with mipafox were similar to those obtained with paraoxon. These observations confirm the consistency of the results and the model applied and may be considered an external validation. The most sensitive component (E{alpha}) for paraoxon (11-23% of activity, I{sub 50} (30 min) = 9-11 nM) is also the most sensitive for mipafox (I{sub 50} (30 min) = 4 nM). This component is spontaneously reactivated after inhibition with paraoxon. The second sensitive component to paraoxon (E{beta}, 71-84% of activity; I{sub 50} (30 min) = 1216 nM) is practically resistant to mipafox. The third component (E{gamma}, 5-8% of activity) is paraoxon resistant and has I{sub 50} (30 min) of 3.4 {mu}M with mipafox, similar to NTE (neuropathy target esterase). The role of these esterases remains unknown. Their high sensitivity suggests that they may either play a role in toxicity in low-level long-term exposure of organophosphate compounds or have a protective effect related with the spontaneous reactivation. They will have to be considered in further metabolic and toxicological studies. -- Research Highlights: Black-Right-Pointing-Pointer Paraoxon and mipafox interactions have been evaluated with chicken soluble brain esterases. Black-Right-Pointing-Pointer The paraoxon inhibition was analyzed considering the simultaneous spontaneous reactivation. Black

  13. Kinetics of the inhibitory interaction of organophosphorus neuropathy inducers and non-inducers in soluble esterases in the avian nervous system

    Mangas, Iris; Vilanova, Eugenio; Estévez, Jorge

    2011-01-01

    Some published studies suggest that low level exposure to organophosphorus esters (OPs) may cause neurological and neurobehavioral effects at long term exposure. These effects cannot be explained by action on known targets. In this work, the interactions (inhibition, spontaneous reactivation and “ongoing inhibition”) of two model OPs (paraoxon, non neuropathy-inducer, and mipafox, neuropathy-inducer) with the chicken brain soluble esterases were evaluated. The best-fitting kinetic model with both inhibitors was compatible with three enzymatic components. The amplitudes (proportions) of the components detected with mipafox were similar to those obtained with paraoxon. These observations confirm the consistency of the results and the model applied and may be considered an external validation. The most sensitive component (Eα) for paraoxon (11–23% of activity, I 50 (30 min) = 9–11 nM) is also the most sensitive for mipafox (I 50 (30 min) = 4 nM). This component is spontaneously reactivated after inhibition with paraoxon. The second sensitive component to paraoxon (Eβ, 71–84% of activity; I 50 (30 min) = 1216 nM) is practically resistant to mipafox. The third component (Eγ, 5–8% of activity) is paraoxon resistant and has I 50 (30 min) of 3.4 μM with mipafox, similar to NTE (neuropathy target esterase). The role of these esterases remains unknown. Their high sensitivity suggests that they may either play a role in toxicity in low-level long-term exposure of organophosphate compounds or have a protective effect related with the spontaneous reactivation. They will have to be considered in further metabolic and toxicological studies. -- Research Highlights: ► Paraoxon and mipafox interactions have been evaluated with chicken soluble brain esterases. ► The paraoxon inhibition was analyzed considering the simultaneous spontaneous reactivation. ► The best-fitting kinetic models were compatible with a three enzymatic components. ► The amplitudes of the

  14. A comprehensive evaluation of the efficacy of leading oxime therapies in guinea pigs exposed to organophosphorus chemical warfare agents or pesticides

    Wilhelm, Christina M., E-mail: wilhelmc@battelle.org [Battelle, 505 King Avenue, JM-7, Columbus, OH 43201-2693 (United States); Snider, Thomas H., E-mail: snidert@battelle.org [Battelle, 505 King Avenue, JM-7, Columbus, OH 43201-2693 (United States); Babin, Michael C., E-mail: babinm@battelle.org [Battelle, 505 King Avenue, JM-7, Columbus, OH 43201-2693 (United States); Jett, David A., E-mail: jettd@ninds.nih.gov [National Institutes of Health/National Institute of Neurological Disorders and Stroke, Bethesda, MD 20892 (United States); Platoff, Gennady E., E-mail: platoffg@niaid.nih.gov [National Institutes of Health/National Institute of Allergy and Infectious Diseases, Bethesda, MD 20892 (United States); Yeung, David T., E-mail: dy70v@nih.gov [National Institutes of Health/National Institute of Neurological Disorders and Stroke, Bethesda, MD 20892 (United States)

    2014-12-15

    The currently fielded pre-hospital therapeutic regimen for the treatment of organophosphorus (OP) poisoning in the United States (U.S.) is the administration of atropine in combination with an oxime antidote (2-PAM Cl) to reactivate inhibited acetylcholinesterase (AChE). Depending on clinical symptoms, an anticonvulsant, e.g., diazepam, may also be administered. Unfortunately, 2-PAM Cl does not offer sufficient protection across the range of OP threat agents, and there is some question as to whether it is the most effective oxime compound available. The objective of the present study is to identify an oxime antidote, under standardized and comparable conditions, that offers protection at the FDA approved human equivalent dose (HED) of 2-PAM Cl against tabun (GA), sarin (GB), soman (GD), cyclosarin (GF), and VX, and the pesticides paraoxon, chlorpyrifos oxon, and phorate oxon. Male Hartley guinea pigs were subcutaneously challenged with a lethal level of OP and treated at approximately 1 min post challenge with atropine followed by equimolar oxime therapy (2-PAM Cl, HI-6 DMS, obidoxime Cl{sub 2}, TMB-4, MMB4-DMS, HLö-7 DMS, MINA, and RS194B) or therapeutic-index (TI) level therapy (HI-6 DMS, MMB4-DMS, MINA, and RS194B). Clinical signs of toxicity were observed for 24 h post challenge and blood cholinesterase [AChE and butyrylcholinesterase (BChE)] activity was analyzed utilizing a modified Ellman's method. When the oxime is standardized against the HED of 2-PAM Cl for guinea pigs, the evidence from clinical observations, lethality, quality of life (QOL) scores, and cholinesterase reactivation rates across all OPs indicated that MMB4 DMS and HLö-7 DMS were the two most consistently efficacious oximes. - Highlights: • First comprehensive evaluation of leading AChE oxime reactivators • All oximes are compared against current U.S. therapy 2-PAM Cl. • Relative therapeutic oxime efficacies against OP CWNA and pesticides • Contribution to more effective

  15. Influence of the nature of the components of extraction systems used for the extraction of radionuclides on the interfacial tension. II. Influence of the structure of neutral organophosphorus reagents

    Shmidt, V.S.; Nikitin, S.D.

    1984-01-01

    Isotherms of the interfacial tension were obtained on the interfaces between water or 3 M HNO 3 and solutions of various neutral organophosphorus compounds (NOPC). The values of the work of adsorption W and the standard free energy of adsorption Δμ/sup theta/ of these compounds on the interface from the organic phase were calculated. It was shown that linear dependence of W and Δμ/sup theta/ on the sum of the Kabachnik parameters sigmaΣ/sub Phi/ of the substituents at the phosphorus atom in the molecules of these extraction reagents are observed; this is an indication of the possibility of using the principle of linear free energy ratios (LFE) for predicting the interfacial activity of NOPC of various structures

  16. The Electrochemistry of Organophosphorus Compounds.

    1988-01-20

    of hydrogen on the electrode surface. Mechanistkc views are further developed with the addition of water resulting in the formation of...the exclusive vlide product. Furthermore, carbonvl compounds were added to the electrolyses to react with the electrochemically-generated ylides via...the Wittig reaction. The resulting olefins were found to catalytically isomerize from the Z isomer to the E isomer upon reduction. The role of water

  17. Mitochondrial dysfunction and organophosphorus compounds

    Karami-Mohajeri, Somayyeh [Department of Toxicology and Pharmacology, Faculty of Pharmacy, and Pharmaceutical Sciences Research Center, Tehran University of Medical Sciences, Tehran (Iran, Islamic Republic of); Department of Toxicology and Pharmacology, Faculty of Pharmacy, and Pharmaceutical Sciences Research Center, Kerman University of Medical Sciences, Kerman (Iran, Islamic Republic of); Abdollahi, Mohammad, E-mail: Mohammad.Abdollahi@UToronto.Ca [Department of Toxicology and Pharmacology, Faculty of Pharmacy, and Pharmaceutical Sciences Research Center, Tehran University of Medical Sciences, Tehran (Iran, Islamic Republic of)

    2013-07-01

    Organophosphorous (OPs) pesticides are the most widely used pesticides in the agriculture and home. However, many acute or chronic poisoning reports about OPs have been published in the recent years. Mitochondria as a site of cellular oxygen consumption and energy production can be a target for OPs poisoning as a non-cholinergic mechanism of toxicity of OPs. In the present review, we have reviewed and criticized all the evidences about the mitochondrial dysfunctions as a mechanism of toxicity of OPs. For this purpose, all biochemical, molecular, and morphological data were retrieved from various studies. Some toxicities of OPs are arisen from dysfunction of mitochondrial oxidative phosphorylation through alteration of complexes I, II, III, IV and V activities and disruption of mitochondrial membrane. Reductions of adenosine triphosphate (ATP) synthesis or induction of its hydrolysis can impair the cellular energy. The OPs disrupt cellular and mitochondrial antioxidant defense, reactive oxygen species generation, and calcium uptake and promote oxidative and genotoxic damage triggering cell death via cytochrome C released from mitochondria and consequent activation of caspases. The mitochondrial dysfunction induced by OPs can be restored by use of antioxidants such as vitamin E and C, alpha-tocopherol, electron donors, and through increasing the cytosolic ATP level. However, to elucidate many aspect of mitochondrial toxicity of Ops, further studies should be performed. - Highlights: • As a non-cholinergic mechanism of toxicity, mitochondria is a target for OPs. • OPs affect action of complexes I, II, III, IV and V in the mitochondria. • OPs reduce mitochondrial ATP. • OPs promote oxidative and genotoxic damage via release of cytochrome C from mitochondria. • OP-induced mitochondrial dysfunction can be restored by increasing the cytosolic ATP.

  18. Mitochondrial dysfunction and organophosphorus compounds

    Karami-Mohajeri, Somayyeh; Abdollahi, Mohammad

    2013-01-01

    Organophosphorous (OPs) pesticides are the most widely used pesticides in the agriculture and home. However, many acute or chronic poisoning reports about OPs have been published in the recent years. Mitochondria as a site of cellular oxygen consumption and energy production can be a target for OPs poisoning as a non-cholinergic mechanism of toxicity of OPs. In the present review, we have reviewed and criticized all the evidences about the mitochondrial dysfunctions as a mechanism of toxicity of OPs. For this purpose, all biochemical, molecular, and morphological data were retrieved from various studies. Some toxicities of OPs are arisen from dysfunction of mitochondrial oxidative phosphorylation through alteration of complexes I, II, III, IV and V activities and disruption of mitochondrial membrane. Reductions of adenosine triphosphate (ATP) synthesis or induction of its hydrolysis can impair the cellular energy. The OPs disrupt cellular and mitochondrial antioxidant defense, reactive oxygen species generation, and calcium uptake and promote oxidative and genotoxic damage triggering cell death via cytochrome C released from mitochondria and consequent activation of caspases. The mitochondrial dysfunction induced by OPs can be restored by use of antioxidants such as vitamin E and C, alpha-tocopherol, electron donors, and through increasing the cytosolic ATP level. However, to elucidate many aspect of mitochondrial toxicity of Ops, further studies should be performed. - Highlights: • As a non-cholinergic mechanism of toxicity, mitochondria is a target for OPs. • OPs affect action of complexes I, II, III, IV and V in the mitochondria. • OPs reduce mitochondrial ATP. • OPs promote oxidative and genotoxic damage via release of cytochrome C from mitochondria. • OP-induced mitochondrial dysfunction can be restored by increasing the cytosolic ATP

  19. Organohalogens in chlorinated cooling waters discharged from nuclear power stations

    Bean, R.M.; Mann, D.C.; Neitzel, D.A.

    1983-01-01

    For the power plant discharges studied to date, measured concentrations of trihalomethanes are lower than might be expected, particularly in cooling tower water, which can lose THMs to the atmosphere. In the cooling towers, where chlorine was added in higher concentrations and for longer residence times, halogenated phenols can contribute significantly to the total organic halogen content of the discharge. The way in which cooling towers are operated may also influence the production of halogenated phenols because they concentrate the incoming water by a factor of 4 or 5. In addition, the phenols, which act as a substrate for the halogenating agent, are also probably concentrated by the cooling tower operation and may be prevented from being biodegraded by addition of the same biocide that produces the halogenated phenols. 8 references, 4 tables

  20. Maternal transfer of organohalogenated compounds in sharks and stingrays.

    Weijs, Liesbeth; Briels, Nathalie; Adams, Douglas H; Lepoint, Gilles; Das, Krishna; Blust, Ronny; Covaci, Adrian

    2015-03-15

    Elasmobranchs can bioaccumulate considerable amounts of persistent organic pollutants (POPs) and utilize several reproductive strategies thereby influencing maternal transfer of contaminants. This study provides preliminary data on the POP transfer from pregnant females to offspring of three species (Atlantic stingrays, bonnethead, blacktip sharks) with different reproduction modes (aplacental, placental viviparity). Polychlorinated biphenyl (PCB) levels were generally higher than any other POPs. Stingrays and blacktip shark embryos contained the lowest POP concentrations while bonnetheads and the blacktip adult female had the highest concentrations. Results suggest that POPs are more readily transferred from the mother to the embryo compared to what is transferred to ova in stingrays. Statistically significant differences in levels of selected POPs were found between embryos from the left and right uterus within the same litter as well as between female and male embryos within the same litter for bonnetheads, but not for the blacktip sharks. Copyright © 2015 Elsevier Ltd. All rights reserved.

  1. Embryo yolk sac membrane kynurenine formamidase of l-tryptophan to NAD+ pathway as a primary target for organophosphorus insecticides (OPI) in OPI-induced NAD-associated avian teratogenesis.

    Seifert, Josef

    2017-10-01

    The objective of this study was to provide in ovo evidence for the proposed role of kynurenine formamidase of l-tryptophan to NAD + pathway in embryo yolk sac membranes as a primary target for organophosphorus insecticide (OPI) teratogens in OPI-induced NAD-associated avian teratogenesis. Slices prepared from yolk sac membranes or embryo livers of chicken eggs treated with the OPI dicrotophos and/or methyl parathion were incubated with l-tryptophan. Yolk sac membrane slices metabolized l-tryptophan in the pathway to NAD + before that function was established in livers. OPI interfered in ovo with the second step of l-tryptophan to NAD + biosynthesis by inhibiting kynurenine formamidase. Its inhibition due to the teratogen dicrotophos occurred in yolk sac membranes during the period of embryo highest susceptibility to OPI teratogens in contrast to delayed and lower inhibition caused by the nonteratogen methyl parathion. Both OPI affected liver kynurenine formamidase in a similar manner. The onsets of liver enzyme inhibition, however, were delayed by about two days and occurred at the time of the reduced embryo susceptibility to teratogens. The early disruption of l-tryptophan metabolism and higher inhibition of kynurenine formamidase in yolk sac membranes may be the factors that determine action of OPI as teratogens in chicken embryos. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Polyol-enhanced dispersive liquid-liquid microextraction coupled with gas chromatography and nitrogen phosphorous detection for the determination of organophosphorus pesticides from aqueous samples, fruit juices, and vegetables.

    Farajzadeh, Mir Ali; Afshar Mogaddam, Mohammad Reza; Alizadeh Nabil, Ali Akbar

    2015-12-01

    Polyol-enhanced dispersive liquid-liquid microextraction has been proposed for the extraction and preconcentration of some organophosphorus pesticides from different samples. In the present study, a high volume of an aqueous phase containing a polyol (sorbitol) is prepared and then a disperser solvent along with an extraction solvent is rapidly injected into it. Sorbitol showed the best results and it was more effective on the extraction recoveries of the analytes than inorganic salts such as sodium chloride, potassium chloride, and sodium sulfate. Under the optimum extraction conditions, the method showed low limits of detection and quantification within the ranges of 12-56 and 44-162 pg/mL, respectively. Enrichment factors and extraction recoveries were in the ranges of 2799-3033 and 84-92%, respectively. The method precision was evaluated at a concentration of 10 ng/mL of each analyte, and relative standard deviations were found to be less than 5.9% for intraday (n = 6) and less than 7.8% for interday (n = 4). Finally, some aqueous samples were successfully analyzed using the proposed method and four analytes (diazinon, dimethoate, chlorpyrifos, and phosalone) were determined, some of them at ng/mL level. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Development and validation of a multiresidue method for the simultaneous determination of organophosphorus insecticides and their toxic metabolites in sugarcane juice and refined sugar by gas chromatography with flame photometric detection.

