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Sample records for carbamate pesticides validation

  1. Analysis of Carbamate Pesticides: Validation of Semi-Volatile Analysis by HPLC-MS/MS by EPA Method MS666

    Owens, J; Koester, C

    2008-05-14

    The Environmental Protection Agency's (EPA) Region 5 Chicago Regional Laboratory (CRL) developed a method for analysis of aldicarb, bromadiolone, carbofuran, oxamyl, and methomyl in water by high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS), titled Method EPA MS666. This draft standard operating procedure (SOP) was distributed to multiple EPA laboratories and to Lawrence Livermore National Laboratory, which was tasked to serve as a reference laboratory for EPA's Environmental Reference Laboratory Network (ERLN) and to develop and validate analytical procedures. The primary objective of this study was to validate and verify the analytical procedures described in MS666 for analysis of carbamate pesticides in aqueous samples. The gathered data from this validation study will be used to: (1) demonstrate analytical method performance; (2) generate quality control acceptance criteria; and (3) revise the SOP to provide a validated method that would be available for use during a homeland security event. The data contained in this report will be compiled, by EPA CRL, with data generated by other EPA Regional laboratories so that performance metrics of Method EPA MS666 can be determined.

  2. Validation and use of a fast sample preparation method and liquid chromatography-tandem mass spectrometry in analysis of ultra-trace levels of 98 organophosphorus pesticide and carbamate residues in a total diet study involving diversified food types.

    Chung, Stephen W C; Chan, Benny T P

    2010-07-16

    This paper reports a comprehensive sensitive multi-residue liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for detection, identification and quantitation of 73 pesticides and their related products, a total of 98 analytes, belonging to organophosphorus pesticides (OPPs) and carbamates, in foods. The proposed method makes use of a modified QuEChERS (quick, easy, cheap, effective, rigged, and safe) procedure that combines isolation of the pesticides and sample clean-up in a single step. Analysis is performed by liquid chromatography-electrospray ionization-tandem mass spectrometry operated in the multiple reaction monitoring (MRM) mode, acquiring two specific precursor-product ion transitions per target compound. Two main fragment ions for each pesticide were obtained to achieve the identification according to the SANCO guidelines 10684/2009. The method was validated with various food samples, including edible oil, meat, egg, cheese, chocolate, coffee, rice, tree nuts, citric fruits, vegetables, etc. No significant matrix effect was observed for tested pesticides, therefore, matrix-matched calibration was not necessary. Calibration curves were linear and covered from 1 to 20 microg L(-1) for all compounds studied. The average recoveries, measured at 10 microg kg(-1), were in the range 70-120% for all of the compounds tested with relative standard deviations below 20%, while a value of 10 microg kg(-1) has been established as the method limit of quantitation (MLOQ) for all target analytes. Similar trueness and precision results were also obtained for spiking at 200 microg kg(-1). Expanded uncertainty values were in the range 21-27% while the HorRat ratios were below 1. The method has been successfully applied to the analysis of 700 food samples in the course of a baseline monitoring study of OPPs and carbamates.

  3. Piezoelectric Biosensors for Organophosphate and Carbamate Pesticides: A Review

    Giovanna Marrazza

    2014-09-01

    Full Text Available Due to the great amount of pesticides currently being used, there is an increased interest for developing biosensors for their detection. Among all the physical transducers, piezoelectric systems have emerged as the most attractive due to their simplicity, low instrumentation costs, possibility for real-time and label-free detection and generally high sensitivity. This paper presents an overview of biosensors based on the quartz crystal microbalance, which have been reported in the literature for organophosphate and carbamate pesticide analysis.

  4. Biodegradation of a carbamate pesticide, Propoxur, in rat tissues.

    Kumar, R; Madhavi, N B; Sharma, C B

    1993-01-01

    Propoxur (Baygon, 2-isopropoxyphenyl N-methylcarbamate) is a carbamate pesticide commonly used against house insects. When the insecticide was administered intramuscularly in rats it was converted to a new metabolite which was found to be present in the serum, liver, kidney and brain 6 h after the administration of the pesticide. The metabolite was purified by high performance liquid to chromatography and comparison of the infrared spectra of Propoxur and the metabolite showed that a deamination reaction was responsible for the formation of the metabolite from the parent pesticide. The pesticide also induced haematological changes such as an increased level of total bilubrin, amylase and glutamic-oxalacetic transaminase and decrease of cholinesterase activity, indicating damage of the liver and nervous system in rats.

  5. 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

    The aim of the study is to evaluate the potential cumulative effects of organophosphorus and carbamate pesticides that act through a common mechanism of toxicity, and to assess the long- and short-term risks for the Danish population. The intake estimates are based on dietary intake data collected...... in the Danish nation-wide food consumption survey in 1995. The pesticide data are based on the Danish pesticide residue-monitoring programme from 1996-2001. The amount of 35 organophosphorus pesticides and carbamates were included in the cumulative risk assessment. Processing factors, such as reduction...... of pesticide levels by rinsing and peeling, were applied in the exposure assessment. The "Toxicity Equivalence Factor" (TEF) approach was used to normalise the toxicity of the different organophosphorus and carbamate pesticides. Cumulative chronic exposure of organophosphorus and carbamates pesticides via...

  6. 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

    Organophosphorus and carbamate pesticides are acetylcholinesterase-inhibiting pesticides and as such have a common mode of action. We assessed the cumulative acute exposure of the population of Denmark to 25 organophosphorus and carbamate pesticide residues from the consumption of fruit, vegetables...... the nationwide dietary survey conducted in 2000-2002. Contributions from 43 commodities were included in the calculations. We used the relative potency factor (RPF) approach to normalize the toxicity of the various organophosphorus and carbamate pesticides to the two index compounds chlorpyriphos...

  7. DETERMINATION OF CARBAMATE, UREA, AND THIOUREA PESTICIDES AND HERBICIDES IN WATER

    Microbe liquid chromatography and positive ion electrospray mass spectrometry are applied to the determination of 16 carbamate, urea, and thiourea pesticides and herbicides in water. The electrospray mass spectra of the analytes were measured and are discussed and mobile phase m...

  8. Investigation of kinetic interactions between approved oximes and human acetylcholinesterase inhibited by pesticide carbamates.

    Wille, Timo; Kaltenbach, Lisa; Thiermann, Horst; Worek, Franz

    2013-12-01

    Carbamates are widely used for pest control and act primarily by inhibition of insect and mammalian acetylcholinesterase (AChE). Accidental or intentional uptake of carbamates may result in typical signs and symptoms of cholinergic overstimulation which cannot be discriminated from those of organophosphorus pesticide poisoning. There is an ongoing debate whether standard treatment with atropine and oximes should be recommended for human carbamate poisoning as well, since in vitro and in vivo animal data indicate a deleterious effect of oximes when used in combination with the N-methyl carbamate carbaryl. Therefore, we performed an in vitro kinetic study to investigate the effect of clinically used oximes on carbamoylation and decarbamoylation of human AChE. It became evident that pralidoxime and obidoxime in therapeutic concentrations aggravate the inhibition of AChE by carbaryl and propoxur, with obidoxime being substantially more potent compared to 2-PAM. However, obidoxime had no impact on the decarbamoylation kinetics. Hence, the administration of 2-PAM and especially of obidoxime to severely propoxur and carbaryl poisoned humans cannot be recommended.

  9. Assessment of Organophosphate and Carbamate Pesticide Residues in Cigarette Tobacco with a Novel Cell Biosensor

    Spiridon Kintzios

    2008-04-01

    Full Text Available The conventional analysis of pesticide residues in analytical commodities, such as tobacco and tobacco products is a labor intensive procedure, since it is necessary to cover a wide range of different chemicals, using a single procedure. Standard analysis methods include extensive sample pretreatment (with solvent extraction and partitioning phases and determination by GC and HPLC to achieve the necessary selectivity and sensitivity for the different classes of compounds under detection. As a consequence, current methods of analysis provide a limited sample capacity. In the present study, we report on the development of a novel cell biosensor for detecting organophosphate and carbamate pesticide residues in tobacco. The sensor is based on neuroblastoma N2a cells and the measurement of changes of the cell membrane potential, according to the working principle of the Bioelectric Recognition Assay (BERA. The presence of pesticide residues is detected by the degree of inhibition of acetylcholine esterase (AChE. The sensor instantly responded to both the organophoshate pesticide chlorpyriphos and the carbamate carbaryl in a concentration-dependent pattern, being able to detect one part per billion (1 ppb. Additionally, tobacco leaf samples (in blended dry form were analyzed with both the novel biosensor and conventional methods, according to a double-blind protocol. Pesticide residues in tobacco samples caused a considerable cell membrane hyperpolarization to neuroblastoma cells immobilized in the sensor, as indicated by the increase of the negative sensor potential, which was clearly distinguishable from the sensor’s response against pesticide-free control samples. The observed response was quite reproducible, with an average variation of +5,6%. Fluorescence microscopy observations showed that treatment of the cells with either chlorpyrifos or carbaryl was associated with increased [Ca2+]cyt . The novel biosensor offers fresh

  10. Medical treatment of acute poisoning with organophosphorus and carbamate pesticides.

    Jokanović, Milan

    2009-10-28

    Organophosphorus compounds (OPs) are used as pesticides and developed as warfare nerve agents such as tabun, soman, sarin, VX and others. Exposure to even small amounts of an OP can be fatal and death is usually caused by respiratory failure. The mechanism of OP poisoning involves inhibition of acetylcholinesterase (AChE) leading to inactivation of the enzyme which has an important role in neurotransmission. AChE inhibition results in the accumulation of acetylcholine at cholinergic receptor sites, producing continuous stimulation of cholinergic fibers throughout the nervous systems. During more than five decades, pyridinium oximes have been developed as therapeutic agents used in the medical treatment of poisoning with OP. They act by reactivation of AChE inhibited by OP. However, they differ in their activity in poisoning with pesticides and warfare nerve agents and there is still no universal broad-spectrum oxime capable of protecting against all known OP. In spite of enormous efforts devoted to development of new pyridinium oximes as potential antidotes against poisoning with OP only four compounds so far have found its application in human medicine. Presently, a combination of an antimuscarinic agent, e.g. atropine, AChE reactivator such as one of the recommended pyridinium oximes (pralidoxime, trimedoxime, obidoxime and HI-6) and diazepam are used for the treatment of OP poisoning in humans. In this article the available data related to medical treatment of poisoning with OP pesticides are reviewed and the current recommendations are presented.

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

    Christo J. Botha

    2015-03-01

    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.

  12. 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.

  13. Adsorption Kinetics of Carbamate Pesticide in Rice Field Soil

    Soontree Khuntong

    2010-07-01

    Full Text Available Ultrasonic extraction (75.55% with petroleum ether:acetone (1:1, v/v was employed for extraction of carbofuran in rice field soil. The amounts of carbofuran were determined by reverse phase HPLC. The analytical method provided high precision and accuracy with the relative error of 0.47%. The percentage of recoveries varied from 84% to 77% in the con¬centration ranges of 10–40 mg/L of spiked soil samples. The carbofuran residues in the rice field soil significantly decreased year by year because of pesticide properties, soil properties and degradation conditions. A high amount of residues was found in the plots that contained high organic contents. The adsorption of carbofuran in soil reached equilibrium within 23 h. The percentage of adsorption varied from almost 30% to 80% depending on concentrations of carbofuran. The adsorption of carbofuran agreed with Freundlich isotherms; q = 7.07 x 10-5Cf2.5092; with the correlation coefficient of 0.9281. Organic carbon coefficient, Koc, was 1.91 x 10-3 mg/L calculated from Kd, and half-life (8.9 d of adsorbed carbofuran. The GUS index (6.37 calculated from Koc presented a high lixiviation potential. The positive ΔG indicated the non-spontaneous reaction. Carbofuran rapidly desorbed from soil at the desorption rate of 0.0228 mg/kg soil d. Kinetic studies provided the first order reaction with the reaction rate of 0.0779 mg/d and half-life of 8.9 days.

  14. From immunotoxicity to carcinogenicity: the effects of carbamate pesticides on the immune system.

    Dhouib, Ines; Jallouli, Manel; Annabi, Alya; Marzouki, Soumaya; Gharbi, Najoua; Elfazaa, Saloua; Lasram, Mohamed Montassar

    2016-05-01

    The immune system can be the target of many chemicals, with potentially severe adverse effects on the host's health. In the literature, carbamate (CM) pesticides have been implicated in the increasing prevalence of diseases associated with alterations of the immune response, such as hypersensitivity reactions, some autoimmune diseases and cancers. CMs may initiate, facilitate, or exacerbate pathological immune processes, resulting in immunotoxicity by induction of mutations in genes coding for immunoregulatory factors and modifying immune tolerance. In the present study, direct immunotoxicity, endocrine disruption and inhibition of esterases activities have been introduced as the main mechanisms of CMs-induced immune dysregulation. Moreover, the evidence on the relationship between CM pesticide exposure, dysregulation of the immune system and predisposition to different types of cancers, allergies, autoimmune and infectious diseases is criticized. In addition, in this review, we will discuss the relationship between immunotoxicity and cancer, and the advances made toward understanding the basis of cancer immune evasion.

  15. Biodegradation of carbamate pesticides by natural river biofilms in different seasons and their effects on biofilm community structure.

    Tien, Chien-Jung; Lin, Mon-Chu; Chiu, Wan-Hsin; Chen, Colin S

    2013-08-01

    This study investigated the ability of natural river biofilms from different seasons to degrade the carbamate pesticides methomyl, carbaryl and carbofuran in single and multiple pesticide systems, and the effects of these pesticides on algal and bacterial communities within biofilms. Spring biofilms had the lowest biomass of algae and bacteria but showed the highest methomyl degradation (>99%) and dissipation rates, suggesting that they might contain microorganisms with high methomyl degradation abilities. Degradation of carbofuran (54.1-59.5%) by biofilms in four seasons was similar, but low degradation of carbaryl (0-27.5%) was observed. The coexistence of other pesticides was found to cause certain effects on pesticide degradation and primarily resulted in lower diversity of diatoms and bacteria than when using a single pesticide. The tolerant diatoms and bacteria potentially having the ability to degrade test pesticides were identified. River biofilms could be suitable biomaterials or used to isolate degraders for bioremediating pesticide-contaminated water.