    Ramasubramanian, Thirumalaiandi; Paramasivam, Mariappan

    2016-06-01

    A multiresidue method has been developed and validated for the simultaneous determination of organophosphorus insecticides and their toxic metabolites in sugarcane juice and refined sugar by gas chromatography with flame photometric detection. Limits of quantification of the method varied between 0.007 and 0.01 μg/g. Ethyl acetate based extraction followed by dispersive solid-phase extraction cleanup with primary secondary amine yielded internationally acceptable recoveries of acephate, chlorpyrifos, dichlorvos, monocrotophos, malathion, malaoxon, phorate, phorate-sulfoxide, phorate-oxon, phorate-sulfone, and quinalphos from selected matrices. The recoveries of target analytes from cane juice were 75.55 ± 0.5-102.57 ± 4.2, 77.45 ± 4.7-103.33 ± 3.3, and 80.55 ± 6.6-105.82 ± 9.8% at 0.01, 0.02, and 0.1 μg/g levels of fortification, respectively. The recoveries from cane sugar were 73.24 ± 3.5-104.47 ± 1.9, 75.23 ± 1.5-116.10 ± 3.7, and 70.75 ± 5.7-110.15 ± 2.7%, respectively at 0.01, 0.02, and 0.1 μg/g levels of fortification. Matrix effect and measurement uncertainty were within the permissible limit (less than 20%) as prescribed for pesticide residue analysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Evaluation of organophosphorus and synthetic pyrethroid insecticides against six vector mosquitoe species Avaliação de inseticidas organofosforados e piretroides sintéticos contra seis mosquitos vetores

    Domingo Montada Dorta

    1993-12-01

    Full Text Available Three organophosphorus compounds- malathion, folithion and temephos- and two synthetic pyrethroids- alphamethrin and deltamethrin- were used for monitoring the susceptibility status of larvae and adults of six vector mosquitoe species: Culex quinquefasciatus (Filariasis and Aedes albopictus (Dengue (both laboratory and field strains; laboratory strains of Aedes aegypti (Dengue, Anopheles slephensi and Anopheles culicifacies (Malaria, and Culex tritaeniorhynchus (Japanese encephalitis in India. From the LC50 values obtained for these insecticides, it was found that all mosquito species including the field strains of Cx. quinquefasciatus and Ae. albopictus were highly susceptible Except for Cx. quinquefasciatus (field strain against malathion, 100% mortality was observed at the discriminating dosages recommended by World Health Organization. The residual effect of alphamethrin, deltamethrin, malathion and folithion at 25 mg (ai/m² on different surfaces against six species of vector mosquitoes showed that alphamethrin was the most effective on all four treated surfaces (mud, plywood, cement and thatch. Nevertheless, residual efficacy lasted longer on thatch than on the other surfaces. Therefore, synthetic pyrethroids such as alphamethrin can be effectively employed in integrated vector control operations.Três compostos organo-fosforados - malation, folition e temefos -e dois piretroides sintéticos - alfametrina e deltametrina - foram usados para controlar o estado da susceptibilidade das larvas e adultos de seis mosquitos vetores na Índia. Foram utilizadas cepas de laboratório e área de Culex quinquefasciatus (filariasis e Aedes albopictus (Dengue e cepas de laboratório de Aedes aegypti (Dengue, Anopheles stephensi e Anopheles culicifacies (Malária e Culex tritaenorhynchus (encefalite japonesa. Os valores de C1(50 obtidos para esses inseticidas mostram que todas as espécies incluindo as cepas de área foram muito susceptíveis. Nos

  5. Validation of GC-IRMS techniques for δ13C and δ2H CSIA of organophosphorus compounds and their potential for studying the mode of hydrolysis in the environment.

    Wu, Langping; Kümmel, Steffen; Richnow, Hans H

    2017-04-01

    Compound-specific stable isotope analysis (CSIA) is among the most promising tools for studying the fate of organic pollutants in the environment. However, the feasibility of multidimensional CSIA was limited by the availability of a robust method for precise isotope analysis of heteroatom-bearing organic compounds. We developed a method for δ 13 C and δ 2 H analysis of eight organophosphorus compounds (OPs) with different chemical properties. In particular, we aimed to compare high-temperature conversion (HTC) and chromium-based HTC (Cr/HTC) units to explore the limitations of hydrogen isotope analysis of heteroatom-bearing compounds. Analysis of the amount dependency of the isotope values (linearity analysis) of OPs indicated that the formation of HCl was a significant isotope fractionation process leading to inaccurate δ 2 H analysis in HTC. In the case of nonchlorinated OPs, by-product formation of HCN, H 2 S, or PH 3 in HTC was observed but did not affect the dynamic range of reproducible isotope values above the limit of detection. No hydrogen-containing by-products were found in the Cr/HTC process by use of ion trap mass spectrometry analysis. The accuracy of gas chromatography - isotope ratio mass spectrometry was validated in comparison with elemental analyzer - isotope ratio mass spectrometry. Dual-isotope fractionation yielded Λ values of 0 ± 0 at pH 7, 7 ± 1 at pH 9, and 30 ± 6 at pH 12, indicating the potential of 2D CSIA to characterize the hydrolysis mechanisms of OPs. This is the first report on the combination of δ 2 H and δ 13 C isotope analysis of OPs, and this is the first study providing a systematic evaluation of HTC and Cr/HTC for hydrogen isotope analysis using OPs as target compounds. Graphical Abstract Comparison of δ 2 H measurement of non-chlorinated and chlorinated OPs via GC-Cr/HTC-IRMS and GC-HTC-IRMS system.

  6. Occurrence of organochlorine and organophosphorus pesticide ...

    ADOWIE PERE

    Most of the concentrations were above the maximum residue limits ... (accuracy), precision tests and detection limits. ... times higher than the noise level. ..... Exposure to highly hazardous pesticides: A major public health concern, WHO ...

  7. Synthesis and Charaterization of organophosphorus extractants

    Allal, F.; Zaoui, B.; Attou, M.

    1997-04-01

    Liquid-Liquid extraction takes an important place within the treatment of nuclear combustible this process has been used to recover uranium from wet process phosphoric acid. The main aim of the present work is the preparation and characterisation of two organophosphoric esters, used as extractant of heavy metal such as uranium and rare earths metals. The synthetized products are: mono and di [4(1.1.3.3 tetramethyl butyl) phenyl] phosphoric acid (MOPPA and DOPPA)

  8. Efficacious Oxime for Organophosphorus Poisoning: A Minireview

    Erah

    University, PO Box 17666, AlAin, United Arab Emirate. Abstract ... poisoning is a major health problem all over the world ... contaminated food in a social ceremony in. Magrawa, India [7] .... either gave null effect or possible harm [19]. According ...

  9. 热应激复合敌敌畏中毒对小鼠全血乙酰胆碱脂酶和组织抗氧化能力的影响%Effects of heat stress with organophosphorus pesticide intoxication on blood AChE activity and tissue anti-oxidation ability in mice

    蔡颖; 谢首佳; 赵远鹏; 董兆君; 邹仲敏

    2012-01-01

    Objective To explore the combined effect of heat stress with organophosphorus O , O-dimethyl-O-2, 2-di-chlorovinylphosphate (DDVP) intoxication on blood acetyl choli nest erase (AChE) activity and tissue lipid peroxidation. Methods Fifty-four mice were randomly divided into control group , heat stress group and heat stress combined with DDVP poisoning group (the combined group). Mice were put into experiment chamber with (60 ±5)% relative humidity. The chamber temperature was 24℃ for control group , and 38 or 40℃; for heat stress group. One hour later, mice in combined group were intraperitoneally given 9 or 15 mg/kg DDVP. Saline of an equal volume was applied to control and heat stress groups. After 30 minutes, the mice were sacrificed and samples of the blood , heart, brain, and liver were collected. Blood AChE activity, tissue SOD activity, MDA content and · OH inhibiting ability in tissue homogenates of the brain , heart and liver were determined respectively. Results Mice became agitated and restless with increased activity when exposed to 38 or 40℃ ambient temperature. Water intake and body mass were decreased . Compared with temperature-matched controls, the heat exposure combined with DDVP poisoning at 38 or 40℃ caused significant decline of blood AChE activity , tissue SOD activity and · OH inhibiting ability, and increase of tissue MDA content in the brain , heart and liver ( P < 0. 05 ). Heat stress and organophosphorus pesticide intoxication showed synergistic interaction between the above parameters . Conclusion Under present experimental conditions , both ambient temperature and organophosphorus poisoning can significant -ly suppress the blood AChE activity while causing enhanced tissue lipid peroxidation . These data suggest that oxidative stress plays a role in the aggregative effect of organophosphorus intoxication under high ambient temperature .%目的 研究热应激复合有机磷敌敌畏(O,O-dimethyl-O-2,2-dichlorovinylphosphate

  10. Levels, trends and determinants of organohalogen compounds in breast milk in the netherlands

    Houweling, D. A.; Steentjes, G. M.; Van Dekken, A.; Baumann, R. A.; Hoogerbrugge, R.; Zeilmaker, M. J.

    2002-07-01

    Since 1968, human milk surveys have been performed in the Netherlands at five year intervals to study trends in human exposure to polychlorinated organic compounds (POCs). From 1988 onwards dioxin-like congeners were analysed. The most recent campaign was carried out in 1998. In the campaign of 1998, in addition to the levels and trends of POCs in breast milk, potential determinants of the levels of POXCs in breast milk (such as the age of the mother, body mass index (BMI) of the mother, smoking behaviour and dietary habits) were also studied. Previously we presented preliminary results of the analysis of 36 breast milk samples. here we present the results of the analysis of 193 breast milk samples and the analysis of potential determinants of POC levels in breast milk. (Author) 8 refs.

  11. Organohalogen Contaminants and Vitamins in Northern Fur Seals (Callorhinus ursinus) Collected During Subsistence Hunts in Alaska.

    Reiner, Jessica L; Becker, Paul R; Gribble, Matthew O; Lynch, Jennifer M; Moors, Amanda J; Ness, Jennifer; Peterson, Danielle; Pugh, Rebecca S; Ragland, Tamika; Rimmer, Catherine; Rhoderick, Jody; Schantz, Michele M; Trevillian, Jennifer; Kucklick, John R

    2016-01-01

    During native subsistence hunts from 1987 to 2007, blubber and liver samples from 50 subadult male northern fur seals (Callorhinus ursinus) were collected on St. Paul Island, Alaska. Samples were analyzed for legacy persistent organic pollutants (POPs), recently phased-out/current-use POPs, and vitamins. The legacy POPs measured from blubber samples included polychlorinated biphenyl congeners, DDT (and its metabolites), chlorobenzenes, chlordanes, and mirex. Recently phased-out/current-use POPs included in the blubber analysis were the flame retardants, polybrominated diphenyl ethers, and hexabromocyclododecanes. The chemical surfactants, perfluorinated alkyl acids, and vitamins A and E were assessed in the liver samples. Overall, concentrations of legacy POPs are similar to levels seen in seal samples from other areas of the North Pacific Ocean and the Bering Sea. Statistically significant correlations were seen between compounds with similar functions (pesticides, flame retardants, vitamins). With sample collection spanning two decades, the temporal trends in the concentrations of POPs and vitamins were assessed. For these animals, the concentrations of the legacy POPs tend to decrease or stay the same with sampling year; however, the concentrations of the current-use POPs increased with sampling year. Vitamin concentrations tended to stay the same across the sampling years. With the population of northern fur seals from St. Paul Island on the decline, a detailed assessment of exposure to contaminants and the correlations with vitamins fills a critical gap for identifying potential population risk factors that might be associated with health effects.

  12. Comprehensive two-dimensional gas chromatography for the analysis of organohalogenated micro-contaminants

    Korytar, P.; Haglund, P.; Boer, de J.; Brinkman, U.A.Th.

    2006-01-01

    We explain the principles of comprehensive two-dimensional gas chromatography (GC × GC), and discuss key instrumental aspects - with emphasis on column combinations and mass spectrometric detection. As the main item of interest, we review the potential of GC × GC for the analysis of

  13. Organohalogen diffuse contamination in Firenze and Prato groundwater bodies. investigative monitoring and definition of background values

    Stefano Menichetti

    2017-03-01

    Full Text Available The experience of the Environmental Protection Agency of Tuscany in the determination of background values start from 2009 with various substances such as metals, non-metals and inorganic, dioxins and various matrices such as soil, groundwater, inland surface waters and coastal marine sediments. The methodologies supplied in literature have been interpreted and integrated to meet the requirements of current legislation and needs for remediation, diffuse pollution and excavated earth in specific areas. The method for diffuse pollution described here focuses on the use of statistical and geostatistical tools and what we present in this paper are some early results of interest obtained from two case studies in the Florence and in the Prato area. The study has been carried out on concentrations of tetrachlorethylene in the two groundwater bodies by identifying a number of frequency classes in the distribution. Each class has been hypothesized as corresponding to a distinct process. The occurrence both in space and time of the classes has been analysed and discussed critically concluding for a background value that has been found similar between the two zones. The investigation conducted on two monitoring stations representing hot-spots, with values in excess on background value has enabled to map spatial distribution of concentrations and to separate plumes from diffuse pollution area. The two areas show some peculiarities: Florence area shows advanced dehalogenation and a clear spatial continuity, whereas in Prato area it is limited with poor spatial continuity suggesting a spreading with vertical motions from still active primary or secondary sources. Observing how the methodological structure would require, to be fully predictive, a greater number of samples, however, the present work want to constitute a first contribution for management of areas subject to diffuse pollution.

  14. Persistent Organohalogens in Paired Fish Fillet and Eggs: Implications for Fish Consumption Advisories.

    Zhang, Xianming; Gandhi, Nilima; Bhavsar, Satyendra P

    2016-04-13

    Fish consumption is associated with both health benefits from high-quality proteins, minerals, vitamins, and fatty acids and risks from contaminants in fish. Fish consumption advisories are issued by many government agencies to keep exposure to contaminants at a safe level. Such advisories are typically based on fillets and neglect consumption of other fish parts such as eggs by certain subpopulations. To evaluate potential for dietary exposure to toxic organic chemicals via fish eggs, we analyzed polybrominated diphenyl ethers (PBDEs), polychlorinated naphthalenes (PCNs), dioxin-like polychlorinated biphenyls (dlPCBs), and polychlorinated dibenzodioxins/furans (PCDD/Fs) in paired fillet and eggs of fish from a tributary to Lake Ontario, one of the North American Great Lakes. All wet weight based concentrations in fish eggs were statistically higher than in the paired fillet samples. In fish eggs, concentrations of Σ14PBDEs, Σ14PCNs, and Σ12dlPCBs were 41-118, 0.3-1.7, and 30-128 ng/g wet weight (ww), respectively; Σ3PCDD/Fs and total (dlPCB+ PCDD/Fs) toxic equivalents (TEQs) were 4-22 and 9-54 pg/g ww, respectively. In fillet samples, Σ14PBDEs, Σ14PCNs, and Σ12dlPCBs were 4-116, 0.05-0.66, and 6-85 ng/g, respectively; Σ3PCDD/Fs and TEQs were 2-10 and 3.4-31 pg/g ww, respectively. In contrast, the fillets had higher lipid normalized concentrations than the paired egg samples, suggesting that these chemicals did not reach equilibrium between the fillets and eggs. Accordingly, measured concentrations in eggs or empirical relationship with fillet rather than prediction from equilibrium partitioning model should be used to evaluate contaminant exposure via consumption of fish eggs. For fatty fish from the lower Great Lakes area, we suggest one fillet meal be reduced from the advised fish consumption frequency for consumptions of 207 ± 37, 39 ± 2, 105 ± 51, and 119 ± 9 g fish eggs of brown trout, Chinook salmon, Coho salmon, and rainbow trout, respectively.

  15. Determination of persistent organohalogenated pollutants in human hair reference material (BCR 397): an interlaboratory study

    Gill, Udai [Health Canada, Product Safety Laboratory, Ottawa, Ontario (Canada); Covaci, Adrian [University of Antwerp, Toxicological Center, Wilrijk (Belgium); Ryan, John Jake [Health Canada, Bureau of Chemical Safety, Health Products and Food Branch, Ottawa, Ontario (Canada); Emond, Andre [Health Canada, Environmental Research Division, First Nations and Inuit Health Branch, Ottawa, Ontario K1A0L2 (Canada)

    2004-12-01

    A human powdered hair material (BCR 397) was tested for its content in persistent organic pollutants (POPs), such as polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs). Using different methods, three laboratories (two from Canada and one from Belgium) analysed a powdered hair sample to evaluate some methodologies and to obtain consensus values for selected POPs. Measured values for all PCB congeners and p,p'-DDE were within a relative standard deviation (RSD) of 15%. These first results contribute to the accuracy and precision for POPs quantification in hair and render test results more comparable among different laboratories. (orig.)

  16. Persistent organohalogen contaminants in plasma from groups of humans with different occupations in Bangladesh.

    Zamir, R; Athanasiadou, M; Nahar, N; Mamun, M I R; Mosihuzzaman, M; Bergman, A

    2009-01-01

    The present study is aimed to assess persistent organic halogenated pollutants in humans living in Bangladesh. The results are compared to other similar studies in the region and globally. Human blood plasma were collected from groups of men and women with different occupations, i.e. being students, garment industry workers, employees at the Power Development Board (PDB), all groups in Dhaka, fishermen and fishermen wife's from Dhaka and another group from Barisal district. The plasma was analysed for hexachlorobenzene (HCB), the hexachlorocyclohexane isomers, alpha-HCH, beta-HCH, gamma-HCH and delta-HCH, the DDT group of chemicals, chlordane compounds, trans-chlordane, cis-chlordane, oxychlordane, trans-nonachlor, trans-heptachlorepoxide, methoxychlor and mirex. The most abundant contaminant, in all groups studied, p,p'-DDE is dominating, with p,p'-DDT/Sigma DDT ratios indicating recent and ongoing DDT exposure. Among the other pesticides analysed beta-HCH is the most abundant indicating the use of technical HCH products instead of Lindane (gamma-HCH). While the Sigma DDT is present in the low ppm range the beta-HCH is detected in up to approx. 400 ppb, lipid basis. The beta-HCH is most abundant in the groups of students. In contrast to the pesticides analysed very low concentrations of polychlorinated biphenyls (PCB) are present in all study groups, with e.g. CB-153 in the range of 5-30 ng g(-1) fat. The concentrations of the DDT group of chemical differ significantly between fishermen and fishermen's wives living and working in the Dhaka area versus those living and working in Barisal. Also, fishermen and their wives had significantly different concentrations of DDT compared to garment industry workers.