  16. Urinary concentrations of organophosphate and carbamate pesticides in residents of a vegetarian community.

    Berman, T; Göen, T; Novack, L; Beacher, L; Grinshpan, L; Segev, D; Tordjman, K

    2016-11-01

    Few population studies have measured urinary levels of pesticides in individuals with vegan, vegetarian, or organic diets. The objectives of this study were to evaluate whether a vegan/vegetarian diet was associated with increased exposure to organophosphate and carbamate pesticides, and to evaluate the impact of organic consumption on pesticide exposure in vegans and vegetarians. In the current pilot study conducted in 2013-2014, we collected spot urine samples and detailed 24h recall dietary data in 42 adult residents of Amirim, a vegetarian community in Northern Israel. We measured urinary levels of non-specific organophosphate pesticide metabolites (dialkylphosphates, (DAPs)) and specific metabolites of the current-use pesticides chlorpyrifos (3,5,6-trichloro-2-pyridinol (TCPy)), propoxur (-isopropoxyphenol (IPPX)), and carbaryl (1-naphthol). Six DAP metabolites were detected in between 67 and 100% of urine samples, with highest geometric mean concentrations for dimethylphosphate (19.2μg/g). Creatinine-adjusted median concentrations of total DAPs and of TCPy were significantly higher in Amirim residents compared to the general Jewish population in Israel (0.29μmol/g compared to 0.16, p25% of the produce they consume is organic (0.065μmol/L compared to 0.22, pvegetarian community, a positive association between vegetable intake and urinary levels of a chlorpyrifos specific metabolite, and lower levels of total dimethyl phosphate in individuals reporting higher intake of organic produce. Results suggest that consumption of organic produce may offer some protection from increased exposure to organophosphate pesticide residues in vegetarians.

  17. 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.

  18. Solid phase extraction and determination of carbamate pesticides in water samples by reverse-phase HPLC

    Moreno-Tovar, J.; Santos-Delgado, M.J. [Departamento de Quimica Analitica, Facultad de ciencias Quimicas, Universidad Complutense de Madrid (Spain)

    1995-12-31

    Solid phase extraction. SPE. using C{sub 1}8 bonded silica cartridges for trace amounts determination of carbaryl, propoxur, thiram, propham and methiocarb in water samples was studied and the breakthrough volume of the cartridges was established. The high enrichment factor and large injection volume admissible in the isocratic reverse-phase HPLC system allows pesticides determination with UV detection at 22o nm even at a concentration lower than 0.05 mug/L. Purified tap natural and underground water samples were spiked with carbamate pesticides in the concentration range 0.16-16.0 mug/L. Large volumes of samples (up to 2L) were passed through available C{sub 1}8, cartridges and eluted with acetonitrile. The preconcentrated samples were analyzed by HPLC using a Spherisorb ODS column with a 42.58 acetonitrile-water mobile phase. From replicate samples, recovery for the pesticides ranged from 79.0 to 103.7% except for thiran which is not retained. Tehe relative standard deviation (n=4 at 0.16 to 1.61 mug/L concetration level) range from 1.1 to 6.8%. (Author) 14 refs.

  19. Preparation of a graphene-based magnetic nanocomposite for the extraction of carbamate pesticides from environmental water samples.

    Wu, Qiuhua; Zhao, Guangying; Feng, Cheng; Wang, Chun; Wang, Zhi

    2011-11-04

    A graphene-based magnetic nanocomposite was synthesized and used for the first time as an effective adsorbent for the preconcentration of the five carbamate pesticides (metolcarb, carbofuran, pirimicarb, isoprocarb and diethofencarb) in environmental water samples prior to high performance liquid chromatography-diode array detection. The properties of the magnetic nanocomposite were characterized by scanning electron microscopy and X-ray diffraction. This novel graphene-based magnetic nanocomposite showed great adsorptive ability towards the analytes. The method, which takes the advantages of both nanoparticle adsorption and magnetic phase separation from the sample solution, could avoid some of the time-consuming experimental procedures related to the traditional solid phase extraction. Various experimental parameters that could affect the extraction efficiencies have been investigated. Under the optimum conditions, the enrichment factors of the method for the analytes were in the range from 474 to 868. A linear response was achieved in the concentration range of 0.1-50 ng mL(-1). The limits of detection of the method at a signal to noise ratio of 3 for the pesticides were 0.02-0.04 ng mL(-1). Compared with the dispersive liquid-liquid microextraction and the ultrasound-assisted surfactant-enhanced emulsification microextraction, much higher enrichment factors and sensitivities were achieved with the developed method. The method has been successfully applied for the determination of the carbamate pesticides in environmental water samples.

  20. 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

    2014-05-30

    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 0.02ng/mL, 0.012ng/mL, 0.04ng/mL, 0.05ng/mL and 0.1ng/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.

  1. Extraction of carbamate pesticides in fruit samples by graphene reinforced hollow fibre liquid microextraction followed by high performance liquid chromatographic detection.

    Ma, Xiaoxing; Wang, Juntao; Wu, Qiuhua; Wang, Chun; Wang, Zhi

    2014-08-15

    Graphene reinforced hollow fibre liquid phase microextraction combined with high performance liquid chromatography-diode array detection was developed for the determination of some carbamate pesticides (metolcarb, carbaryl, isoprocarb, and diethofencarb) in fruit samples. The main parameters that affect the extraction efficiency for the carbamates were investigated. Under the optimum conditions, a good linearity was observed in the range of 1.0-100.0 ng g(-1) for carbaryl and 3.0-100.0 ng g(-1) for the other three analytes, with the correlation coefficients (r) of 0.9965-0.9993. The limits of detection of the method ranged from 0.2 to 1.0 ng g(-1). The relative standard deviations were in the range from 6.2% to 7.8%. The results indicated that the developed method is sensitive and efficient for the determination of the carbamate pesticides in fruit samples.

  2. 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.

  3. Fluorescence biosensing strategy based on mercury ion-mediated DNA conformational switch and nicking enzyme-assisted cycling amplification for highly sensitive detection of carbamate pesticide.