  17. Organohalide respiration in pristine environments

    Atashgahi, Siavash; Häggblom, Max M.; Smidt, Hauke

    2018-01-01

    Halogenated organic compounds, also termed organohalogens, were initially considered to be of almost exclusively anthropogenic origin. However, over 5000 naturally synthesized organohalogens are known today. This has also fuelled the hypothesis that the natural and ancient origin of organohalogens

  18. Multiresidue determination of pesticides in malt beverages by capillary gas chromatography with mass spectrometry and selected ion monitoring.

    Wong, Jon W; Webster, Michael G; Bezabeh, Dawit Z; Hengel, Mathew J; Ngim, Kenley K; Krynitsky, Alexander J; Ebeler, Susan E

    2004-10-20

    A method was developed to determine pesticides in malt beverages using solid phase extraction on a polymeric cartridge and sample cleanup with a MgSO4-topped aminopropyl cartridge, followed by capillary gas chromatography with electron impact mass spectrometry in the selected ion monitoring mode [GC-MS(SIM)]. Three GC injections were required to analyze and identify organophosphate, organohalogen, and organonitrogen pesticides. The pesticides were identified by the retention times of peaks of the target ion and qualifier-to-target ion ratios. GC detection limits for most of the pesticides were 5-10 ng/mL, and linearity was determined from 50 to 5000 ng/mL. Fortification studies were performed at 10 ng/mL for three malt beverages that differ in properties such as alcohol content, solids, and appearance. The recoveries from the three malt beverages were greater than 70% for 85 of the 142 pesticides (including isomers) studied. The data showed that the different malt beverage matrixes had no significant effect on the recoveries. This method was then applied to the screening and analysis of malt beverages for pesticides, resulting in the detection of the insectide carbaryl and the fungicide dimethomorph in real samples. The study indicates that pesticide levels in malt beverages are significantly lower than the tolerance levels set by the United States Environmental Protection Agency for malt beverage starting ingredients. The use of the extraction/cleanup procedure and analysis by GC-MS(SIM) proved effective in screening malt beverages for a wide variety of pesticides. Copyright 2004 American Chemical Society

  19. Portable Sensor for Chemical Nerve Agents and Organophosphorus Compounds

    2015-08-18

    as pesticides in crop, livestock, and poultry products and as chemical and biological warfare agents. As a result of the high toxicity and the...biomedical applications such as: tissue engineering, wound dressing materials, molecular imprinting, drug delivery, etc. In this experiment the hydrogel...agents have been exploited for use as pesticides in crop, livestock, and poultry products and as chemical and biological warfare agents. As a result of

  20. Treatment Strategies for the NMDA Component of Organophosphorus Convulsions

    Peterson, Steven

    2003-01-01

    .... The strychnine-insensitive glycine site partial agonists 1-aminocyclopropanecarboxylic acid (ACPC) and D-cycloserine had no anticonvulsant activity but ACPC induced significant neuroprotection...

  1. Third International Meeting on Esterases Reacting with Organophosphorus Compounds

    1998-01-01

    cassette for negative selection, 884 bp of ACHE including exon 1, 1.6 kb of a Neor gene cassette for positive selection, 5.2 kb of the ACHE Bam HI...fragment including exon 6, and 3 kb of Bluescript. Deletion of exons 2-5 removed 80% of the ACHE coding sequence. The gene targeting vector was...expression due to environmental influences on CYP3A4 and the presence or absence of CYP3A5 which may be under genetic control in man. Plasma

  2. Sonochemical degradation of organophosphorus pesticide in dilute aqueous solutions

    Robina Farooq; FENG Kai-lin; S. F. Shaukat; HUANG Jian-jun

    2003-01-01

    Ultrasonic irradiation was found to accelerate the rate of hydrolysis of omethoate in aqueous solution over the pH range of 2-12. Process parameters studied include pH, steady-state temperature, concentration, and the type of gases. Greater than 96% hydrolysis was observed in 30 minutes through this process and the rate of destruction increased with the help of more soluble and low thermal inert gas. So with Krypton, omethoate was found to undergo rapid destruction as compared with Argon. In the presence of ultrasound, the observed first-order rate of hydrolysis of omethoate is found to be independent of pH. The formation of transient supercritical water(SCW) appears to be an important factor in the acceleration of chemical reactions in the presence of ultrasound. A detailed chemical reaction mechanism for omethoate destruction in water was formulated. Experimental results and theoretical kinetic mechanism demonstrated that the most of the omethoate undergo destruction inside the cavitating holes. A very less effect of temperature on the degradation of omethoate within a temperature range of 20-70℃ proves that a small quantity of omethoate undergoes secondary destruction in the bulk liquid.

  3. Fluid extraction using carbon dioxide and organophosphorus chelating agents

    Smart, Neil G.; Wai, Chien M.; Lin, Yuehe; Kwang, Yak Hwa

    1998-01-01

    Methods for extracting metalloid and metal species from a solid or liquid material by exposing the material to a fluid solvent, particularly supercritical CO.sub.2, and a chelating agent are described. The chelating agent forms a chelate with the species, the chelate being soluble in the fluid to allow removal of the species from the material. In preferred embodiments the extraction solvent is supercritical CO.sub.2 and the chelating agent comprises an organophosphorous chelating agent, particularly sulfur-containing organophosphorous chelating agents, including mixtures of chelating agents. Examples of chelating agents include monothiophosphinic acid, di-thiophosphinic acid, phosphine sulfite, phosphorothioic acid, and mixtures thereof. The method provides an environmentally benign process for removing metal and metalloids from industrial waste solutions, particularly acidic solutions. Both the chelate and the supercritical fluid can be regenerated and the contaminant species recovered to provide an economic, efficient process.

  4. Miniaturised sample preparation method for the multiresidual determination of regulated organohalogenated pollutants and related compounds in wild bird eggs.

    Roscales, Jose L; Vicente, Alba; Ramos, Lourdes; Jiménez, Begoña

    2017-08-01

    A simplified, miniaturised matrix solid-phase dispersion (MSPD)-based method allowing the simultaneous extraction and purification of contaminants belonging to selected families of regulated persistent organic pollutants (POPs), i.e. polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and penta- to octa-polybrominated diphenyl ethers (PBDEs), and related contaminants of emerging concern, such as deca-BDE and Dechlorane Plus (DP), has been proposed. Wild bird eggs were used as biotic fat-containing model matrices. Once optimised, the procedure allowed sample preparation to be accomplished within 30 min, in a single step, and with minimal sample and reagent consumption and waste generation. These features contributed to speeding up and greening the analytical process as compared to the large-scale multistep procedures for these types of analyses. The method was combined with gas chromatography-quadrupole mass spectrometry (GC-qMS) for PCB and OCP analysis and with GC-negative ion chemical ionisation-quadrupole mass spectrometry (NCI-qMS) for PBDE and DP determination. The complete analytical method provided satisfactory recoveries of the target compounds (above 83% for all analytes, except for PBDE 209, 63%), although as small an amount of sample as 0.300 g was used. The repeatability of the complete procedure was less than 16% (with the only exception for PCB 153, which looked to be affected by an interference). The limits of detection were in all cases lower than 34 pg g -1 dry weight (as calculated for real samples), demonstrating the feasibility of the proposed procedure for accurate determination of the target compounds in biological samples. The proposed procedure was applied to the analysis of the target POPs in unhatched eggs of wild bird species. Graphical abstract Scheme of the miniaturised methodology proposed for environmental monitoring of POPs and related compounds in wild bird eggs.

  5. Organohalogen contaminants and Blood plasma clinical-chemical parameters in three colonies of North Atlantic Great skua (Stercorarius skua)

    Sonne, Christian; Rigét, Frank F; Leat, Eliza H K

    2013-01-01

    to compare Great skua BCCPs in different exposure scenarios. Persistent organic pollutants (organochlorines: PCB, DDT, chlordanes, HCB, HCH, mirex and brominated flame retardants: PBDEs) and nineteen BCCPs were analysed in 114 adult Great skuas sampled during summer 2009 in North Atlantic colonies...

  6. Body burdens of brominated flame retardants and other persistent organo-halogenated compounds and their descriptors in US girls

    Windham, Gayle C., E-mail: gayle.windham@cdph.ca.gov [CA Department of Public Health, DEODC, 850 Marina Bay Pkwy, Bldg. P, Richmond, CA 94804 (United States); Pinney, Susan M. [University of Cincinnati College of Medicine, Cincinnati, OH 45267 (United States); Sjodin, Andreas [Centers for Disease Control and Prevention, Atlanta, GA 30341 (United States); Lum, Raymond [Impact Assessment Inc., San Diego, CA (United States); Jones, Richard S.; Needham, Larry L. [Centers for Disease Control and Prevention, Atlanta, GA 30341 (United States); Biro, Frank M. [University of Cincinnati College of Medicine, Cincinnati, OH 45267 (United States); Hiatt, Robert A. [University of California Medical School, San Francisco, CA (United States); Kushi, Lawrence H. [Kaiser Permanente Northern California, Oakland, CA 94612 (United States)

    2010-04-15

    Background: Levels of brominated flame retardants are increasing in US populations, yet little data are available on body burdens of these and other persistent hormonally active agents (HAAs) in school-aged children. Exposures to such chemicals may affect a number of health outcomes related to development and reproductive function. Objective: Determine the distribution of biomarkers of polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and organo-chlorinated pesticides (OCPs), such as DDT/DDE, in children, and their variation by key descriptor variables. Methods: Ethnically diverse cohorts of girls 6-8 y old at baseline are being followed for growth and pubertal development in a multi-site, longitudinal study. Nearly 600 serum samples from the California and Ohio sites were analyzed for lipids, 35 PCB congeners, 11 PBDE congeners, and 9 OCPs. The biomarker distributions were examined and geometric means compared for selected analytes across categories of age, race, site, body mass index (BMI), parental education, maternal age at delivery, and breast feeding in adjusted models. Results: Six PBDE congeners were detected among greater than 70% of samples, with BDE-47 having the highest concentration (median 42.2, range 4.9-855 ng/g lipid). Girls in California had adjusted geometric mean (GM) PBDE levels significantly higher than girls in Ohio. Furthermore, Blacks had significantly higher adjusted GMs of all six PBDE congeners than Whites, and Hispanics had intermediate values. GMs tended to be lower among more obese girls, while other variables were not strongly associated. In contrast, GMs of the six PCB congeners most frequently detected were significantly lower among Blacks and Hispanics than Whites. PCBs and the three pesticides most frequently detected were also consistently lower among girls with high BMI, who were not breast-fed, whose mothers were younger, or whose care-givers (usually parents) were less educated. Girls in California had higher GMs than in Ohio for the pesticides and most PCB congeners, but the opposite for CB-99 and -118. Conclusions: Several of these potential HAAs were detected in nearly all of these young girls, some at relatively high levels, with variation by geographic location and other demographic factors that may reflect exposure pathways. The higher PBDE levels in California likely reflect differences in fire regulation and safety codes, with potential policy implications.

  7. Body burdens of brominated flame retardants and other persistent organo-halogenated compounds and their descriptors in US girls

    Windham, Gayle C.; Pinney, Susan M.; Sjodin, Andreas; Lum, Raymond; Jones, Richard S.; Needham, Larry L.; Biro, Frank M.; Hiatt, Robert A.; Kushi, Lawrence H.

    2010-01-01

    Background: Levels of brominated flame retardants are increasing in US populations, yet little data are available on body burdens of these and other persistent hormonally active agents (HAAs) in school-aged children. Exposures to such chemicals may affect a number of health outcomes related to development and reproductive function. Objective: Determine the distribution of biomarkers of polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and organo-chlorinated pesticides (OCPs), such as DDT/DDE, in children, and their variation by key descriptor variables. Methods: Ethnically diverse cohorts of girls 6-8 y old at baseline are being followed for growth and pubertal development in a multi-site, longitudinal study. Nearly 600 serum samples from the California and Ohio sites were analyzed for lipids, 35 PCB congeners, 11 PBDE congeners, and 9 OCPs. The biomarker distributions were examined and geometric means compared for selected analytes across categories of age, race, site, body mass index (BMI), parental education, maternal age at delivery, and breast feeding in adjusted models. Results: Six PBDE congeners were detected among greater than 70% of samples, with BDE-47 having the highest concentration (median 42.2, range 4.9-855 ng/g lipid). Girls in California had adjusted geometric mean (GM) PBDE levels significantly higher than girls in Ohio. Furthermore, Blacks had significantly higher adjusted GMs of all six PBDE congeners than Whites, and Hispanics had intermediate values. GMs tended to be lower among more obese girls, while other variables were not strongly associated. In contrast, GMs of the six PCB congeners most frequently detected were significantly lower among Blacks and Hispanics than Whites. PCBs and the three pesticides most frequently detected were also consistently lower among girls with high BMI, who were not breast-fed, whose mothers were younger, or whose care-givers (usually parents) were less educated. Girls in California had higher GMs than in Ohio for the pesticides and most PCB congeners, but the opposite for CB-99 and -118. Conclusions: Several of these potential HAAs were detected in nearly all of these young girls, some at relatively high levels, with variation by geographic location and other demographic factors that may reflect exposure pathways. The higher PBDE levels in California likely reflect differences in fire regulation and safety codes, with potential policy implications.

  8. Exposure to mixtures of organohalogen contaminants and associative interactions with thyroid hormones in East Greenland polar bears (Ursus maritimus)

    Villanger, Gro D.; Jenssen, Bjørn M.; Fjeldberg, Rita R.

    2011-01-01

    influence on total 3,5,3′-triiodothyronine (TT3) in AdF_S, and that a group of 17 higher chlorinated ortho-PCBs had a positive influence on total 3,5,3′,5′-tetraiodothyronine (thyroxine, TT4) in AdF_N. TH levels in AdM seemed less influenced by OHCs because of non-significant PLS models. TH levels were also...

  9. Organohalogen exposure in a Eurasian owl (Bubo bubo) population from Southeastern Spain: Temporal-spatial trends and risk assessment

    Gomez-Ramirez, P.; Martinez-Lopez, E.; Garcia-Fernandez, A.; Zweers, A.J.; Brink, van den N.W.

    2012-01-01

    Polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs) and organochlorine insecticides (OCs) were analysed in 58 Eurasian Eagle owl (Bubo bubo) unhatched eggs collected between 2004 and 2009 in Southeastern Spain. Levels of p,p'-DDE were found to be higher than in eggs laid by

  10. Relationships between organohalogen contaminants and blood plasma clinical-chemical parameters in chicks of three raptor species from Northern Norway

    Sonne, Christian; Bustnes, Jan Ove; Herzke, Dorte

    2010-01-01

    :creatinine were significantly positively correlated to various OHCs (all: praptor chicks of Northern Scandinavia may impact blood plasma biochemistry in a way that indicates impacts on liver, kidney, bone...

  11. Effects of organohalogen pollutants on haematological and urine clinical-chemical parameters in Greenland sledge dogs (Canis familiaris)

    Sonne, Christian; Dietz, Rune; Kirkegaard, Maja

    2008-01-01

    :05) in the control group, while glucose was signi.cantly highest (ANCOVA: po0:05) in the exposed group. Furthermore, the blood cholesterol levels indicate that exposure via the diet to marine mammal blubber has a preventive effect on the development of cardiovascular diseases. We therefore suggest...

  12. Does the nutrition profile of vitamins, fatty acids and microelements counteract the negative impact from organohalogen pollutants on bone mineral density in Greenland sledge dogs (Canis familiaris)?

    Sonne, Christian; Rigét, Frank F; Beck Jensen, Jens-Erik

    2008-01-01

    an impact on BMD using the present time frame and OHC concentrations (threshold levels not reached), or the difference in food composition (mainly vitamins and n3 fatty acids) conceal the potential OHC impact on BMD. Such information is important when evaluating the positive and negative health consequences...

  13. Does the nutrition profile of vitamins, fatty acids and microelements counteract the negative impact from organohalogen pollutants on bone mineral density in Greenland sledge dogs (Canis familiaris)?

    Sonne, Christian; Riget, Frank F.; Jensen, Jens-Erik Beck

    2008-01-01

    using the present time frame and OHC concentrations (threshold levels not reached), or the difference in food composition (mainly vitamins and n3 fatty acids) conceal the potential OHC impact on BMD. Such information is important when evaluating the positive and negative health consequences from eating...

  14. Organohalogens in A Whale-Blubber-Supplemented Diet Affects Hepatic Retinol and Renal Tocopherol Concentrations in Greenland Sled Dogs (Canis familiaris)

    Kirkegaard, M.; Sonne, C.; Jakobsen, Jette

    2010-01-01

    The aim of this study was to examine the plasma, liver, and kidney status of vitamin A (retinol) and vitamin E (-tocopherol) in two groups of Greenland sled dogs (Canis familiaris), with a total number of 16 bitches and 8 pups. The dogs were fed either minke whale (Balaenoptera acuterostrata...... polychlorinated biphenyls [PCB]). Retinol was approximately 18% and -tocopherol 22% higher in the diet of the exposed dogs compared to controls. In adipose tissue, mean of sigma OHC was 92 ng/g lipid weight (lw) and 5005 ng/g lw for all control (n = 12) and exposed dogs (n = 10), respectively. Hepatic retinol...... correlated negatively with sigma-dichlorodiphenyldichloroethane (sigma DDT) and and sigma-polybrominated diphenyl ethers (sigma PBDE) for all exposed animals. A negative correlation between kidney -tocopherol and sigma PCB concentrations was observed, whereas two positive significant correlations were...

  15. Effects of long-term dietary exposure to organohalogen contaminants on vitamin and hormonestatus in the Greenland Sledge dog (Canis familiaris)

    Kirkegaard, Maja

    conducted on Greenland sledge dogs. This aimed at exploring how a diet rich in OHCs affects vitamin and hormone status in Arctic top predator mammals. The dogs were supplemented with fat containing high (exposed group: minke whale blubber) or low (control group: porcine fat) amounts of OHCs, polyunsaturated...... weights in male offspring were signifi cantly lower in the exposed group, while plasma testosterone concentrations (and other male parameters) showed no signifi cant difference between groups. The exposed females had signifi cantly lower concentrations of thyroid hormone (Free T4) across all observations...

  16. Organohalogen pollutants in surface particulates from workshop floors of four major e-waste recycling sites in China and implications for emission lists

    Zeng, Yan-Hong [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Tang, Bin [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Graduate University of Chinese Academy of Sciences, Beijing 100049 (China); Luo, Xiao-Jun [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Zheng, Xiao-Bo [College of Natural Resources and Environment, South China Agricultural University, Guangzhou 510642 (China); Peng, Ping-An [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Mai, Bi-Xian, E-mail: nancymai@gig.ac.cn [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China)

    2016-11-01

    To examine the environmental pollution associated with e-waste recycling activities, the concentrations of organohologenated pollutants (OHPs), i.e., short- and medium-chain chlorinated paraffins (SCCPs and MCCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and several other halogenated flame retardants (OHFRs), were investigated in surface particulates from the workshop floors of four major e-waste recycling sites (Taizhou, Guiyu, Dali and Qingyuan) in China. The mean levels of SCCPs, MCCPs, PCBs, PBDEs and OHFRs in surface particulates ranged from 30,000–61,000, 170,000–890,000, 2700–27,000, 52,000–240,000, and 62,000–140,000 ng/g dry weight (dw), respectively. OHFRs, including decabromodiphenyl ethane, dechlorane plus, 1,2-bis(2,4,6-tribromophenoxy)ethane, tetrabromobisphenol A, hexabromocyclododecanes, polybrominated biphenyls, hexabromobenzene, pentabromotoluene, and pentabromoethylbenzene, were frequently (> 50% detection frequency) detected in surface particulates with mean concentration ranges of 39,000–63,000, 310–2700, 98–16,000, 21,000–56,000, 55–5700, 1700–27,000, 42–1600, 3.2–220, and 5.8–12 ng/g dw, respectively. The composition of OHPs varied depend on the e-waste items processing in different regions. Guiyu and Dali were typical sites contaminated by halogenated flame retardants (HFRs) and CPs, respectively, while Qingyuan, and Taizhou were representative PCB-polluted regions. The evidence produced by this preliminary study indicated that electronic devices and plastics may account for the high content of HFRs and the metal products are likely the major source of CPs in these e-waste sites. - Highlights: • Report of characterizing the types and possible sources of OHPs in e-waste sites • Guiyu was a typical site contaminated by HFRs, while Dali was dominated by CPs. • Qingyuan and Taizhou were representative PCB-polluted regions. • Electronic devices and plastics may account for the high content of HFRs. • Metal products are likely the major source of CPs.

  17. Perinatal exposure to organohalogen pollutants decreases vasopressin content and its mRNA expression in magnocellular neuroendocrine cells activated by osmotic stress in adult rats

    Polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) are environmental pollutants that produce neurotoxicity and neuroendocrine disruption. They affect the vasopressinergic system but their disruptive mechanisms are not well understood. Our group reported t...

  18. Different profiles of anthropogenic and naturally produced organohalogen compounds in serum from residents living near a coastal area and e-waste recycling workers in India.

    Eguchi, Akifumi; Nomiyama, Kei; Devanathan, Gnanasekaran; Subramanian, Annamalai; Bulbule, Kesav A; Parthasarathy, Peethambaram; Takahashi, Shin; Tanabe, Shinsuke

    2012-10-15

    We determined the contamination status and accumulation profiles of polychlorinated biphenyls (PCBs), hydroxylated PCB congeners (OH-PCBs), polybrominated diphenyl ethers (PBDEs), hydroxylated PBDEs (OH-PBDEs), methoxylated PBDEs (MeO-PBDEs), and bromophenols (BPhs) in serum from e-waste recycling workers and residents near a coastal area in India. Residue levels of penta- to octa-chlorinated PCBs, penta- to octa-chlorinated OH-PCBs, 6MeO-BDE47, 6OH-BDE47, and 2,4,6-tri-BPh in serum from residents living near the coastal area were significantly higher than those in serum from e-waste recycling workers. Residue levels of tri- to tetra-chlorinated PCBs, tri- to tetra-chlorinated OH-PCBs, PBDEs, octa-brominated OH-PBDEs, and tetra-BPhs in serum from e-waste recycling workers were higher than those in serum from residents living near the coastal area. Principal component analysis revealed that residents living near the coastal area and e-waste recycling workers had different serum profiles of chlorinated and brominated compounds. Copyright © 2012 Elsevier Ltd. All rights reserved.

  19. Association between exposure to persistent organohalogen pollutants and epididymal and accessory sex gland function: Multicentre study in Inuit and European populations

    Elzanaty, Saad; Rignell-Hydbom, Anna; Jönsson, Bo A.G.

    2006-01-01

    Exposure to persistent organochlorine pollutants (POPs) may have negative impact on male reproductive function. We, therefore, investigated the association between serum levels of POPs and epididymal and accessory sex gland function. Serum levels of CB-153, p,p′-DDE and seminal markers of epididy......Exposure to persistent organochlorine pollutants (POPs) may have negative impact on male reproductive function. We, therefore, investigated the association between serum levels of POPs and epididymal and accessory sex gland function. Serum levels of CB-153, p,p′-DDE and seminal markers...... with the activity of NAG were found among Greenlandic men (mean difference 7.0 mU/ejaculate, 95% CI 3.0, 34), and in the aggregated cohort (mean difference 4.0 mU/ejaculate, 95% CI -0.2, 8.0). A positive association was observed between CB-153 and PSA as well as zinc among Kharkiv men. In the Swedish cohort...

  20. Organohalogen pollutants in surface particulates from workshop floors of four major e-waste recycling sites in China and implications for emission lists.

    Zeng, Yan-Hong; Tang, Bin; Luo, Xiao-Jun; Zheng, Xiao-Bo; Peng, Ping-An; Mai, Bi-Xian

    2016-11-01

    To examine the environmental pollution associated with e-waste recycling activities, the concentrations of organohologenated pollutants (OHPs), i.e., short- and medium-chain chlorinated paraffins (SCCPs and MCCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and several other halogenated flame retardants (OHFRs), were investigated in surface particulates from the workshop floors of four major e-waste recycling sites (Taizhou, Guiyu, Dali and Qingyuan) in China. The mean levels of SCCPs, MCCPs, PCBs, PBDEs and OHFRs in surface particulates ranged from 30,000-61,000, 170,000-890,000, 2700-27,000, 52,000-240,000, and 62,000-140,000ng/g dry weight (dw), respectively. OHFRs, including decabromodiphenyl ethane, dechlorane plus, 1,2-bis(2,4,6-tribromophenoxy)ethane, tetrabromobisphenol A, hexabromocyclododecanes, polybrominated biphenyls, hexabromobenzene, pentabromotoluene, and pentabromoethylbenzene, were frequently (>50% detection frequency) detected in surface particulates with mean concentration ranges of 39,000-63,000, 310-2700, 98-16,000, 21,000-56,000, 55-5700, 1700-27,000, 42-1600, 3.2-220, and 5.8-12ng/g dw, respectively. The composition of OHPs varied depend on the e-waste items processing in different regions. Guiyu and Dali were typical sites contaminated by halogenated flame retardants (HFRs) and CPs, respectively, while Qingyuan, and Taizhou were representative PCB-polluted regions. The evidence produced by this preliminary study indicated that electronic devices and plastics may account for the high content of HFRs and the metal products are likely the major source of CPs in these e-waste sites. Copyright © 2016. Published by Elsevier B.V.

  1. Organohalogen pollutants in surface particulates from workshop floors of four major e-waste recycling sites in China and implications for emission lists

    Zeng, Yan-Hong; Tang, Bin; Luo, Xiao-Jun; Zheng, Xiao-Bo; Peng, Ping-An; Mai, Bi-Xian

    2016-01-01

    To examine the environmental pollution associated with e-waste recycling activities, the concentrations of organohologenated pollutants (OHPs), i.e., short- and medium-chain chlorinated paraffins (SCCPs and MCCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and several other halogenated flame retardants (OHFRs), were investigated in surface particulates from the workshop floors of four major e-waste recycling sites (Taizhou, Guiyu, Dali and Qingyuan) in China. The mean levels of SCCPs, MCCPs, PCBs, PBDEs and OHFRs in surface particulates ranged from 30,000–61,000, 170,000–890,000, 2700–27,000, 52,000–240,000, and 62,000–140,000 ng/g dry weight (dw), respectively. OHFRs, including decabromodiphenyl ethane, dechlorane plus, 1,2-bis(2,4,6-tribromophenoxy)ethane, tetrabromobisphenol A, hexabromocyclododecanes, polybrominated biphenyls, hexabromobenzene, pentabromotoluene, and pentabromoethylbenzene, were frequently (> 50% detection frequency) detected in surface particulates with mean concentration ranges of 39,000–63,000, 310–2700, 98–16,000, 21,000–56,000, 55–5700, 1700–27,000, 42–1600, 3.2–220, and 5.8–12 ng/g dw, respectively. The composition of OHPs varied depend on the e-waste items processing in different regions. Guiyu and Dali were typical sites contaminated by halogenated flame retardants (HFRs) and CPs, respectively, while Qingyuan, and Taizhou were representative PCB-polluted regions. The evidence produced by this preliminary study indicated that electronic devices and plastics may account for the high content of HFRs and the metal products are likely the major source of CPs in these e-waste sites. - Highlights: • Report of characterizing the types and possible sources of OHPs in e-waste sites • Guiyu was a typical site contaminated by HFRs, while Dali was dominated by CPs. • Qingyuan and Taizhou were representative PCB-polluted regions. • Electronic devices and plastics may account for the high content of HFRs. • Metal products are likely the major source of CPs.

  2. Perfluorooctane sulfonic acid and organohalogen pollutants in liver of three freshwater fish species in Flanders (Belgium): relationships with biochemical and organismal effects

    Hoff, Philippe Tony [Department of Biology, Research Unit Ecophysiology, Biochemistry and Toxicology, Antwerp University, Groenenborgerlaan 171, B-2020 Antwerp (Belgium)]. E-mail: philippe.hoff@ua.ac.be; Van Campenhout, Karen [Department of Biology, Research Unit Ecophysiology, Biochemistry and Toxicology, Antwerp University, Groenenborgerlaan 171, B-2020 Antwerp (Belgium); Van de Vijver, Kristin [Department of Biology, Research Unit Ecophysiology, Biochemistry and Toxicology, Antwerp University, Groenenborgerlaan 171, B-2020 Antwerp (Belgium); Covaci, Adrian [Toxicological Centre, Antwerp University, Universiteitsplein 1, B-2610 Wilrijk (Belgium); Bervoets, Lieven [Department of Biology, Research Unit Ecophysiology, Biochemistry and Toxicology, Antwerp University, Groenenborgerlaan 171, B-2020 Antwerp (Belgium); Moens, Lotte [Department of Biology, Research Unit Ecophysiology, Biochemistry and Toxicology, Antwerp University, Groenenborgerlaan 171, B-2020 Antwerp (Belgium); Huyskens, Geert [Department of Biology, Research Unit Ecophysiology, Biochemistry and Toxicology, Antwerp University, Groenenborgerlaan 171, B-2020 Antwerp (Belgium); Goemans, Geert [Institute for Forestry and Game Management, Duboislaan 14, B-1560 Groenendaal (Belgium); Belpaire, Claude [Institute for Forestry and Game Management, Duboislaan 14, B-1560 Groenendaal (Belgium); Blust, Ronny [Department of Biology, Research Unit Ecophysiology, Biochemistry and Toxicology, Antwerp University, Groenenborgerlaan 171, B-2020 Antwerp (Belgium); Coen, Wim de [Department of Biology, Research Unit Ecophysiology, Biochemistry and Toxicology, Antwerp University, Groenenborgerlaan 171, B-2020 Antwerp (Belgium)

    2005-09-15

    A perfluorooctane sulfonic acid (PFOS) assessment was conducted on gibel carp (Carassius auratus gibelio), carp (Cyprinus carpio), and eel (Anguilla anguilla) in Flanders (Belgium). The liver PFOS concentrations in fish from the Ieperlee canal (Boezinge, 250-9031 ng/g wet weight, respectively) and the Blokkersdijk pond (Antwerp, 633-1822 ng/g wet weight) were higher than at the Zuun basin (Sint-Pieters-Leeuw, 11.2-162 ng/g wet weight) and among the highest in feral fish worldwide. Eel from the Oude Maas pond (Dilsen-Stokkem) and Watersportbaan basin (Ghent) had PFOS concentrations ranging between 212 and 857 ng/g wet weight. The hepatic PFOS concentration was significantly and positively related with the serum alanine aminotransferase activity, and negatively with the serum protein content in eel and carp. The hepatic PFOS concentration in carp correlated significantly and negatively with the serum electrolyte concentrations whereas a significant positive relation was found with the hematocrit in eel. Although 13 organochlorine pesticides, 22 polychlorinated biphenyl (PCB) congeners and 7 polybrominated diphenyl ethers (PBDEs) were also measured in the liver tissue, only PCB 28, PCB 74, {gamma}-hexachlorocyclohexane ({gamma}-HCH) and hexachlorobenzene (HCB) were suggested to contribute to the observed serological alterations in eel. - Hepatic perfluorooctane sulfonic acid contamination in Flanders (Belgium) might affect serological endpoints in feral carp and eel.

  3. Extraction of rare earth elements with organophosphorus extractants as carriers in supported liquid membranes

    Kopunec, R.; Benitez, J.C.

    1991-01-01

    The membrane extraction of Y, Ce, Eu, Tm and their binary mixtures Ce-Y, Ce-Eu, Ce-Tm with supported liquid membranes containing TBP and HDEHP as carriers in decane-dodecane hydrocarbon solvent, has been studied. Upon extraction with TBP aqueous nitrate solutions of rare earth elements (REE) were used as feed phase. In some cases they also contained EDTA or DCTA. In most cases, the receiving phase was an aqueous solution of EDTA. Extraction with HDEHP was performed from nitrate and chloride solutions and the receiving phase was the corresponding dilute acid. Pertraction of an element through a membrane was studied as a function of time and of initial composition of phases. The results are presented in the following forms: flux of metal through membrane, coefficients of permeability, separation factors and effective diffusion coefficients. (author) 24 refs.; 8 figs.; 3 tabs

  4. Degradation of organophosphorus pesticide parathion methyl on nanostructured titania-iron mixed oxides

    Henych, Jiří; Štengl, Václav; Slušná, Michaela; Matys Grygar, Tomáš; Janoš, P.; Kuráň, P.; Šťastný, M.

    2015-01-01

    Roč. 344, JUL (2015), s. 9-16 ISSN 0169-4332 R&D Projects: GA ČR(CZ) GAP106/12/1116 Institutional support: RVO:61388980 Keywords : Titania-iron oxides * Homogeneous hydrolysis * Degradation of organophosphates * Parathion methyl Subject RIV: CA - Inorganic Chemistry Impact factor: 3.150, year: 2015

  5. Extraction of Tetravalent Uranium by Certain Acidic Organophosphorus Extractants from Phosphate Medium

    Daoud, J.A.; Zeid, M.M.; Aly, H.F.

    1998-01-01

    The extraction of U(IV) by octylphenyl acid phosphate (OPAP) or di-2-ethylhexyl phosphoric acid (HDEHP) in kerosene from phosphoric acid was carried out. The effect of extractant, phosphoric acid, uranium, Fe(II) and Fe(III) concentration on the extraction process was separately investigated. The effect of different reagents and temperature on the stripping of U(IV) was also investigated. The results obtained for the extraction of U(IV) by HDEHP showed that the extraction with the increase in HDEHP and Fe(III) concentration while it decreases with the increase in phosphoric acid, uranium and Fe(II) concentration. In case of extraction with OPAP, the extraction of U(IV) was found to decrease with the phosphoric acid, Fe(II) and initial uranium concentration while the increase in OPAP concentration slightly affected the extraction. The use of high phosphoric acid concentration as stripper at low temperature was found to give the best stripping results

  6. Determination of the Partition Coefficients of Organophosphorus Compounds Using High-Performance Liquid Chromatography.

    1987-12-01

    have claimed an advantage to deter- mining values of k’ in 100% aqueous mobile phases by extrapolation of linear plots of log k’ vs. percent organic...im parti- cle size chemically bonded octadecylsilane (ODS) packing ( Alltech Econo- sphere). As required, this column was saturated with I-octanol by in

  7. A nuclear magnetic resonance and electron spin resonance study on the dynamics of pentacoordinated organophosphorus compounds

    Keijzer, A.E.H. de.