    Wang, Xiuzhong; Hou, Ting; Dong, Shanshan; Liu, Xiaojuan; Li, Feng

    2016-03-15

    Pesticides are of great importance in agricultural and biological fields, but pesticide residues may harm the environment and human health. A highly sensitive fluorescent biosensor for the detection of carbamate pesticide has been developed based on acetylcholinesterase (AChE)-catalyzed hydrolysis product triggered Hg(2+) release coupled with subsequent nicking enzyme-induced cleavage of a duplex DNA for cycling amplification. In this protocol, two DNA probes, an unmodified single-stranded helper DNA probe 1 (HP1) and a quencher-fluorophore probe (QFP) are ingeniously designed. HP1 can be folded into hairpin configuration through T-Hg(2+)-T base pair formation. QFP, labeled with FAM and BHQ1 at its two terminals, contains the recognition sequence and the cleavage site of the nicking enzyme. In the presence of carbamate pesticide, the activity of AChE is inhibited, and the amount of the product containing the thiol group generated by the hydrolysis reaction of acetylthiocholine chloride (ACh) decreases, resulting in the release of a low concentration of Hg(2+). The number of HP1 that can be selectively unfolded would be reduced and the subsequent nicking enzyme-assisted cleavage processes would be affected, resulting in decreased fluorescence signals. The fluorescence intensity further decreases with the increase of the pesticide concentration. Therefore, the pesticide content can be easily obtained by monitoring the fluorescence signal change, which is inversely proportional to the logarithm of the pesticide concentration. The detection limit of aldicarb, the model analyte, is 3.3 μgL(-1), which is much lower than the Chinese National Standards or those previously reported. The as-proposed method has also been applied to detect carbamate pesticide residues in fresh ginger and artificial lake water samples with satisfactory results, which demonstrates that the method has great potential for practical application in biological or food safety field.

  4. A simple electrochemical biosensor based on AuNPs/MPS/Au electrode sensing layer for monitoring carbamate pesticides in real samples.

    Song, Yonghai; Chen, Jingyi; Sun, Min; Gong, Coucong; Shen, Yuan; Song, Yonggui; Wang, Li

    2016-03-01

    A simple electrochemical biosensor for quantitative determination of carbamate pesticide was developed based on a sensing interface of citrate-capped gold nanoparticles (AuNPs)/(3-mercaptopropyl)-trimethoxysilane (MPS)/gold electrode (Au). The biosensor was fabricated by firstly assembling three-dimensional (3D) MPS networks on Au electrode and subsequently assembling citrate-capped AuNPs on 3D MPS network via AuS bond. The interface of AuNPs/MPS/Au was negatively charged originating from the citrate coated on AuNPs that would repulse the negatively charged ferricyanide ([Fe(CN)6](3-/4-)) to produce a negative response. In the presence of acetylcholinesterase (AChE) and acetylthiocholine (ATCl), the AChE catalyzes the hydrolysis of ATCl into positively charged thiocholine which would replace the citrate on AuNPs through the strong AuS bond and convert the negative charged surface to be positively charged. The resulted positively charged AuNPs/MPS/Au then attracted the [Fe(CN)6](3-/4-) to produce a positive response. Based on the inhibition of carbamate pesticides on the activity of AChE, the pesticide could be quantitatively determined at a very low potential. The linear range was from 0.003 to 2.00 μM. The sensing platform was also proved to be suitable for carbamate pesticides detection in practical sample.

  5. Studies on the Purification and Characterization of Soybean Esterase,and Its Sensitivity to Organophosphate and Carbamate Pesticides

    LI Jian-ke; ZHOU Yan-li; WEN Yan-xia; WANG Jian-hua; HU Qiu-hui

    2009-01-01

    Soybean esterase,a cholinesterase-like enzyme,was purified by differential centrifugation firstly,then,ammonium sulfate precipitation,dialysis,and finally,DEAE-cellulose-32 ion-exchange chromatography after extracting it from soybean seeds with phosphate buffer(0.3 mol L-1,pH 7.0).The extract recovery rate of the purified enzyme was 8.18% and purification fold was 91.58.The soybean esterase appeared as two bands on the denaturing SDS-PAGE with molecular weights of 24 and 37.2 kDa,respectively,which proved that it is a dimer protein consisting of two subunits.The result of nondenaturing PAGE revealed that the soybean esterase is a single band with cholinesterase-like activity using α-naphthyl acetate as the substrate and fast blue B salt as coloring agent.The esterase showed very high sensitivity to 18 kinds of organophosphate pesticides and 6 kinds of carbamate pesticides with the lowest detective limits of 0.03125-0.0625 and 0.03 125-0.25 mg kg-1,respectively,and can meet the demands of MRL specified by the most countries.

  6. 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.

  7. Poisoning of cats and dogs by the carbamate pesticides aldicarb and carbofuran.

    de Siqueira, Adriana; Salvagni, Fernanda Auciello; Yoshida, Alberto Soiti; Gonçalves-Junior, Vagner; Calefi, Atilio Sersun; Fukushima, André Rinaldi; Spinosa, Helenice de Souza; Maiorka, Paulo César

    2015-10-01

    The intentional and accidental poisoning of animals and people is a threat to public health and safety worldwide. Necropsies and histopathological examinations of 26 cats and 10 dogs poisoned by the carbamates aldicarb and carbofuran, confirmed by thin layer chromatography (TLC) and high performance liquid chromatography with diode-array detector (HPLC-DAD) were analysed, with variable post mortem interval and conservation of the carcass. Biological matrices were collected for toxicological and histopathological analyses. High performance liquid chromatography with diode-array detector (HPLC-DAD) was utilized to detect aldicarb and its metabolites, aldicarb sulphoxide and aldicarb sulphone, and carbofuran. The variable post mortem interval and the method of conservation of the carcass may be harmful to toxicological, necroscopic and histopathological analyses, that should be performed in order to provide reliable evidences to investigate possible poisoning of animals, which is cruel crime, and are usually linked to domestic or social conflict.

  8. SELECTIVE ISOLATION OF A GRAM NEGATIVE CARBAMATE PESTICIDE DEGRADING BACTERIUM FROM BRINJAL CULTIVATED SOIL

    Dilara Islam Sharif

    2013-01-01

    Full Text Available A bacterial species having the ability to grow in the presence of carbosulfan pesticide “Marshall” was isolated from Solanum melongena (brinjal cultivated soil in Khulna region, Bangladeh, having a history of pesticide usage. The strain was morphologically and biochemically identified to belong to the genera Pseudomonas. A comparative study of growth of this strain with other isolated bacteria showed its ability to grow in the presence of different concentrations of Marshall. The susceptibility of the stain to Marshall was also assessed through disk diffusion assay which showed the strain to be resistant at concentrations of Marshal commonly used under field conditions. The selected strain also showed its capability to degrade Marshall through observed characteristics on sublimated agar plates. The biodegradation capability of the strain isolated in this study can be valuable for further study towards bioremediation of pesticide contaminated soils.