    1988-01-01

    In this thesis the role of the steric and electronic effects on the fundamental dynamic behaviour of pentacoordinated phosporus compounds is further elaborated. In chapter 2 a variable temperature 13 C NMR study, performed on a series of monocyclic oxyphosphoranes, is presented. The investigations were carried out to determine the influence of the conformational transmission effect on the barriers to pseudorotation in pentacoordinated phosphorus compounds. Chapter 3 also comprises a variable temperature 13 C NMR study on pentacoordinated phosphorus compounds. In this chapter, however, an additional high-resolution 1 H NMR study on the conformational equilibria around the P-O-C-C-O fragments is included. These studies were performed in order to determine whether the enhancement of the reorganization rates around phosphorus is brought about by accelerated pseudorotation or by the involvement of hexacoordinated zwitterionic phosphorus intermediates. In chapter 4, a 31 P NMR study on the solvolysis rate of several phosphinate esters is described. This study was performed in order to determine the influence of the conformational transmission effect on the solvolysis rate of phosphate esters. A number of phosphates is examined in which, during the course of the solvolysis reaction, the conformational transmission effect is bound to be present or absent respectively. Moreover, it is discussed in which way the concept of conformational transmission induced differences in solvolysis rates can be used as a probe to examine the reactions of biologically important phosphate esters. In chapters 5 and 6 ESR studies on the influence of steric and electronic factors on phosphoranyl formation in solution, and on the intramolecular electron transfer in phosphoranyl radicals are presented. (author). 121 refs.; 33 figs.; 17 figs

  8. EPA Method 614: The Determination of Organophosphorus Pesticides in Municipal and Industrial Wastewater

    Method 614 describes procedures for preparation and analysis of samples for determination of organophosphate pesticides in industrial and municipal discharges using a GC with a phosphorus-specific flame photometric detector (FPD).

  9. Multivariate curve resolution applied to infrared reflection measurements of soil contaminated with an organophosphorus analyte.

    Gallagher, Neal B; Blake, Thomas A; Gassman, Paul L; Shaver, Jeremy M; Windig, Willem

    2006-07-01

    Multivariate curve resolution (MCR) is a powerful technique for extracting chemical information from measured spectra of complex mixtures. A modified MCR technique that utilized both measured and second-derivative spectra to account for observed sample-to-sample variability attributable to changes in soil reflectivity was used to estimate the spectrum of dibutyl phosphate (DBP) adsorbed on two different soil types. This algorithm was applied directly to measurements of reflection spectra of soils coated with analyte without resorting to soil preparations such as grinding or dilution in potassium bromide. The results provided interpretable spectra that can be used to guide strategies for detection and classification of organic analytes adsorbed on soil. Comparisons to the neat DBP liquid spectrum showed that the recovered analyte spectra from both soils showed spectral features from methyl, methylene, hydroxyl, and P=O functional groups, but most conspicuous was the absence of the strong PO-(CH2)3CH3 stretch absorption at 1033 cm(-1). These results are consistent with those obtained previously using extended multiplicative scatter correction.

  10. CELL SURFACE DISPLAY OF ORGANOPHOSPHORUS HYDROLASE USING ICE NUCLEATION PROTEIN. (R827227)

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

  11. Optimizing Organophosphorus Fire Resistant Finish for Cotton Fabric Using Box-Behnken Design

    Sohail, Y.; Parag, B.; Nemeshwaree, B.; Giorgio, R.

    2016-01-01

    N-methylol dimethyl phosphono propionamide (MDPA) is one of the most utilized fire resistant (FR) finishes for cotton fabrics, utilized as part of a formulation with trimethylol melamine (TMM) to acquire better crosslinking and enhanced FR properties. The system parameters of the finishing treatment were upgraded for better FR properties and low mechanical loss to the fabric by the response surface methodology utilizing Box-Behnken statistical designed experimental strategy. The impacts of concentration on the cotton fabric’s properties (fire resistance and mechanical properties) were assessed with the regression equations. The optimum conditions by predicting the FR reagents focusing intact mechanical properties of the fabric were additionally studied. It was found that the parameters of crosslinking agents in the FR formulation have a prime role in the general FR properties of the cotton fabrics. The R-squared estimations of the considerable number of responses were above 92%, demonstrating the level of relationship between the predicted values by the Box-Behnken frameworks and the real test results.

  12. Bidentate organophosphorus extractants: purification, properties and applications to removal of actinides from acidic waste solutions

    Schulz, W.W.; McIsaac, L.D.

    1977-05-01

    At both Hanford and Idaho, DHDECMP (dihexyl-N, N-diethylcarbamylmethylene phosphonate) continuous counter-current solvent extraction processes are being developed for removal of americium, plutonium, and, in some cases, other actinides from acidic wastes generated at these locations. Bench and, eventually, pilot and plant-scale testing and application of these processes have been substantially enhanced by the discovery of suitable chemical and physical methods of removing deleterious impurities from technical-grade DHDECMP. Flowsheet details, as well as various properties of purified DHDECMP extractants, are enumerated

  13. Cumulative risk assessment of the intake of organophosphorus and carbamate pesticides in the Danish diet

    Jensen, A. F.; Petersen, Annette; Granby, Kit

    2003-01-01

    fruit, vegetables and cereals is for adults 0.8-2% of the Acceptable Daily Intake (ADI) in chlorpyrifos equivalents, and 0.03-11% of the ADI in methamidophos equivalents; and for children 2-5% of the ADI in the chlorpyrifos equivalents, and 0.07-27% of the ADI in methamidophos equivalents. Neither Acute...

  14. Optimization of Nano-TiO Photocatalytic Reactor for Organophosphorus Degradation

    Ilin Sadeghi

    2012-01-01

    Full Text Available The photocatalytic decontamination of triethyl phosphate (TEP is studied by the UV/nano-TiO2 process. The nano-TiO2 concentration and pH value for the complete oxidation of TEP were investigated in different concentrations of TEP. The kinetic reaction was calculated for TEP as a function of initial concentration of TEP. Results of adsorptions showed that TEP was adsorbed better in alkalinity pH, and the natural pH had the highest reaction rate for complete degradation. Also, the zero-kinetic order with the lag time as a function of initial concentration of TEP and TiO2 was suggested for oxidation of TEP. The optimized concentration of nano-TiO2 was 400 mg/lit which had the best conversion and the lowest lag time in the reaction.

  15. Denaturation/Renaturation of Organophosphorus Acid Anhydrolase (OPAA) Using Guanidinium Hydrochloride and Urea

    Ong, K. K; Sun, Z; Cheng, T. C; Wei, Y; Yuan, J. M; Yin, R

    2004-01-01

    ...; thereby indicating conformational changes. Similar results were obtained with circular dichroism as the peak representing the alpha-helix conformation decreased as denaturant concentration was increased...

  16. Terminal residues of the organophosphorus pesticides, malathion and dimethoate, in tea

    Manchanda, A.H.; Dougan, J.

    1975-01-01

    A study on the fate of 14 C malathion and 14 C dimethoate applied under field conditions to tea was made. The aqueous infusion of tea extracted ca. 50% of the total radioactivity of either pesticide. In the case of malathion this activity was mainly due to the presence of the parent compound and its oxygen analogue while dimethoate was metabolized to a considerable extent and the oxygen analogue was the major component found. (author)

  17. Extraction of cerium (III) by polymer gels swollen with bidentate organophosphorus compounds

    Takeshita, Kenji; Takashima, Yoichi; Matsumoto, Shiro; Yamanaka, Hiromitsu.

    1995-01-01

    The extraction of Ce (III) from aqueous solutions containing Al (NO 3 ) 3 was examined by using styrene-divinylbenzene copolymer (SDB) gels swollen with dihexyl-N, N-diethylcarbamoylmethylphosphonate (CMP), octyl(phenyl)-N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and an equimolar mixture of CMP and CMPO. The extraction constants (K ex ) for the gels with CMP and CMPO were evaluated. The distribution ratio of Ce (III) for the gel with an equimolar mixture of CMP and CMPO was described as K d = (K ex CMP [CMP] 3 + K ex CMPO [CMPO] 3 ) [NO 3 - ] 3 by using these extraction constants. The extraction rate was found to be controlled by diffusion of Ce-complex [Ce(NO 3 ) 3 (CMPO) 3 or Ce(NO 3 ) 3 (CMP) 3 ] through the gel. The diffusion coefficient (D s ) was inversely proportional to the viscosity of extractant (η) and represented by an expression similar to the Stokes-Einstein equation, D s η/T = constant. A decrease in the viscosity of extractant was effective for increasing the extraction rate. (author)

  18. Chemistry of Destroying of Organophosphorus Compounds in Flame and Mechanism of Their Action as Fire Suppressants

    Korobeinichev, Oleg

    2002-01-01

    .... An influence of TMP additive on the structure of atmospheric flames was demonstrated. A strong influence of equivalence ratio of a flame on the concentration of PO, PO2, HOPO, HOPO2 and OP(OH)3 has been observed...

  19. Uptake, Translocation, and Biotransformation of Organophosphorus Esters in Wheat (Triticum aestivum L.).

    Wan, Weining; Huang, Honglin; Lv, Jitao; Han, Ruixia; Zhang, Shuzhen

    2017-12-05

    The uptake, translocation and biotransformation of organophosphate esters (OPEs) by wheat (Triticum aestivum L.) were investigated by a hydroponic experiment. The results demonstrated that OPEs with higher hydrophobicity were more easily taken up by roots, and OPEs with lower hydrophobicity were more liable to be translocated acropetally. A total of 43 metabolites including dealkylated, oxidatively dechlorinated, hydroxylated, methoxylated, and glutathione-, and glucuronide- conjugated products were detected derived from eight OPEs, with diesters formed by direct dealkylation from the parent triesters as the major products, followed with hydroxylated triesters. Molecular interactions of OPEs with plant biomacromolecules were further characterized by homology modeling combined with molecular docking. OPEs with higher hydrophobicity were more liable to bind with TaLTP1.1, the most important wheat nonspecific lipid transfer protein, consistent with the experimental observation that OPEs with higher hydrophobicity were more easily taken up by wheat roots. Characterization of molecular interactions between OPEs and wheat enzymes suggested that OPEs were selectively bound to TaGST4-4 and CYP71C6v1 with different binding affinities, which determined their abilities to be metabolized and form metabolite products in wheat. This study provides both experimental and theoretical evidence for the uptake, accumulation and biotransformation of OPEs in plants.

  20. Investigation of the chemical identity of soluble organophosphorus compounds found in natural waters. Research report

    Minear, R.A.

    1978-04-01

    Four algal species (Chlamydomonas reinhardtii, Chlorella pyrenoidosa, Anacystis nidulans, and Anabaena flos-aquae) were grown in batch culture on 32 P labelled media to yield dissolved organic phosphorus (DOP) compounds containing a radioactive tag. The DOP compounds of filtered culture solutions were characterized by Sephadex gel filtration and thin layer chromatography (TLC) as a function of culture age. Additional TLC of individual Sephadex fractions was conducted. Time, culture and known compounds (inositol mono- and hexaphosphate) comparisons were made. High performance liquid chromatography was used to separate inositol mono- and hexaphosphates and to compare the DOP components of one algal species (C. reinhardtii) with inositol phosphates. Combinations of alkaline bromination and Sephadex pretreatment were examined

  1. Interaction of some organophosphorus compounds in susceptible and resistant houseflies (Musca domestica L.)

    Abdallah, M.D.

    1963-01-01

    The effect of tri-ortho-cresylphosphate (TOCP) on poisoning by parathion and paraoxon in susceptible and resistant houseflies (Musca domestica L.) was investigated.

    TOCP influenced the penetration of parathion and paraoxon, and this could explain the contradictory results of both an

  2. Liquid-liquid extraction from molten alkaline nitrates by using nitrogenous and organophosphorus derivatives

    Vittori, Olivier

    1971-01-01

    This research thesis reports the use of a system made of the LiNO 3 -KNO 3 eutectic at 160 deg. C and poly-phenyls in order to study the behaviour of phosphine and arsine oxides as extracting agents in a liquid-liquid process. In a first part, the author presents the studied system, its physical characteristics and its preparation, and the various analytical methods which have used. He discusses existing computation methods adapted to the separation of molten salts and organic phase, and proposes a specific method. Then, he reports the study of the behaviour of a phosphine oxide with Cobalt II and Nickel II, and discusses its application to the separation of this pair, Co II and Ni II. He highlights the different possibilities of three agents which are derivatives of phosphine and arsine in their ability to extract rare earths. A study of separation of rare earths is then addressed. The author reports the application of extraction equilibriums to the study of equilibriums in environments of molten salts with the Co II - chloride ions system. The author finally addresses the synergic phenomenon that pairs of neutral complexing agents of neighbouring structure or different donor central atom may display in liquid-liquid extraction

  3. Mechanisms of Organophosphorus (OP) Injury: Sarin-Induced Hippocampal Gene Expression Changes and Pathway Perturbation

    2012-01-01

    activities in frontal cortex and blood were analyzed. Frozen brain tissue were homogenized in a buffer (containing 0.1 M sodium phosphate buffer...organic anion transporter), member 8): Slc22a8 is involved in the sodium -independent transport and excretion of organic anions, some of which are...CSNK1 ( casein kinase 1) leads to its cytoplasmic retention and subsequent ubiquitination and degradation. Per1 is phosphorylated upon DNA damage

  4. [Isomeric derivatives of lupinine and epilupinine--organophosphorus inhibitors of cholinesterases].

    Basova, N E; Kormilitsyn, B N; Perchenok, A Iu; Rosengart, E V; Saakov, V S; Suvorov, A A

    2012-01-01

    The isomeric-structure analysis data of anticholinesterase action of organophosphorous inhibitors with similar structure help in the search of specific effectors and detection of differences in reactivity of various animals' enzymes. This study compared the data of efficacy in respect of 4 mammal and 5 arthropoda cholinesterase preparations for 26 quinolizidine inhibitors, which molecules contain both the isomeric unbranched and branched alkoxyl radicals in the phosphoryl group, and the epimeric lupinine and epilupinine derivatives in the leaving group. The changes in the alkoxyl radical structure of inhibitor molecules act on their efficacy only with respect to the mammal enzymes ("group" inhibitor specificity). The differences between lupinine and epilupinine derivatives were revealed. Highly specific inhibitors of different enzymes were detected among the tested compounds.

  5. Repeated Exposure to Sublethal Doses of the Organophosphorus Compound VX Activates BDNF Expression in Mouse Brain

    2012-01-01

    urinary and fecal incontinence , and bronchial constriction (reviewed in Russell and Overstreet, 1987). Acute toxic levels of CWNA, particularly at...neuronal remodeling, including brain-derived neurotrophic factor (BDNF). We examined the time course of BDNF expression in C57BL/6 mouse brain following...with known trophic effects may be unique targets of intoxication and important factors in the recovery of surviving subjects. In addition, some

  6. Toxicity and medical countermeasure studies on the organophosphorus nerve agents VM and VX.

    Rice, Helen; Dalton, Christopher H; Price, Matthew E; Graham, Stuart J; Green, A Christopher; Jenner, John; Groombridge, Helen J; Timperley, Christopher M

    2015-04-08

    To support the effort to eliminate the Syrian Arab Republic chemical weapons stockpile safely, there was a requirement to provide scientific advice based on experimentally derived information on both toxicity and medical countermeasures (MedCM) in the event of exposure to VM, VX or VM-VX mixtures. Complementary in vitro and in vivo studies were undertaken to inform that advice. The penetration rate of neat VM was not significantly different from that of neat VX, through either guinea pig or pig skin in vitro . The presence of VX did not affect the penetration rate of VM in mixtures of various proportions. A lethal dose of VM was approximately twice that of VX in guinea pigs poisoned via the percutaneous route. There was no interaction in mixed agent solutions which altered the in vivo toxicity of the agents. Percutaneous poisoning by VM responded to treatment with standard MedCM, although complete protection was not achieved.

  7. Degradation of organophosphorus pesticide parathion methyl on nanostructured titania-iron mixed oxides

    Henych, Jiří, E-mail: henych@iic.cas.cz [Department of Material Chemistry, Institute of Inorganic Chemistry AS CR v.v.i., 25068 Řež (Czech Republic); Štengl, Václav; Slušná, Michaela; Matys Grygar, Tomáš [Department of Material Chemistry, Institute of Inorganic Chemistry AS CR v.v.i., 25068 Řež (Czech Republic); Janoš, Pavel; Kuráň, Pavel; Štastný, Martin [Faculty of the Environment, J.E. Purkyně University, Králova Výšina 7, 400 96 Ústí nad Labem (Czech Republic)

    2015-07-30

    Highlights: • Ti–Fe mixed oxides were synthesized via low-temperature one-pot method. • Mixed oxides were used for degradation of parathion methyl. • Pure reference oxide samples showed no degradation ability. • Mixed oxides reached 70% degree of conversion of parathion methyl. - Abstract: Titania-iron mixed oxides with various Ti:Fe ratio were prepared by homogeneous hydrolysis of aqueous solutions of titanium(IV) oxysulphate and iron(III) sulphate with urea as a precipitating agent. The synthesized samples were characterized by X-ray diffraction, Raman and infrared spectroscopy, scanning and transmission electron microscopy, XRF analysis, specific surface area (BET) and porosity determination (BJH). These oxides were used for degradation of organophosporus pesticide parathion methyl. The highest degradation efficiency approaching <70% was found for the samples with Ti:Fe ratio 0.25:1 and 1:0.25. Contrary, parathion methyl was not degraded on the surfaces of pure oxides. In general, the highest degradation rate exhibited samples consisted of the iron or titanium oxide containing a moderate amount of the admixture. However, distinct correlations between the degradation rate and the sorbent composition were not identified.

  8. Experimental chemotherapy of Schistosomiasis III: laboratory and clinical trials with trichlorphone, an organophosphorus compound

    Naftale Katz

    1968-10-01

    Full Text Available Oogram studies have been carried out on mice, hamsters, and Cebus morikeys experimentally infected with Schistosoma mansoni and treated with trichlorphone (0,0-dimethyl 1-hydroxy-2, 2, 2-trichloroethylphosphonate. In mice, despite a slight hepatic shift of schistosomes, all animais presented oogram changes when dosed, per os, at the schedules of 200, and 100 mg/kg/day × 7. In hamsters, antischistosomal activity could be detected only at toxic leveis. In monkeys, trichlorphone showed insignificant action even after oral administration of 30 mg/kg/day for 10 consecutive days. In 5 volunteers, a sharp drop in cholinesterase plasma level was observed 24 hours after a single oral dose of 7.5 mg/kg. However, cholinesterase levels returned to the initial values within a period of 11 to 27 days. Trichlorphone was then administered to 12 schistosome patients (7.5 mg/kg/day, every fort- night, × 5. One month after therapy, interruption of egg laying was observed in 6 patients. Late parasitological control showed that all treated patients continued to pass viable S. mansoni eggs with their stools.

  9. 40 CFR 798.6560 - Subchronic delayed neuro-toxicity of organophosphorus substances.

    2010-07-01

    ..., but not produce an incidence of fatalities which would prevent a meaningful evaluation. The lowest... termination. (iii) The day of observation of each abnormal sign and its subsequent course. (iv) Body weight... the findings of preceding studies and considered in terms of the incidence and severity of observed...

  10. Interaction of organophosphorus pesticides with DNA nucleotides on a Boron-doped diamond electrode

    Garbellini, Gustavo S.; Uliana, Carolina V.; Yamanaka, Hideko, E-mail: gustgarb@yahoo.com.br [Universidade Estadual Paulista Julio de Mesquita Filho (UNESP), Bauru, SP (Brazil). Dept. de Quimica Analitica

    2013-12-01

    Diamond electrode was used to evaluate the interaction of the nucleotides guanosine monophosphate (GMP) and adenosine monophosphate (AMP) with the pesticides chlorpyrifos, methamidophos and monocrotophos. Changes were observed in the currents and peak potentials of the nucleotide voltammograms in the presence of the pesticides, with dependence on the pesticide concentration (from 5.0 Multiplication-Sign 10{sup -7} to 5.0 Multiplication-Sign 10{sup -5} mol L{sup -1}) and the interaction time (from 1 min to 4 h). This is probably due to binding of the pesticides to the nitrogenous bases present in the nucleotides, which could lead to problems in the DNA replication and biological functions of nucleotides. The pesticides showed stronger interaction with AMP than with GMP. Studies of the interaction of 50 Micro-Sign g mL{sup -1} DNA with the pesticides (from 30 min to 4 h and from 1.0 Multiplication-Sign 10{sup -6} to 6.0 Multiplication-Sign 10{sup -5} mol L{sup -1}) did not reveal any peaks relating to double helix opening or DNA unwinding. (author)

  11. Dissipation kinetics of organophosphorus pesticides in milled toasted maize and wheat flour (gofio) during storage.

    González-Curbelo, Miguel Ángel; Socas-Rodríguez, Bárbara; Herrero, Miguel; Herrera-Herrera, Antonio V; Hernández-Borges, Javier

    2017-08-15

    The dissipation/degradation of the pesticides dimethoate, terbufos, disulfoton, and pirimiphos-methyl were evaluated in milled toasted maize and wheat flour (gofio) during three months of storage. Their dissipation kinetics and residual levels were determined, as well as their possible decomposition into some of their main transformation products (disulfoton sulfoxide, terbufos sulfone and disulfoton sulfone). For this purpose, pesticide-free milled toasted maize and wheat samples were spiked with the pesticides, and they were then stored in the darkness at ambient temperature in a closed container to simulate current storage conditions of such packed food. A multiresidue analysis based on the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method was performed for the simultaneous determination of these pesticides and their metabolites. After three months of storage, the dissipation of residues ranged between 34% (pirimiphos-methyl) and 86% (disulfoton) for maize gofio and between 69% (terbufos) and 92% (disulfoton and pirimiphos-methyl) for wheat gofio. The results demonstrated that the degradation was slower in gofio than in wheat gofio and that none of the selected metabolites were detected in any of the samples. Dissipation curves of all studied pesticides fitted to a first-order decay curve in both types of cereals. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. Tetra-cationic imidazoliumyl-substituted phosphorus-sulfur heterocycles from a cationic organophosphorus sulfide

    Henne, F. D.; Watt, F. A.; Schwedtmann, K.; Hennersdorf, F.; Kokoschka, Malte; Weigand, J. J.

    2016-01-01

    Roč. 52, č. 10 (2016), s. 2023-2026 ISSN 1359-7345 Institutional support: RVO:61388963 Keywords : crystal structures * density * carbene Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 6.319, year: 2016 http://pubs.rsc.org/en/content/articlepdf/2016/cc/c5cc08182c

  13. Wearable Flexible and Stretchable Glove Biosensor for On-Site Detection of Organophosphorus Chemical Threats

    2017-03-03

    finger molds (10.0 × 2.3 × 1.3 cm3 dimensions) were designed using SolidWorks 3D CAD (DS SolidWorks, Waltham, MA) and printed using a Mojo 3D printer ...Australia. The OPH enzyme stability in Nafion was evaluated for several days with a stable electrochemical response observed for up to 3 days, after which...prepolymer B provided by the supplier. The fabrication process utilized a semiautomatic MPM-SPM screen printer (Speedline Technologies, Franklin, MA). The

  14. Retrospective detection of exposure to organophosphorus anti-cholinesterases: Mass spectrometric analysis of phosphylated human butyrylcholinesterase

    Fidder, A.; Hulst, A.G.; Noort, D.; Ruiter, R. de; Schans, M.J. van der; Benschop, H.P.; Langenberg, J.P.

    2002-01-01

    In this paper a novel and general procedure is presented for detection of organophosphate-inhibited human butyrylcholinesterase (HuBuChE), which is based on electrospray tandem mass spectrometric analysis of phosphylated nonapeptides obtained after pepsin digestion of the enzyme. The utility of this

  15. Persistence and fate of some organophosphorus pesticides in sea sediments along east coast of India

    Sarkar, A.; SenGupta, R.

    and fate of these pesticides Rate of hydrolysis of these pesticides in freshwater, brackish water and sea-sediments followed the path of pseudo first order reaction The rate constants (K1) and the half life periods (T2) of these pesticides were determined...

  16. Can activated sludge treatments and advanced oxidation processes remove organophosphorus flame retardants?

    Cristale, Joyce [Department of Environmental Chemistry, IDAEA-CSIC, Jordi Girona 18-2, 08034 Barcelona, Catalonia (Spain); Ramos, Dayana D. [Institute of Chemistry, Federal University of Mato Grosso do Sul, Av. Senador Filinto Muller, 1555, CP 549, CEP 79074-460 Campo Grande, MS (Brazil); Dantas, Renato F. [Department of Chemical Engineering, University de Barcelona, Marti i Franques 1, 08028 Barcelona, Catalonia (Spain); School of Technology, University of Campinas-UNICAMP, Paschoal Marmo 1888, 13484-332 Limeira, SP (Brazil); Machulek Junior, Amilcar [Institute of Chemistry, Federal University of Mato Grosso do Sul, Av. Senador Filinto Muller, 1555, CP 549, CEP 79074-460 Campo Grande, MS (Brazil); Lacorte, Silvia [Department of Environmental Chemistry, IDAEA-CSIC, Jordi Girona 18-2, 08034 Barcelona, Catalonia (Spain); Sans, Carme; Esplugas, Santiago [Department of Chemical Engineering, University de Barcelona, Marti i Franques 1, 08028 Barcelona, Catalonia (Spain)

    2016-01-15

    This study aims to determine the occurrence of 10 OPFRs (including chlorinated, nonchlorinated alkyl and aryl compounds) in influent, effluent wastewaters and partitioning into sludge of 5 wastewater treatment plants (WWTP) in Catalonia (Spain). All target OPFRs were detected in the WWTPs influents, and the total concentration ranged from 3.67 µg L{sup −1} to 150 µg L{sup −1}. During activated sludge treatment, most OPFRs were accumulated in the sludge at concentrations from 35.3 to 9980 ng g{sup −1} dw. Chlorinated compounds tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP) and tris(2,3-dichloropropyl) phosphate (TDCPP) were not removed by the conventional activated sludge treatment and they were released by the effluents at approximately the same inlet concentration. On the contrary, aryl compounds tris(methylphenyl) phosphate (TMPP) and 2-ethylhexyl diphenyl phosphate (EHDP) together with alkyl tris(2-ethylhexyl) phosphate (TEHP) were not detected in any of the effluents. Advanced oxidation processes (UV/H{sub 2}O{sub 2} and O{sub 3}) were applied to investigate the degradability of recalcitrant OPFRs in WWTP effluents. Those detected in the effluent sample (TCEP, TCIPP, TDCPP, tributyl phosphate (TNBP), tri-iso-butyl phosphate (TIBP) and tris(2-butoxyethyl) phosphate (TBOEP)) had very low direct UV-C photolysis rates. TBOEP, TNBP and TIBP were degraded by UV/H{sub 2}O{sub 2} and O{sub 3}. Chlorinated compounds TCEP, TDCPP and TCIPP were the most recalcitrant OPFR to the advanced oxidation processes applied. The study provides information on the partitioning and degradability pathways of OPFR within conventional activated sludge WWTPs. - Highlights: • OPFRs were detected in wastewater and sludge of all studied WWTPs. • Alkyl and chloroalkyl phosphates were present in secondary treatment effluents. • TBOEP, TNBP and TIBP were degraded by UV/H{sub 2}O{sub 2} and O{sub 3} treatment. • TCEP, TCIPP and TDCPP were resistant to both secondary and tertiary treatment.

  17. Fate of the organophosphorus insecticide methoxy-14 C-Azinphos-methyl in baladi egyptian goats

    Hamdy, N.A.; Fakhr, I.M.I.; Abdalla, E.A.M.; Fouzy, A.S.M.; Hassan, M.N.A.

    1998-01-01

    Consecutive feeding of lactating goats with methoxy- 14 C-azinphos-methyl fo 4 days at dietary levels of 25 mg and 50 mg/goat per day resulted in the presence 0 the insecticide residues in milk 0.028ppm, 0.068ppm respectively at the end of the administration period. The residue levels were marckedly reduced after a withdrawa period of one week and completely disappeared after two weeks. Analysis of milk an urine residues showed similar metabolites in addition to a very small amount of the parent compound in the milk only. The major part of the residues consisted of mon demethylatedl azinophos-methyl, dimethyl phosphorohthioic, dimethyl phosphoro dithioic acids, dimethyl and mono-methyl phosphates. The animals remaine symptoms-frce during the experimental period

  18. Vapor Pressure Data and Analysis for Selected Organophosphorus Compounds: DIBMP, DCMP, IMMP, IMPA, EMPA, and MPFA

    2017-04-01

    methylphosphonique. Bulletin de la Societe Chimique de France 1962, 1645–1648. 34. Keay, L. The Preparation and Hydrolysis of Alkyl Hydrogen ...Properties of Phosphonic Anhydrides. I. Alkyl (or Aryl) Hydrogen Methylphosphonates. Journal of General Chemistry USSR (Zhurnal Obshchei Khimii) 1965, 35...4), 723–728. 32. Neimysheva, A.A.; Savchuk, V.I.; Knunyants, I.L. S-Alkyl Hydrogen Alkyl- and Aryl- Phosphonothioates and Their Derivatives. I

  19. Occurrence and distribution of organophosphorus flame retardants and plasticizers in anthropogenically affected groundwater.

    Regnery, J; Püttmann, W; Merz, C; Berthold, G

    2011-02-01

    Occurrence and distribution of chlorinated and non-chlorinated organophosphates in 72 groundwater samples from Germany under different recharge/infiltration conditions were investigated. Tris(2-chloro-1-methylethyl) phosphate (TCPP) and tris(2-chloroethyl) phosphate (TCEP) were the most frequently detected organophosphates in groundwater samples. Highest individual organophosphate concentrations (>0.1 µg L(-1)) were determined in groundwater polluted by infiltrating leachate and groundwater recharged via riverbank filtration of organophosphate-loaded recipients. In samples from springs and deep groundwater monitoring wells that are not affected by surface waters, organophosphate concentrations were mostly below the limit of detection. The occurrence (3-9 ng L(-1)) of TCPP and TCEP in samples from aquifers with groundwater ages between 20 and 45 years indicates the persistence of both compounds within the aquifer. At urban sites organophosphate-loaded precipitation, surface runoff, and leakage of wastewater influenced groundwater quality. For rural sites, where groundwater recharge is only influenced by precipitation, organophosphates were very rarely detectable in groundwater.

  20. Recovery of uranium from phosphoric acid medium by polymeric composite beads encapsulating organophosphorus extractants

    Singh, D.K.; Yadav, K.K.; Varshney, L.; Singh, H. [Bhabha Atomic Research Centre, Mumbai 400 085 (India)

    2013-07-01

    The present study deals with the preparation and evaluation of the poly-ethersulfone (PES) based composite beads encapsulating synergistic mixture of D2EHPA and Cyanex 923 (at 4:1 mole ratio) for the separation of uranium from phosphoric acid medium. SEM was used for the characterization of the composite materials. Addition of 1% PVA (polyvinyl alcohol) improved the internal morphology and porosity of the beads. Additionally, microscopic examination of the composite bead confirmed central coconut type cavity surrounded by porous polymer layer of the beads through which exchange of metal ions take place. Effect of various experimental variables including aqueous acidity, metal ion concentration in aqueous feed, concentration of organic extractant inside the beads, extractant to polymer ratio, liquid to solid (L/S) ratio and temperature on the extraction of uranium was studied. Increase in acidity (1-6 M), L/S ratio (1- 10), metal ion concentration (0.2-3 g/L U{sub 3}O{sub 8}) and polymer to extractant ratio (1:4 -1:10) led to decrease in extraction of uranium. At 5.5 M (comparable to wet process phosphoric acid concentration) the extraction of uranium was about 85% at L/S ratio 5. Increase in extractant concentration inside the bead resulted in enhanced extraction of metal ion. Increase in temperature in the range of 30 to 50 Celsius degrees increased the extraction, whereas further increase to 70 C degrees led to the decrease in extraction of uranium. Amongst various reagents tested, stripping of uranium was quantitative by 12% Na{sub 2}CO{sub 3} solution. Polymeric beads were found to be stable and reusable up-to 10 cycles of extraction/stripping. (authors)

  1. Measured Mass-Normalized Optical Cross Sections For Aerosolized Organophosphorus Chemical Warfare Simulants

    Gurton, Kristan P; Felton, Melvin; Dahmani, Rachid; Ligon, David

    2007-01-01

    We present newly measured results of an ongoing experimental program established to measure optical cross sections in the mid and long wave infrared for a variety of chemical and biologically based aerosols...

  2. Chemical decontamination. I. Dephosphorylation of organophosphorus compounds; Decontamination chimique. I. Dephosphorylation des composes organophosphores

    Segues, B.; Perez, E.; Rico-Lattes, I.; Riviere, M.; Lattes, A. [Toulouse-3 Univ., 31 (France)

    1996-12-31

    This work describes investigations of methods for the destruction of wastes containing toxic phosphorus esters due to the use of pesticides or chemical weapons. Compounds are destroyed by basic hydrolysis in various structured media (micellar catalysis) in the presence and absence of additives, in both water and mixed micellar media. Different methods are compared and evaluated 40 refs.

  3. Neurocognitive, mental health, and glucose disorders in farmers exposed to organophosphorus pesticides.

    Malekirad, Ali Akbar; Faghih, Mahya; Mirabdollahi, Mansuoreh; Kiani, Mahdi; Fathi, Arezoo; Abdollahi, Mohammad

    2013-01-01

    About 25 million agricultural workers in the developing world suffer from at least one episode of poisoning each year, mainly by anticholinesterase-like organophosphates (OPs). The objective of this cross-sectional study was to establish the OP toxicity in 187 occupationally exposed farmers in terms of neurocognitive impairment, mental health status, clinical symptoms, diabetes, and haematological factors. The exposed group was compared to 187 healthy age-, sex-, and education-matching controls. Neurocognitive impairment was measured using the Subjective Neurocognition Inventory (SNI) and mental health status using the General Health Questionnaire-28 (GHQ-28). The subjects were also tested for fasting blood glucose (FBG), blood urea nitrogen (BUN), cholesterol (CL), triglycerides (TG), creatinine, oral glucose tolerance test (GTT), high-density lipoprotein (HDL), aspartate aminotransferase (AST), alanine aminotransferase (ALT), and alkaline phosphatase (ALP). The exposed farmers showed higher FBG (peczema, saliva secretion, fatigue, headache, sweating, abdominal pain, nausea, superior distal muscle weakness, inferior distal muscle weakness, inferior proximal muscle weakness, breath muscle weakness, hand tingling, foot tingling, epiphoria, polyuria, miosis, dyspnoea, bradycardia, and rhinorrhoea, which all significantly correlated with the number of working years. These findings indicate that farmers who work with OPs are prone to neuropsychological disorders and diabetes.

  4. Interrelation of Glycemic Status and Neuropsychiatric Disturbances in Farmers with Organophosphorus Pesticide Toxicity.

    Jamal, Farrukh; Haque, Quazi S; Singh, Sangram

    2016-01-01

    Diverse group of agro-chemicals are indiscriminately sprayed by the farmers for pest control to enhance crop yield. About 25 million agricultural workers in the developing world suffer from at least one episode of poisoning each year, mainly by anticholinesterase- like organophosphates (OPs). The present study was aimed to establish the OP toxicity in 187 occupationally exposed pesticide sprayers of mango plantation in rural Malihabad, Lucknow, in terms of neuro-cognitive impairment, mental health status, clinical symptoms, diabetes, and hematological factors. The exposed group was compared to 187 pesticides-unexposed normal healthy persons engaged in normal usual agricultural work (age, sex and education corresponding to age group of selected subject group) from Rural Malihabad, Lucknow (India). Neuro-cognitive impairment was measured using the Subjective Neurocognition Inventory and mental health status using the General Health questionnaire-28. The subjects were also tested for biochemical and enzymatic parameters. The exposed farmers showed alterations in enzymatic and clinical parameters. While the rates of anxiety / insomnia and severe depression were also significantly higher in the pesticide sprayers, disorders affecting psychomotor speed, selective attention, divided attention, verbal memory, nonverbal memory, prospective memory, spatial functioning, and initiative/energy were all lower in the sprayers. Pesticide sprayers showed a number of clinical symptoms like eczema, saliva secretion, fatigue, headache, sweating, abdominal pain, nausea, superior distal muscle weakness, inferior distal muscle weakness, hand tingling and etc. which all significantly correlated with the number of working years. These findings suggested that farmers who work with OPs are prone to neuro-psychological disorders and diabetes.