  9. The Stepwise Behavioral Responses: Behavioral Adjustment of the Chinese Rare Minnow (Gobiocypris rarus in the Exposure of Carbamate Pesticides

    Zongming Ren

    2013-01-01

    Full Text Available In order to illustrate the behavioral regulation in environmental stress, the behavioral responses of the Chinese rare minnow (Gobiocypris rarus to arprocarb, carbofuran, and oxamyl were analyzed with an online monitoring system. The Self-Organizing Map (SOM was used to define the patterns of the behavioral data obtained from treatments at concentrations of 0.1 toxic unit (TU, 1 TU, 2 TU, 5 TU, 10 TU, and 20 TU and a control. In certain cases, differences among the carbamate pesticides (CPs tested were observed. The profiles of behavioral strength (BS in SOM varied according to the concentration used. The time of the first significant decrease of the BS varied inversely with the CP concentrations. The results suggested that the behavioral regulation in the stepwise behavioral responses (SBR was evident. The primary movement behaviors shown by the SBR model included no effect, stimulation, acclimation, adjustment (readjustment, and toxic effect, especially at the lower concentrations. However, higher stress (10 TU and 20 TU might limit the function of the behavioral adjustment produced by the intrinsic response mechanisms. It was concluded that SBR, which were affected by both the concentration and the exposure time, could be used as a suitable indicator in the ecotoxicological risk assessment of CPs.

  10. Sequential injection kinetic spectrophotometric determination of quaternary mixtures of carbamate pesticides in water and fruit samples using artificial neural networks for multivariate calibration

    Chu, Ning; Fan, Shihua

    2009-12-01

    A new analytical method was developed for the simultaneous kinetic spectrophotometric determination of a quaternary carbamate pesticide mixture consisting of carbofuran, propoxur, metolcarb and fenobucarb using sequential injection analysis (SIA). The procedure was based upon the different kinetic properties between the analytes reacted with reagent in flow system in the non-stopped-flow mode, in which their hydrolysis products coupled with diazotized p-nitroaniline in an alkaline medium to form the corresponding colored complexes. The absorbance data from SIA peak time profile were recorded at 510 nm and resolved by the use of back-propagation-artificial neural network (BP-ANN) algorithms for multivariate quantitative analysis. The experimental variables and main network parameters were optimized and each of the pesticides could be determined in the concentration range of 0.5-10.0 μg mL -1, at a sampling frequency of 18 h -1. The proposed method was compared to other spectrophotometric methods for simultaneous determination of mixtures of carbamate pesticides, and it was proved to be adequately reliable and was successfully applied to the simultaneous determination of the four pesticide residues in water and fruit samples, obtaining the satisfactory results based on recovery studies (84.7-116.0%).

  11. Surface display of recombinant Drosophila melanogaster acetylcholinesterase for detection of organic phosphorus and carbamate pesticides.

    Jingquan Li

    Full Text Available Acetylcholinesterase (AChE is commonly used for the detection of organophosphate (OP and carbamate (CB insecticides. However, the cost of this commercially available enzyme is high, making high-throughput insecticide detection improbable. In this study we constructed a new AChE yeast expression system in Saccharomyces cerevisiae for the expression of a highly reactive recombinant AChE originating from Drosophila melanogaster (DmAChE. Specifically, the coding sequence of DmAChE was fused with the 3'-terminal half of an α-agglutinin anchor region, along with an antigen tag for the detection of the recombinant protein. The target sequence was cloned into the yeast expression vector pYes-DEST52, and the signal peptide sequence was replaced with a glucoamylase secretion region for induced expression. The resultant engineered vector was transformed into S. cerevisiae. DmAChE was expressed and displayed on the cell surface after galactose induction. Our results showed that the recombinant protein displayed activity comparable to the commercial enzyme. We also detected different types of OP and CB insecticides through enzyme inhibition assays, with the expressed DmAChE showing high sensitivity. These results show the construction of a new yeast expression system for DmAChE, which can subsequently be used for detecting OP and CB insecticides with reduced economic costs.

  12. [Determination of 51 carbamate pesticide residues in vegetables by liquid chromatography-tandem mass spectrometry based on optimization of QuEChERS sample preparation method].

    Wang, Lianzhu; Zhou, Yu; Huang, Xiaoyan; Wang, Ruilong; Lin, Zixu; Chen, Yong; Wang, Dengfei; Lin, Dejuan; Xu, Dunming

    2013-12-01

    The raw extracts of six vegetables (tomato, green bean, shallot, broccoli, ginger and carrot) were analyzed using gas chromatography-mass spectrometry (GC-MS) in full scan mode combined with NIST library search to confirm main matrix compounds. The effects of cleanup and adsorption mechanisms of primary secondary amine (PSA) , octadecylsilane (C18) and PSA + C18 on co-extractives were studied by the weight of evaporation residue for extracts before and after cleanup. The suitability of the two versions of QuEChERS method for sample preparation was evaluated for the extraction of 51 carbamate pesticides in the six vegetables. One of the QuEChERS methods was the original un-buffered method published in 2003, and the other was AOAC Official Method 2007.01 using acetate buffer. As a result, the best effects were obtained from using the combination of C18 and PSA for extract cleanup in vegetables. The acetate-buffered version was suitable for the determination of all pesticides except dioxacarb. Un-buffered QuEChERS method gave satisfactory results for determining dioxacarb. Based on these results, the suitable QuEChERS sample preparation method and liquid chromatography-positive electrospray ionization-tandem mass spectrometry under the optimized conditions were applied to determine the 51 carbamate pesticide residues in six vegetables. The analytes were quantified by matrix-matched standard solution. The recoveries at three levels of 10, 20 and 100 microg/kg spiked in six vegetables ranged from 58.4% to 126% with the relative standard deviations of 3.3%-26%. The limits of quantification (LOQ, S/N > or = 10) were 0.2-10 microg/kg except that the LOQs of cartap and thiofanox were 50 microg/kg. The method is highly efficient, sensitive and suitable for monitoring the 51 carbamate pesticide residues in vegetables.

  13. Determination of poorly fluorescent carbamate pesticides in water, bendiocarb and promecarb, using cyclodextrin nanocavities and related media

    Pacioni, Natalia L. [Instituto de Investigaciones en Fisico Quimica de Cordoba (INFIQC), Departamento de Quimica Organica, Facultad de Ciencias Quimicas, Universidad Nacional de Cordoba, Ciudad Universitaria, 5000 Cordoba (Argentina); Veglia, Alicia V. [Instituto de Investigaciones en Fisico Quimica de Cordoba (INFIQC), Departamento de Quimica Organica, Facultad de Ciencias Quimicas, Universidad Nacional de Cordoba, Ciudad Universitaria, 5000 Cordoba (Argentina)]. E-mail: aveglia@mail.fcq.unc.edu.ar

    2007-01-30

    The effect of native cyclodextrins ({alpha}, {beta}, or {gamma}CD with six, seven and eight glucose units, respectively), hydroxypropyl-{beta}-cyclodextrin (HPCD), chitosan (CHT) and glucose in water solution or water with n-propylamine (PA) as co-solvent upon the UV-vis and fluorescence properties of poorly fluorescent N-methyl carbamates pesticides (C) as bendiocarb (2,2-dimethyl-1,3-benzodioxol-4-ol methylcarbamate, BC) and promecarb (3-methyl-5-(1-methylethyl)phenol methylcarbame, PC) was examined. Fluorescent enhancement was found for both substrates with all CDs in water or PA-water except from PC with {alpha}CD. The addition of CHT increases the fluorescence of BC but decreases the fluorescence of PC, and glucose addition gives in both cases no spectral changes. Host-guest interaction was clearly determined by fluorescence enhancement with {beta}CD and HPCD with a 1:1 stoichiometry for the complexes (C:CD). The values obtained for the association constants (K {sub A}, M{sup -1}) were (6 {+-} 2) x 10{sup 2} and (2.3 {+-} 0.3) x 10{sup 2} for BC:{beta}CD and BC:HPCD complexes, respectively. For PC:{beta}CD and PC:HPCD the values of K {sub A} were (19 {+-} 2) x 10{sup 2} and (21 {+-} 2) x 10{sup 2}, respectively. The ratio of the fluorescence quantum yields for the bound and free substrates ({phi} {sup CCD}/{phi} {sup C}) was in the range 1.74-3.8. The limits of detection (L {sub D}, {mu}g mL{sup -1}) for the best conditions were (0.57 {+-} 0.02) for BC with HPCD and (0.091 {+-} 0.002) for PC with {beta}CD in water. Application to the analysis in pesticide spiked samples of tap water and fruit yields satisfactory apparent recoveries (84-114%), and for the extraction procedure in fruits and a commercial formulation, recoveries were of 81-98% and 104%, respectively. The method is rapid, simple, direct, sensitive and useful for pesticide analysis.

  14. Ionic liquid polymer functionalized carbon nanotubes-doped poly(3,4-ethylenedioxythiophene) for highly-efficient solid-phase microextraction of carbamate pesticides.

    Wu, Mian; Wang, Liying; Zeng, Baizhao; Zhao, Faqiong

    2016-04-29

    A poly(3,4-ethylenedioxythiophene)-ionic liquid polymer functionalized multiwalled carbon nanotubes (PEDOT-PIL/MWCNTs) composite solid-phase microextraction (SPME) coating was fabricated by electrodeposition. After being dipped in Nafion solution, a Nafion-modified coating was obtained. The outer layer Nafion played a crucial role in enhancing the durability and stability of the coating, thus it was robust enough for replicated extraction for at least 150 times without decrease of extraction performance. The Nafion-modified coating exhibited much higher sensitivity than commercial coatings for the direct extraction of carbamate pesticides in aqueous solutions, due to its strong hydrophobic effect and π-π affinity based enrichment. When it was used for the determination of carbamate pesticides in combination with gas chromatography-flame ionization detection, good linearity (correlation coefficients higher than 0.9981), low limits of detection (15.2-27.2 ng/L) and satisfactory precision (relative standard deviation pesticides in apple and lettuce samples, and acceptable recoveries (i.e. 87.5-106.5%) were obtained for the standard addition.

  15. Novel method for the determination of five carbamate pesticides in water samples by dispersive liquid-liquid microextraction combined with high performance liquid chromatography

    Zhi Mei Liu; Xiao Huan Zang; Wei Hua Liu; Chun Wang; Zhi Wang

    2009-01-01

    A novel method for the determination of five carbamate pesticides(metolcarb,carbofuran,carbaryl,isoprocard and diethofencard)in water samples was developed by dispersive liquid-liquid microextraction(DLLME)coupled with high performance liquid chromatography-diode array detector(HPLC-DAD).Some experimental parameters that influence the extraction efficiency were studied and optimized to obtain the best extraction results.Under the optimum conditions for the method,the calibration curve was linear in the concentration range from 5 to I000 ng mL-1 for all the five carbamate pesticides,with the correlation coefficients(r2)varying from 0.9984 to 0.9994.Good enrichment factors were achieved ranging from 80 to 177-fold,depending on the compound.The limits of detection(LODs)(S/N = 3)were ranged from 0.1 to 0.5 ng mL-1.The method has been successfully applied to the analysis of the pesticide residues in environmental water samples.

  16. Organophosphate and carbamate poisoning.

    King, Andrew M; Aaron, Cynthia K

    2015-02-01

    Organophosphates (OPs) and carbamates have a wide variety of applications, most commonly as pesticides used to eradicate agricultural pests or control populations of disease-carrying vectors. Some OP and carbamates have therapeutic indications such as physostigmine. Certain organophosphorus compounds, known as nerve agents, have been employed in chemical warfare and terrorism incidents. Both classes inhibit acetylcholinesterase (AChE) enzymes, leading to excess acetylcholine accumulation at nerve terminals. In the setting of toxicity from either agent class, clinical syndromes result from excessive nicotinic and muscarinic neurostimulation. The toxic effects from OPs and carbamates differ with respect to reversibility, subacute, and chronic effects. Decontamination, meticulous supportive care, aggressive antimuscarinic therapy, seizure control, and administration of oximes are cornerstones of management.

  17. Optimization and validation of liquid-liquid extraction with low temperature partitioning for determination of carbamates in water

    Machado Goulart, Simone; Domingos Alves, Renata; Neves, Antonio Augusto; Queiroz, Jose Humberto de; Conde de Assis, Tamires [Departamento de Quimica, Universidade Federal de Vicosa, Vila Gianetti, Casa 24, 36 570-000 Vicosa, MG (Brazil); Queiroz, Maria Eliana L.R. de, E-mail: meliana@ufv.br [Departamento de Quimica, Universidade Federal de Vicosa, Vila Gianetti, Casa 24, 36 570-000 Vicosa, MG (Brazil)

    2010-06-25

    Using a 2{sup 3} experimental design, liquid-liquid extraction with low temperature partitioning (LLE-LTP) was optimized and validated for analysis of three carbamates (aldicarb, carbofuran and carbaryl) in water samples. In this method, 2.0 mL of sample is placed in contact with 4.0 mL of acetonitrile. After agitation, the sample is placed in a freezer for 3 h for phase separation. The organic extract is analyzed by high performance liquid chromatography with ultraviolet detection (HPLC-UV). For validation of the technique, the following figures of merit were evaluated: accuracy, precision, detection and quantification limits, linearity, sensibility and selectivity. Extraction recovery percentages of the carbamates aldicarb, carbofuran and carbaryl were 90%, 95% and 96%, respectively. Even though extremely low volumes of sample and solvent were used, the extraction method was selective and the detection and quantification limits were between 5.0 and 10.0 {mu}g L{sup -1}, and 17.0 and 33.0 {mu}g L{sup -1}, respectively.

  18. Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory; determination of selected carbamate pesticides in water by high-performance liquid chromatography

    Werner, S.L.; Johnson, S.M.