  5. Interrelation of Glycemic Status and Neuropsychiatric Disturbances in Farmers with Organophosphorus Pesticide Toxicity

    Jamal, Farrukh; Haque, Quazi S.; Singh, Sangram

    2016-01-01

    Background: Diverse group of agro-chemicals are indiscriminately sprayed by the farmers for pest control to enhance crop yield. About 25 million agricultural workers in the developing world suffer from at least one episode of poisoning each year, mainly by anticholinesterase- like organophosphates (OPs). Objective: The present study was aimed to establish the OP toxicity in 187 occupationally exposed pesticide sprayers of mango plantation in rural Malihabad, Lucknow, in terms of neuro-cogniti...

  6. Ethephon, an organophosphorus, a fruit and vegetable ripener: Has potential hepatotoxic effects.

    Pooja Bhadoria

    2015-01-01

    Full Text Available Introduction: Ethephon, 2-choloroethylphosphonic acid, has been recognized as one of the most widely used plant growth regulator. Currently it is commonly used on fruits, vegetables, cereals, for promoting pre-harvest and post-harvest ripening and has become one of the major health concerns as we are exposed to this constantly.Rationale: Liver plays an important role in the first pass metabolism of ethephon and its metabolites are known to cause various disturbances in the liver enzymes.Objectives: The present study was conducted to study the effects of ethephon on histomorphology and morphometry of liver of adult wistar albino rats.Material and Methods: Ten experimental rats were administered 200mg/kg bodyweight by oral gavage for fourteen days. Ten Controls were also maintained.  Animals of both groups were sacrificed within twenty four hours of the last dose; liver was dissected and processed for light microscopy. Haematoxylin and eosin stained sections were studied using an image pro-express analyzer. The data obtained from control and experimental groups was tabulated and statistically analyzed.Results: The mean body weight of the experimental rats was found to be decreased significantly (p<0.05. The liver capsule was thickened and infiltrated with inflammatory and red blood cells. The orderly arrangement of hepatocytes was disrupted and was replaced by blood filled large sinusoids. At sites hepatocytes appeared to be degenerated. Councilman bodies with pyknotic nuclei and inflammatory infiltrations were observed. The hepatocyte count per unit area was significantly decreased among experimental rats (29.53±10.65 when compared with control rats (44.18±10.31. However, the kupffer cell count per unit area was significantly higher among experimental rats (25.12 ± 4.41 as compared to control rats (13.05±6.5.Conclusion: The changes observed in the liver suggest that ethephon, which is commonly used a fruit and vegetable ripener possesses a serious hepatotoxic potential. Thus a habit of thorough cleaning and washing of fruits and vegetables, before consumption, should be adopted to prevent the ingestion of this potential hepatotoxin.

  7. Toxicity of organophosphorus pesticide sumithion on larval stages of stinging catfish Heteropneustes fossilis

    Shahjahan, M.; Kabir, M.F.; Sumon, Kizar Ahmed; Bhowmik, Lipi Rani; Rashid, Harunur

    2017-01-01

    Sumithion is widely used to control brittle in paddy fields and tiger bug in fish larval rearing ponds. The objective of this study was to elucidate the toxic effects of sumithion on larval stages of stinging catfish Heteropneustes fossilis. Larvae were exposed to two concentrations (150 and 250

  8. Structure–property relationships of synthetic organophosphorus flame retardant oligomers by thermal analysis

    Bai, Zhiman; Wang, Xin; Tang, Gang; Song, Lei; Hu, Yuan; Yuen, Richard K.K.

    2013-01-01

    Highlights: • Oligomers with different chemical components in molecular chains were synthesized. • FP-3 containing three IFR components possessed high thermal stability. • FP-3 possessed lowest flammability. • FP-3 exhibited a synergistic interaction between gas and condensed phase. - Abstract: A series of flame retardant oligomers with different chemical components in molecular chains, designated as FP-1, FP-2 and FP-3, respectively, were successfully synthesized using solution polycondensation and well characterized. The thermal properties and flammability of these oligomers were investigated by thermogravimetric analysis (TGA) and microscale combustion calorimeter (MCC). The results demonstrated that FP-3 had the lowest flammability in terms of the lowest maximum mass loss rate, and FP-1 possessed the highest thermal stability and char yield, due to its higher stable hexatomic ring structure of piperazine compared with the linear alkane chain structure of neopentyl glycol. The gases evolved during decomposition were analyzed using Fourier transform infrared coupled with the thermogravimetric analyzer (TG–IR) technique. The char residues of the flame retardant oligomers were investigated by scanning electron microscopy (SEM) and Raman spectroscopy. The results demonstrated that FP-3 exhibited a synergistic interaction between the gas phase and condensation phase, increasing its flame retardancy

  9. Production of Self-Purifying Proteins in a Variety of Expression Hosts with Focus on Organophosphorus Hydrolase

    2012-08-17

    Manley ,  R.G.  Options  for...0.0015 0.001 0 .0005 0 4 Average Product Yields .... ..... ... • • 5 6 7 8 9 ELP (SOX) Amino Acids • 10 11 12 160 140 "’C 120 -0 LL ...0.005 0 4 5 6 7 8 9 10 11 12 ELP Length (SOX) Amino Acids so 45 "’C 40 -0 35 LL c:: 0 30 ·-..... 25 ro u 20 ·-’+-·-s... ::s 15 0.. 10

  10. Organophosphorus insecticides in honey, pollen and bees (Apis mellifera L.) and their potential hazard to bee colonies in Egypt.

    Al Naggar, Yahya; Codling, Garry; Vogt, Anja; Naiem, Elsaied; Mona, Mohamed; Seif, Amal; Giesy, John P

    2015-04-01

    There is no clear single factor to date that explains colony loss in bees, but one factor proposed is the wide-spread application of agrochemicals. Concentrations of 14 organophosphorous insecticides (OPs) in honey bees (Apis mellifera) and hive matrices (honey and pollen) were measured to assess their hazard to honey bees. Samples were collected during spring and summer of 2013, from 5 provinces in the middle delta of Egypt. LC/MS-MS was used to identify and quantify individual OPs by use of a modified Quick Easy Cheap Effective Rugged Safe (QuEChERS) method. Pesticides were detected more frequently in samples collected during summer. Pollen contained the greatest concentrations of OPs. Profenofos, chlorpyrifos, malation and diazinon were the most frequently detected OPs. In contrast, ethoprop, phorate, coumaphos and chlorpyrifos-oxon were not detected. A toxic units approach, with lethality as the endpoint was used in an additive model to assess the cumulative potential for adverse effects posed by OPs. Hazard quotients (HQs) in honey and pollen ranged from 0.01-0.05 during spring and from 0.02-0.08 during summer, respectively. HQs based on lethality due to direct exposure of adult worker bees to OPs during spring and summer ranged from 0.04 to 0.1 for best and worst case respectively. It is concluded that direct exposure and/or dietary exposure to OPs in honey and pollen pose little threat due to lethality of bees in Egypt. Copyright © 2014 Elsevier Inc. All rights reserved.

  11. Biosensor Detection of Neuropathy Target Esterase in Whole Blood as a Biomarker of Exposure to Neuropathic Organophosphorus Compounds

    Makhaeva, Galina F; Sigolaeva, Larisa V; Zhuravleva, Lyudmila Z; Eremenko, Arkady V; Kurochkin, Ilya N; Malygin, Vladimir V; Richardson, Rudy J

    2002-01-01

    .... Lymphocyte NTE has also found use as a biomarker of human exposure to neuropathic OPs. Recently, a sensitive NTE biosensor was developed using a tyrosinase carbon-paste electrode for amperometric (Amp...

  12. Probabilistic assessment of the cumulative dietary acute exposure of the population of Denmark to organophosphorus and carbamate pesticides

    Jensen, Bodil Hamborg; Petersen, Annette; Christensen, Tue

    2009-01-01

    and methamidophos. RPF values derived from the literature were used in the calculations. We calculated the cumulative acute exposure to 1.8% and 0.8% of the acute reference dose (ARfD) of 100 mu g kg(-1) body weight (bw) day(-1) of chlorpyrifos as an index compound at the 99.9th percentile (P99.5) for children...

  13. Reconstructing Organophosphorus Pesticide Doses Using the Reversed Dosimetry Approach in a Simple Physiologically-Based Pharmacokinetic Model

    Chensheng Lu

    2012-01-01

    Full Text Available We illustrated the development of a simple pharmacokinetic (SPK model aiming to estimate the absorbed chlorpyrifos doses using urinary biomarker data, 3,5,6-trichlorpyridinol as the model input. The effectiveness of the SPK model in the pesticide risk assessment was evaluated by comparing dose estimates using different urinary composite data. The dose estimates resulting from the first morning voids appeared to be lower than but not significantly different to those using before bedtime, lunch or dinner voids. We found similar trend for dose estimates using three different urinary composite data. However, the dose estimates using the SPK model for individual children were significantly higher than those from the conventional physiologically based pharmacokinetic (PBPK modeling using aggregate environmental measurements of chlorpyrifos as the model inputs. The use of urinary data in the SPK model intuitively provided a plausible alternative to the conventional PBPK model in reconstructing the absorbed chlorpyrifos dose.

  14. Recovery and Separation of Valuable Metals from Spent Nickel-Metal Hydride Batteries using some Organophosphorus Extractants

    Aly, M.I.; Daoud, J.A.; ALy, H.F.

    2012-01-01

    The separation of cobalt, nickel, and rare earth elements from NiMH battery residues is evaluated in this paper. A hydrometallurgical process is developed for the recovery of metals from spent batteries and a selective separation of RE by precipitation of sodium RE double sulfate is performed. The methodology used benefits the solubility of the battery electrode materials in sulfuric or hydrochloric acids. The results obtained show that sulfuric acid is slightly less powerful in leaching (NiMH) compared to HCl acid. However, sulfuric acid was used on economic basis. Leaching solution was obtained by using 3 M H 2 SO 4 at 70 +1 degree C + 3% wt. H 2 O 2 for 5 hours. It has been shown that it is possible to recover about 98 % of the RE contained in spent NiMH batteries. The maximum recovery of nickel and cobalt metals was 99.9% and 99.4%, respectively. The effects of the main operating variables of both leaching and solvent extraction steps of nickel (II) and cobalt (II) from the leach solution using HDEHP (di-2-ethylhexyl phosphoric acid) and CYANEX 272 (di-(2,4,4 trimethyl pentyl) phosphinic acid) in kerosene were investigated aiming to maximize metal separation for recycling purposes. The developed process for the recovery and separation of nickel (II) , cobalt (II), and rare earth from spent NiMH batteries is tested and the obtained sulfate salts CoSO 4 and NiSO 4 have a high purity, suggesting that these recovered products could be used as chemical materials without further purification

  15. Synergistic solvent extraction of Eu(III) and Tb(III) with mixtures of various organophosphorus extractants

    Reddy, B.V.; Reddy, L.K.; Reddy, A.S.

    1994-01-01

    Synergistic solvent extraction of Eu(III) and Tb(III) from thiocyanate solutions with mixtures of 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (EHPNA) and di-2-ethylhexylphosphoric acid (DEHPA) or tributyl phosphate (TBP) or trioctylphosphine oxide (TOPO) or triphenylphosphine oxide (TPhPO) in benzene has been studied. The mechanism of extraction can be explained by a simple chemically based model. The equilibrium constants of the mixed-ligand species of the various neutral donors have been determined by non-linear regression analysis. (author) 13 refs.; 9 figs.; 2 tabs

  16. Possible mechanisms for sensitivity to organophosphorus and carbamate insecticides in eastern screech-owls and American kestrels.

    Vyas, N B; Thiele, L A; Garland, S C

    1998-07-01

    Effects of a single dietary exposure to fenthion and carbofuran on the survival, feeding behavior and brain ChE activity of eastern screech-owls, Otus asio and American kestrels, Falco sparverius, were evaluated. Birds were exposed to fenthion (23.6-189.0 ppm) or carbofuran (31.7-253.6 ppm) via meatballs. Carbofuran-exposed owls ate either or = 80% of the meatball whereas all kestrels ate meatball before exhibiting acute signs of toxicity. Fenthion-exposed owls and kestrels displayed a wide spectrum of meatball consumption (< 10-100%). Significant brain ChE inhibition was observed in dead and surviving kestrels exposed to fenthion and carbofuran and dead owls exposed to fenthion (P < 0.0001). Brain ChE activity of owls exposed to carbofuran that survived was not different from that of controls (P = 0.25). Data suggest: (1) slow feeding on a carbamate-contaminated item may provide limited protection from the toxicity of the chemical at certain rates of exposure; (2) the degree of ChE inhibition at neuromuscular junctions may be critical in determining the sensitivity of a species to a carbamate insecticide; (3) sensitivity may be a function of the ChE affinity for the carbamate inhibitor; and (4) the importance of neuromuscular junction ChE depression in determining the sensitivity of an animal may be species-specific.

  17. [New approaches to early diagnosis of chronic organophosphorus chemicals intoxication in workers at chemical weapons extermination objects].

    Babakov, V N; Goncharov, N V; Radilov, A S; Glashkina, E P; Podol'skaia, E P; Ermolaeva, E E; Shilov, V V; Prokof'eva, D S; Voĭtenko, N G; Egorov, N A

    2009-01-01

    Mass spectrum analysis revealed differences in general contents of low-molecular peptides spectrums in chemical weapons extermination object staffers, in comparison with the reference group. Findings are that serum paraoxonase activity in chemical weapons extermination object staffers in significantly increased.

  18. Possible mechanisms for sensitivity to organophosphorus and carbamate insecticides in eastern screech-owls and American kestrels

    Vyas, N.B.; Thiele, L.A.; Garland, S.C.

    1998-01-01

    Effects of a single dietary exposure to fenthion and carbofuran on the survival, feeding behavior and brain ChE activity of eastern screech-owls, Otus asio and American kestrels, Falco sparverius, were evaluated. Birds were exposed to fenthion (23.6–189.0 ppm) or carbofuran (31.7–253.6 ppm) via meatballs. Carbofuran-exposed owls ate either ≤10% or ≥80% of the meatball whereas all kestrels ate ≤10% of the meatball before exhibiting acute signs of toxicity. Fenthion-exposed owls and kestrels displayed a wide spectrum of meatball consumption (<10–100%). Significant brain ChE inhibition was observed in dead and surviving kestrels exposed to fenthion and carbofuran and dead owls exposed to fenthion (P<0.0001). Brain ChE activity of owls exposed to carbofuran that survived was not different from that of controls (P=0.25). Data suggest: (1) slow feeding on a carbamate-contaminated item may provide limited protection from the toxicity of the chemical at certain rates of exposure; (2) the degree of ChE inhibition at neuromuscular junctions may be critical in determining the sensitivity of a species to a carbamate insecticide; (3) sensitivity may be a function of the ChE affinity for the carbamate inhibitor; and (4) the importance of neuromuscular junction ChE depression in determining the sensitivity of an animal may be species-specific.

  19. Design and Synthesis of Candidate Prophylactic and Therapeutic Compounds for Use in the Management of Organophosphorus Poisoning.

    1985-01-01

    yielded material with an Rf of 0.0 to 0.10. This fraction consisted of primarily amine hydrochloride salt and traces of what may be the desired...diethyl phosphite . The latter undoubtedly arose from the reaction of phosphorus trichloride with ethanol followed by partial hydrolysis during workup...Acid (1): - Diethyl phosphite (55.2 g, 0.040 mol) was added dropwise to a 3 L flask containing a 2 M ethereal solution of 1-butylmagnesium bromide (650

  20. Covalent Coupling of Organophosphorus Hydrolase Loaded Quantum Dots to Carbon Nanotube/Au Nanocomposite for Enhanced Detection of Methyl Parathion

    Du, Dan; Chen, Wenjuan; Zhang, Weiying; Liu, Deli; Li, Haibing; Lin, Yuehe

    2010-02-15

    An amperometric biosensor for highly selective and sensitive determination of methyl parathion (MP) was developed based on dual signal amplification: (1) a large amount of introduced enzyme on the electrode surface and (2) synergistic effects of nanoparticles towards enzymatic catalysis. The fabrication process includes (1) electrochemical deposition of gold nanoparticles by a multi-potential step technique at multiwalled carbon nanotube (MWCNT) film pre-cast on a glassy carbon electrode and (2) immobilization of methyl parathion degrading enzyme (MPDE) onto a modified electrode through CdTe quantum dots (CdTe QDs) covalent attachment. The introduced MWCNT and gold nanoparticles significantly increased the surface area and exhibited synergistic effects towards enzymatic catalysis. CdTe QDs are further used as carriers to load a large amount of enzyme. As a result of these two important enhancement factors, the proposed biosensor exhibited extremely sensitive, perfectly selective, and rapid response to methyl parathion in the absence of a mediator.

  1. Dependence of the extraction capacity of neutral bidentate organophosphorus compounds on their structure: a quantum chemical study

    Sudarushkin, S.K.; Morgalyuk, V.P.; Tananaev, I.G.; Gribov, L.A.; Myasoedov, B.F.