    1994-01-01

    As part of its primary responsibility concerning water as a national resource, the U.S. Geological Survey collects and analyzes samples of ground water and surface water to determine water quality. This report describes the method used since June 1987 to determine selected total-recoverable carbamate pesticides present in water samples. High- performance liquid chromatography is used to separate N-methyl carbamates, N-methyl carbamoyloximes, and an N-phenyl carbamate which have been extracted from water and concentrated in dichloromethane. Analytes, surrogate compounds, and reference compounds are eluted from the analytical column within 25 minutes. Two modes of analyte detection are used: (1) a photodiode-array detector measures and records ultraviolet-absorbance profiles, and (2) a fluorescence detector measures and records fluorescence from an analyte derivative produced when analyte hydrolysis is combined with chemical derivatization. Analytes are identified and confirmed in a three-stage process by use of chromatographic retention time, ultraviolet (UV) spectral comparison, and derivatization/fluorescence detection. Quantitative results are based on the integration of single-wavelength UV-absorbance chromatograms and on comparison with calibration curves derived from external analyte standards that are run with samples as part of an instrumental analytical sequence. Estimated method detection limits vary for each analyte, depending on the sample matrix conditions, and range from 0.5 microgram per liter to as low as 0.01 microgram per liter. Reporting levels for all analytes have been set at 0.5 microgram per liter for this method. Corrections on the basis of percentage recoveries of analytes spiked into distilled water are not applied to values calculated for analyte concentration in samples. These values for analyte concentrations instead indicate the quantities recovered by the method from a particular sample matrix.

  19. Microwave accelerated selective Soxhlet extraction for the determination of organophosphorus and carbamate pesticides in ginseng with gas chromatography/mass spectrometry.

    Zhou, Ting; Xiao, Xiaohua; Li, Gongke

    2012-07-03

    Microwave accelerated selective Soxhlet extraction (MA-SSE), a novel selective extraction technique, was investigated in this study. A Soxhlet extraction system containing a glass filter was designed as an extractor. During the procedure of MA-SSE, both the target analytes and the interfering components were extracted from the sample into the extraction solvent enhanced by microwave irradiation. After the solvent flowed though the sorbent, the interfering components were adsorbed by the sorbent, and the target analytes remaining in the solvent were collected in the extraction bottle. No cleanup or filtration was required after extraction. The efficiency of the MA-SSE approach was demonstrated in the determination of organophosphorus and carbamate pesticide residues in ginseng by gas chromatography/mass spectrometry (GC/MS). Under the optimized conditions, low limits of detection (0.050-0.50 μg/kg) were obtained. The recoveries were in the range of 72.0-110.1% with relative standard deviations less than 7.1%. Because of the effect of microwave irradiation, MA-SSE showed significant advantage compared with other extraction techniques. The sorbent used in this study showed good cleanup ability. The mechanism of MA-SSE was demonstrated to be based on the rupture of the cell walls according to the structural changes of ginseng samples. On the basis of the results, MA-SSE as a simple and effective sample preparation technique for the analysis of pesticide residues in complex matrixes shows great promise.

  20. A novel miniaturized zinc oxide/hydroxylated multiwalled carbon nanotubes as a stir-brush microextractor device for carbamate pesticides analysis

    Makkliang, Fonthip; Kanatharana, Proespichaya [Trace Analysis and Biosensor Research Center, Prince of Songkla University, Hat Yai, Songkhla 90112 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla 90112 (Thailand); Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla 90112 (Thailand); Thavarungkul, Panote [Trace Analysis and Biosensor Research Center, Prince of Songkla University, Hat Yai, Songkhla 90112 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla 90112 (Thailand); Department of Physics, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla 90112 (Thailand); Thammakhet, Chongdee, E-mail: chongdee.t@psu.ac.th [Trace Analysis and Biosensor Research Center, Prince of Songkla University, Hat Yai, Songkhla 90112 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla 90112 (Thailand); Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla 90112 (Thailand)

    2016-04-21

    A novel miniaturized “stir-brush microextractor” was prepared using a zinc oxide/hydroxylated multiwalled carbon nanotubes (ZnO/MWCNTs–OH) coated stainless steel brush connected to a small dc motor. The synthesized zinc oxide on each strand of stainless steel had a flower-like nanostructure when observed by a scanning electron microscope (SEM). This structure produced a large surface area before it was coated with the hydroxylated multiwalled carbon nanotubes sorbent. Under optimal conditions, the developed device provided a good linearity for the extraction of carbofuran and carbaryl, in the range of 25–500 ng mL{sup −1} and 50–500 ng mL{sup −1}, respectively, with low limits of detection of 17.5 ± 2.0 ng mL{sup −1} and 13.0 ± 1.8 ng mL{sup −1}. It also provided a good stir-brush-to-stir-brush reproducibility (% relative standard deviation < 5.6%, n = 6). The device was applied for the extraction and preconcentration of carbamate pesticides in fruit and vegetable samples prior to analysis with a gas chromatograph coupled with a flame ionization detector (GC–FID). Carbofuran was found at 9.24 ± 0.93 ng g{sup −1} and carbaryl was detected at 7.05 ± 0.61 ng g{sup −1} with good recoveries in the range of 73.7 ± 10.0% to 108.4 ± 2.6% for carbofuran and 75.7 ± 10.0% to 111.7 ± 5.7% for carbaryl. - Highlights: • A brush as the sampling tool was first introduced. • A novel miniaturized and portable stir brush microextractor was developed for carbamate pesticides extraction. • Large surface area of ZnO flower-like nanostructure coated with MWCNTs–OH on each brush fiber was observed.

  1. A novel miniaturized zinc oxide/hydroxylated multiwalled carbon nanotubes as a stir-brush microextractor device for carbamate pesticides analysis.

    Makkliang, Fonthip; Kanatharana, Proespichaya; Thavarungkul, Panote; Thammakhet, Chongdee

    2016-04-21

    A novel miniaturized "stir-brush microextractor" was prepared using a zinc oxide/hydroxylated multiwalled carbon nanotubes (ZnO/MWCNTs-OH) coated stainless steel brush connected to a small dc motor. The synthesized zinc oxide on each strand of stainless steel had a flower-like nanostructure when observed by a scanning electron microscope (SEM). This structure produced a large surface area before it was coated with the hydroxylated multiwalled carbon nanotubes sorbent. Under optimal conditions, the developed device provided a good linearity for the extraction of carbofuran and carbaryl, in the range of 25-500 ng mL(-1) and 50-500 ng mL(-1), respectively, with low limits of detection of 17.5 ± 2.0 ng mL(-1) and 13.0 ± 1.8 ng mL(-1). It also provided a good stir-brush-to-stir-brush reproducibility (% relative standard deviation < 5.6%, n = 6). The device was applied for the extraction and preconcentration of carbamate pesticides in fruit and vegetable samples prior to analysis with a gas chromatograph coupled with a flame ionization detector (GC-FID). Carbofuran was found at 9.24 ± 0.93 ng g(-1) and carbaryl was detected at 7.05 ± 0.61 ng g(-1) with good recoveries in the range of 73.7 ± 10.0% to 108.4 ± 2.6% for carbofuran and 75.7 ± 10.0% to 111.7 ± 5.7% for carbaryl.

  2. Adsorption of toxic carbamate pesticide oxamyl from liquid phase by newly synthesized and characterized graphene quantum dots nanomaterials.