    2006-01-01

    Correlations between the extraction capacities and molecular structures of organic phosphorus compounds (reagents for extraction of transplutonium elements from spent nuclear fuel) were studied using a quantum chemical approach. The results of calculations are in qualitative agreement with experimental data. The approach proposed can be used for analysis of the extraction properties of all classes of organic phosphorus compounds and also for prediction of the most efficient organic phosphorus extractants with preset properties [ru

  2. Rate and mechanism of facilitated americium(III) transport through a supported liquid membrane containing a bifunctional organophosphorus mobile carrier

    Danesi, P.R.; Horwitz, E.P.; Rickert, P.G.

    1983-01-01

    The facilitated transport of Am(III) from aqueous nitrate solutions to formic acid aqueous solutions through a supported liquid membrane (SLM) is described. The supported liquid membrane consists of a solution of a new (carbamoylmethyl)phosphine oxide in diethylbenzene (DEB) absorbed into a 48 μm thick microporous polypropylene film. The transport mechanism consists of a diffusion process through an aqueous diffusion film, a fast interfacial chemical reaction, and diffusion through the membrane itself. Equations describing the rate of transport are derived. They correlate the membrane permeability coefficient to diffusional parameters and to the chemical composition of the system. Different rate-controlling processes are shown to control the membrane permeability when the composition of the system is varied and as long as the transport occurs. The experimental data are quantitatively explained with the derived equations. The diffusion coefficient of the permeating species and the equilibrium constant of the fast interfacial reactions are evaluated. 13 figures, 1 table

  3. Photocatalytic degradation of an organophosphorus pesticide from agricultural waste by immobilized TiO2 under solar radiation

    Marcia Regina Assalin

    2016-11-01

    Full Text Available This paper describes solar heterogeneous photocatalysis using immobilized TiO2 applied in the treatment of agricultural waste resulting from the application of commercial formulations of methyl parathion. The disappearance of the insecticide, as well as the formation of its metabolite, was monitored by high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS, while mineralization efficiency was monitored by measurements of total organic carbon (TOC. Toxicity studies were performed using the microcrustacean Artemia salina. The TOC removal efficiency by photocatalytic process was 48.5%. After 45 minutes of treatment, the removal efficiency of methyl parathion was 90%, being completely mineralized at the end of treatment. The formation and removal of the metabolite methyl paraoxon was observed during the photocatalytic process. The photocatalytic treatment resulted in increased microcrustacean mobility, indicating a reduction of acute toxicity.

  4. effect of interaction of praziquantel and an organophosphorus pesticide on some biochemical parameters in murine schistosomiasis mansoni

    Abd-El Menem, H.A.

    2003-01-01

    in egypt schistosomiasis is still a major public health problem and PZQ is the drug of choice for its treatment, whereas DZN is globally used as pesticide for controlling pests. they adversely affect the environment . therefore, this investigation aimed to study the effect of 1/20 LD 5 0 DZN given orally to healthy and S. mansoni infected mice, for 5 successive days up to 9 and 17 weeks coupled with a therapeutic dose (2 x 500 mg/kg b wt) of PZQ , 2 weeks before sacrificing . the results showed that the different treatments significantly reduced the activity of liver ALT. the highest inhibition was recorded in the infected-DZN - PZQ group at week 9. the maximum inhibition of brain ACHE activity was noticed in DZN-PZQ treated group after 9 and 17 weeks. although,the different treatments did not significantly affect the levels of plasma TP,ALB,G,and A/G ratio, significant differences were revealed from the G- fractions α 1 , α 2 , β 1 , β 2 and γ in addition to plasma ceruloplasmin

  5. Dataset of Atmospheric Environment Publication in 2016, Characterization of organophosphorus flame retardants’ sorption on building materials and consumer products

    U.S. Environmental Protection Agency — The data presented in this data file is a product of a journal publication. The dataset contains OPFR sorption concentrations on building materials and consumer...

  6. Application of a radiometric enzymic method for monitoring organophosphorus and carbamate insecticide residues in water of the Danube River

    Horvath, L.; Volford, J.; Bursics, L.; Forster, T.

    1983-01-01

    Pesticide residue analyses are conventionally based on gas chromatography. These analytic procedures include tedious extraction and clear-up manipulations prior to the actual gas chromatographic determinations. Radioenzymatic method was recently applied in a residue monitoring programme on the Danube River. The programme has demonstrated that the radioenzymatic method has many advantages as a monitoring procedure in aquatic environment. Quick information can be gained without tedious sample clear-up procedure. The anticholinesteratic pesticides and the anticholinesteratic activities can be detected

  7. The influence of the organophosphorus insecticides acephate and parathion upon the heterotrophic bacteria of two freshwater ecosystems

    Albright, L.J.; Geen, G.H.; Gasith, A.; Mozel, Y.; Perry, A.S.

    1983-01-01

    The effect of acephate and parathion on the heterotrophic bacteria of freshwater ecosystems was studied in a dystrophic west coast Canadian lake and in an eutrophic Israeli fish pond. The limnocorrals were treated with 1-25 ppm of acephate and 30-40 ppb of parathion respectively. Bacterial populations, glucose heterotrophic activities and bacterial and algal productivities were studied using 3 H and 14 C radioisotopes. It is concluded that the two ecosystems are not extensively affected by the pesticide concentrations used

  8. Determination of organophosphorus pesticides and their major degradation product residues in food samples by HPLC-UV.

    Peng, Guilong; He, Qiang; Lu, Ying; Mmereki, Daniel; Zhong, Zhihui

    2016-10-01

    A simple method based on dispersive solid-phase extraction (DSPE) and dispersive liquid-liquid microextraction method based on solidification of floating organic droplets (DLLME-SFO) was developed for the extraction of chlorpyrifos (CP), chlorpyrifos-methyl (CPM), and their main degradation product 3,5,6-trichloro-2-pyridinol (TCP) in tomato and cucumber samples. The determination was carried out by high performance liquid chromatography with ultraviolet detection (HPLC-UV). In the DSPE-DLLME-SFO, the analytes were first extracted with acetone. The clean-up of the extract by DSPE was carried out by directly adding activated carbon sorbent into the extract solution, followed by shaking and filtration. Under the optimum conditions, the proposed method was sensitive and showed a good linearity within a range of 2-500 ng/g, with the correlation coefficients (r) varying from 0.9991 to 0.9996. The enrichment factors ranged from 127 to 138. The limit of detections (LODs) were in the range of 0.12-0.68 ng/g, and the relative standard deviations (RSDs) for 50 ng/g of each analytes in tomato samples were in the range of 3.25-6.26 % (n = 5). The proposed method was successfully applied for the extraction and determination of the mentioned analytes residues in tomato and cucumber samples, and satisfactory results were obtained.

  9. Allergic reaction induced by dermal and/or respiratory exposure to low-dose phenoxyacetic acid, organophosphorus, and carbamate pesticides

    Fukuyama, Tomoki; Tajima, Yukari; Ueda, Hideo; Hayashi, Koichi; Shutoh, Yasufumi; Harada, Takanori; Kosaka, Tadashi

    2009-01-01

    Several types of pesticides, such as organophosphates, phenoxyacetic acid, and carbamate have a high risk of affecting human health, causing allergic rhinitis and bronchial asthma-like diseases. We used our long-term sensitization method and a local lymph node assay to examine the allergic reactions caused by several types of pesticides. BALB/c mice were topically sensitized (9 times in 3 weeks), then challenged dermally or intratracheally with 2,4-D, BRP, or furathiocarb. One day post-challenge, the mice were processed to obtain biologic materials for use in assays of total IgE levels in serum and bronchoalveolar lavage fluid (BALF); differential cell counts and chemokine levels in BALF; lymphocyte counts and surface antigen expression on B-cells within regional lymph nodes (LNs); and, ex situ cytokine production by cells from these LNs. 2,4-D-induced immune responses characteristic of immediate-type respiratory reactions, as evidenced by increased total IgE levels in both serum and BALF; an influx of eosinophils, neutrophils, and chemokines (MCP-1, eotaxin, and MIP-1β) in BALF; increased surface antigen expression on B-cells IgE and MHC class II production) in both auricular and the lung-associated LNs; and increased Th2 cytokine production (IL-4, IL-5, IL-10, and IL-13) in both auricular and the lung-associated LN cells. In contrast, BRP and furathiocarb treatment yielded, at most, non-significant increases in all respiratory allergic parameters. BRP and furathiocarb induced marked proliferation of MHC Class II-positive B-cells and Th1 cytokines (IL-2, TNF-α, and IFN-γ) in only auricular LN cells. These results suggest that 2,4-D is a respiratory allergen and BRP and furathiocarb are contact allergens. As our protocol detected classified allergic responses to low-molecular-weight chemicals, it thus may be useful for detecting environmental chemical-related allergy.

  10. In Search of an Effective in vivo Reactivator for Organophosphorus Nerve Agent-Inhibited Acetylcholinesterase in the Central Nervous System

    2012-01-01

    nerve agents, such as sarin (GB), cyclosarin (GF), and VX, are potent inhibitors of the enzyme cholinesterase (ChE). Their toxic effects are due to...three nerve agents. Keywords: acetylcholinesterase; brain; cholinesterase inhibition; cholinesterase reactivation; cyclosarin; diacetylmonoxime...attributed, at least in part, to nuclophilic impedance [Ekstrom et al., 2006a; b; Hoskovcova et al., 2007]. Other AChE- inhibitors , such as soman, become

  11. Metal Ion-Catalyzed Alcoholysis as a Strategy for the High Loading Destruction of Chemical Warfare Organophosphorus Agents

    2013-11-01

    agents (CWAs). Whether these inhibitors are used as pesticides or CWAs, all act in the same way by inhibiting an enzyme (a cholinesterase ), thereby...phosphinate, and phosphonate esters are potent acetylcholinesterase inhibitors that are used as animal and crop protectants and chemical warfare...for these inhibitors are used annually, accounting for 70% of all insecticides used for agriculture, in homes and gardens, and for government

  12. A Characterization of Carboxylesterases in Rat and Guinea Pig - Their Heterogeneity and Role in Detoxication of Organophosphorus Compounds

    1993-09-01

    of the glycoside detergent The rates of inactivation of different esterases. including saponin (final concn. I ’). w/w) to extract the microsomal...to be solubilized from rat liver microsomal membranes by treatment with a detergent like saponin (Mentlein et al., 1980), the CarbE activity of rat...coupled with the excellent selectivity of the Q and S substituents results in the high resolution separations characteristic of FPLC technology

  13. Studies on electronic spectrum and electron spin resonance of vanadium (IV) complexes with organophosphorus compounds and high molecular weight amines

    Sato, Taichi; Nakamura, Takato

    1981-01-01

    In the extraction of vanadium (IV) from aqueous solutions containing hydrochloric acid and/or a mixture of hydrochloric acid and lithium chloride by bis(2-ethylhexyl) hydrogenphosphate (DEHPA; HX), trioctylmethylammonium chloride (Aliquat-336), trioctylamine (TOA), trioctylphosphine oxide (TOPO) and tributyl phosphate (TBP), the complexes formed in the organic phases have been examined by spectrophotometry and electron spin resonance spectroscopy. It is found that in the extraction by DEHPA, the vanadium in the organic phase exists as the monomeric species, VO(X 2 H) 2 , or the polymeric one, (VOX 2 )sub(n), and that in the extractions by Aliquat-336, TOA, TOPO, and TBP, tetravalent vanadium complexes are stable in the organic phases extracted from a mixed solution of hydrochloric acid and lithium chloride, while complexes containing pentavalent vanadium and VOV 4+ ions are formed in the organic phases extracted from hydrochloric acid solutions. (author)

  14. The design and synthesis of biologically active organophosphorus compounds--the role of a central research laboratory.

    Hall, Roger G

    2010-01-01

    The properties and benefits offered by incorporating phosphorus into molecules are varied and numerous as shown by the many divisional research programs within Ciba-Geigy in the early eighties. This paper describes how a Central Research Group developed new materials in organophosphorous chemistry and identified new leads for life science applications.

  15. Structural and optical properties of tin (II) sulfide thin films deposited using organophosphorus precursor (Ph3PS)

    Assili, Kawther; Alouani, Khaled; Vilanova, Xavier

    2017-02-01

    Tin sulfide (SnS) thin films have been deposited onto glass substrates using triphenylphosphine sulfide (Ph3PS) as a sulfur precursor in a chemical vapor deposition reactor in a temperature range of 250 °C-400 °C. The influence of the sulphidisation temperature in the crystal structure, surface morphology, chemical composition and optical properties has been investigated. X-ray diffraction, energy dispersive analysis of x-rays, and Raman spectroscopy showed that pure SnS thin films have been successfully obtained at 250 °C. All the deposited films were polycrystalline and showed orthorhombic structure, with a preferential orientation according to the direction . The optical measurements showed that the films deposited exhibited a direct allowed transition and have a relatively high absorption coefficient. The presence of mixed tin sulfide phases granted by the variation of the sulphidisation temperature has affected the optical properties of the deposited films. The refractive index (n) and extinction coefficient (k), has low values compared to conventional semiconductor materials. The grown films can be considered as a good light absorbing material and a promising candidate for application in optoelectronic devices.

  16. Occurrence and distribution of organophosphorus esters in soils and wheat plants in a plastic waste treatment area in China.

    Wan, Weining; Zhang, Shuzhen; Huang, Honglin; Wu, Tong

    2016-07-01

    This study for the first time reported the occurrence, distribution and concentrations of organophosphate esters (OPEs) in soils caused by plastic waste treatment, as well as their influence on OPE accumulation in wheat (Triticum aestivum L.). Eight OPEs were detected with the total concentrations of 38-1250 ng/g dry weight in the soils from the treatment sites, and tributoxyethyl phosphate and tri(2-chloroethyl) phosphate present as the dominant OPEs. There were similar distribution patterns of OPEs and significant correlations between the total OPE concentrations in the soils from the plastic waste treatment sites with those in the nearby farmlands (P plastic waste treatment caused the OPE contamination of farmland soils. The uptake and translocation of OPEs by wheat were determined, with OPEs of high hydrophobicity more easily taken up from soils and OPEs with low hydrophobicity more liable to be translocated acropetally. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Solar photocatalytic activity of TiO2 modified with WO3 on the degradation of an organophosphorus pesticide

    Ramos-Delgado, N.A.; Gracia-Pinilla, M.A.; Maya-Treviño, L.; Hinojosa-Reyes, L.; Guzman-Mar, J.L.; Hernández-Ramírez, A.

    2013-01-01

    Highlights: • TiO 2 and WO 3 /TiO 2 (2 and 5%) were tested in the photocatalytic malathion degradation. • The use of solar radiation in the photocatalytic degradation process was evaluated. • Modified catalyst showed greater photocatalytic activity than pure TiO 2 . • The mineralization rate was improved when WO 3 content on TiO 2 was 2%. -- Abstract: In this study, the solar photocatalytic activity (SPA) of WO 3 /TiO 2 photocatalysts synthesized by the sol–gel method with two different percentages of WO 3 (2 and 5%wt) was evaluated using malathion as a model contaminant. For comparative purpose bare TiO 2 was also prepared by sol–gel process. The powders were characterized by X-ray diffraction (XRD), Raman spectroscopy, diffuse reflectance UV–vis spectroscopy (DRUV–vis), specific surface area by the BET method (SSA BET ), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM) and scanning transmission electron microscopy with a high annular angle dark field detector (STEM-HAADF). The XRD, Raman, HRTEM and STEM-HAADF analyses indicated that WO 3 was present as a monoclinic crystalline phase with nanometric cluster sizes (1.1 ± 0.1 nm for 2% WO 3 /TiO 2 and 1.35 ± 0.3 nm for 5% WO 3 /TiO 2 ) and uniformly dispersed on the surface of TiO 2 . The particle size of the materials was 19.4 ± 3.3 nm and 25.6 ± 3 nm for 2% and 5% WO 3 /TiO 2 , respectively. The SPA was evaluated on the degradation of commercial malathion pesticide using natural solar light. The 2% WO 3 /TiO 2 photocatalyst exhibited the best photocatalytic activity achieving 76% of total organic carbon (TOC) abatement after 300 min compared to the 5% WO 3 /TiO 2 and bare TiO 2 photocatalysts, which achieved 28 and 47% mineralization, respectively. Finally, experiments were performed to assess 2% WO 3 /TiO 2 catalyst activity on repeated uses; after several successive cycles its photocatalytic activity was retained showing long-term stability

  18. Wastewater analysis of Census day samples to investigate per capita input of organophosphorus flame retardants and plasticizers into wastewater

    O'Brien, J.W.; Thai, P.K.; Brandsma, S.H.; Leonards, P.E.G.; Ort, C.; Mueller, J.F.

    2015-01-01

    The use of organophosphate esters (PFRs) as flame retardants and plasticizers has increased due to the ban of some brominated flame retardants. There is however some concern regarding the toxicity, particularly carcinogenicity and neurotoxicity, of some of the PFRs. In this study we applied

  19. FLOW INJECTION AMPEROMETRIC DETECTION OF OP NERVE AGENTS BASED ON AN ORGANOPHOSPHORUS-HYDROLASE BIOSENSOR DETECTOR. (R828160)

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

  20. A 1000-L Scale-Up Fermentation of Escherichia Coli Containing PVSEOP7 for Production of Organophosphorus Hydrolase

    Lukens, Dennis C; Rastogi, Vipin K; Cheng, Tu-c; DeFrank, Joseph J; Valdes, James J; Kim, Michael H

    2003-01-01

    .... coli XL1 containing pVSEOP7. The specific OPH activity was monitored during each 20-L batch fermentation culture by assaying several times between the IPTG induction point (OD of 0.4 to 0.5 at 600 nm...