    Agarwal, Shilpi; Sadeghi, Nima; Tyagi, Inderjeet; Gupta, Vinod Kumar; Fakhri, Ali

    2016-09-15

    Graphene quantum dots have been synthesized using the microwave-assisted hydrothermal route. The surface textural and morphological structure of synthesized adsorbent i.e. graphene quantum dots was analyzed using various analytical techniques such as X-ray diffraction, Transmission electron Microscopy, Atomic Force Microscopy and N2 adsorption-desorption instrumental techniques. The application of graphene quantum dots as an adsorbent for the removal of noxious pesticide compound i.e. oxamyl from aqueous solutions was well investigated and elucidated. The impact of several effective parameters such as effect of agitation speed, pH, adsorbent dose, contact time, temperature and initial concentration on sorption efficiency was studied and optimized using batch adsorption experiments. The optimized pH for maximum oxamyl adsorption was found to be 8.0 and for the maximum adsorption rates the adsorbent dose of 0.6g was found to be optimum to carry out the adsorption with in less than 25min of contact time. From the results obtained, it is clear that for all contact times, an increase in oxamyl concentration resulted in increase in the percent oxamyl removal. The adsorption equilibrium and kinetic data were well fitted and found to be in good agreement with the Langmuir isotherm and pseudo-second-order kinetic model.

  3. Study on the Interaction between Humic Substances in Soil and Carbamate Pesticides Using Fluorescence Quenching Titration Method%荧光猝灭滴定法研究土壤腐殖质与氨基甲酸酯类农药相互作用

    施国兰; 郑博福; 白英臣; 吴丰昌; 吴代赦

    2012-01-01

    为研究氨基甲酸酯类农药在溶解有机质参与下的迁移转化过程,利用荧光猝灭滴定法研究了土壤HS(腐殖质)与氨基甲酸酯类农药的相互作用.结果表明,呋喃丹和西维因的荧光都能不同程度地被FA(富里酸)和HA(腐殖酸)猝灭,主要猝灭机理为静电结合猝灭.采用静态猝灭模型计算出氨基甲酸酯类农药与HS的K(结合常数),lg K由大到小为呋喃丹-HA(4.96)>西维因-HA(4.93)>呋喃丹-FA(4.72)>西维因-FA(4.68).HA与氨基甲酸酯类农药的lgK明显大于FA与氨基甲酸酯类农药,表明HS与氨基甲酸酯类农药间的作用力有疏水作用.进一步研究表明,氢键作用对HS与氨基甲酯类农药结合有一定的影响.%To reveal the mechanisms of transport and conversion of carbamate pesticides in the presence of dissolved organic matters, the fluorescence quenching titration method was applied to investigate the interactions between carbamate pesticides and humic substances in soil. The results showed that the intrinsic fluorescence of carbofuran and carbaryl was quenched by the fulvic and humic acids to varying degrees. Static quenching was the primary mechanism during this process. The binding constants (K) of carbamate pesticides and humic substances were estimated using the fluorescence static quenching model. The order of lg K were: those of carbofuran and humic acid (4. 96) > those of carbaryl and humic acid (4. 93) > those of carbofuran and fulvic acid (4. 72) > those of carbaryl and fulvic acid (4. 68). The values of lg K of carbamate pesticides and humic acids were clearly higher than those of carbamate pesticides and fulvic acids. This result indicated that the hydrophobic force is one of the main interactions between carbamate pesticides and humic substances, and further proved that hydrogen bonding could slightly affect the bonding of carbamate pesticides and humic substances.

  4. 杭州市市供豇豆有机磷类和氨基甲酸酯类农药残留监测结果分析%The monitoring results of organophosphate and carbamate pesticide residues in cowpea in Hangzhou

    金旭忠; 徐庭巧; 何良兴

    2012-01-01

    目的:分析杭州市市供豇豆农药残留情况,为蔬菜质量安全的监管提供科学依据.方法:采集豇豆样品750批次,测定19种有机磷类农药残留量和10种氨基甲酸酯类农药残留量.结果:26批次样品为阳性,超标率为3.47%,其中,3批次样品有机磷类农药超标,超标率为0.40%,23批次样品氨基甲酸酯类农药残留超标,超标率为3.07%.结论:豇豆中农药超标较为严重,检出农药中涉及克百威、氧化乐果、水胺硫磷等禁用农药,需进一步加强监管.%Objective:To investigate the conditions of organophosphate and carbamate pesticide residues in cow-pea in Hangzhou in order to provide the basis for surveillance and control of vegetables safety. Methods: The total 750 samples of cowpea were collected and organophosphorus residues and carbamate pesticide residues in these samples were measured. Results: The disqualification rate of cowpea was 3.47 %. The disqualification rate of organophosphate and carbamate pesticide residues in cowpea were 0.40% , 3.07% respectively. Conclusion:The situation of pesticide residues in cowpea was relatively severe. Some forbidden pesticides were found. So the supervision and administration on the forbidden pesticides should be strengthened.

  5. A mechanism-based 3D-QSAR approach for classification and prediction of acetylcholinesterase inhibitory potency of organophosphate and carbamate analogs

    Lee, Sehan; Barron, Mace G.

    2016-04-01

    Organophosphate (OP) and carbamate esters can inhibit acetylcholinesterase (AChE) by binding covalently to a serine residue in the enzyme active site, and their inhibitory potency depends largely on affinity for the enzyme and the reactivity of the ester. Despite this understanding, there has been no mechanism-based in silico approach for classification and prediction of the inhibitory potency of ether OPs or carbamates. This prompted us to develop a three dimensional prediction framework for OPs, carbamates, and their analogs. Inhibitory structures of a compound that can form the covalent bond were identified through analysis of docked conformations of the compound and its metabolites. Inhibitory potencies of the selected structures were then predicted using a previously developed three dimensional quantitative structure-active relationship. This approach was validated with a large number of structurally diverse OP and carbamate compounds encompassing widely used insecticides and structural analogs including OP flame retardants and thio- and dithiocarbamate pesticides. The modeling revealed that: (1) in addition to classical OP metabolic activation, the toxicity of carbamate compounds can be dependent on biotransformation, (2) OP and carbamate analogs such as OP flame retardants and thiocarbamate herbicides can act as AChEI, (3) hydrogen bonds at the oxyanion hole is critical for AChE inhibition through the covalent bond, and (4) π-π interaction with Trp86 is necessary for strong inhibition of AChE. Our combined computation approach provided detailed understanding of the mechanism of action of OP and carbamate compounds and may be useful for screening a diversity of chemical structures for AChE inhibitory potency.

  6. GC-MS法高灵敏检测蔬菜中氨基甲酸酯农药残留%Detection of pesticides residues of carbamate in vegetables by GC-MS

    王俊; 管有志; 于微; 谭洪兴; 朱李佳; 刘小立

    2013-01-01

    目的 建立使用气质联用法同时检测蔬菜中多种氨基甲酸酯快速灵敏的检测方法.方法 样品经乙腈提取,固相萃取柱净化,并建立一种快速测定蔬菜中6种氨基甲酸酯类农药残留(异丙威、仲丁威、残杀威、抗芽威、速灭威、甲奈威)的气相色谱质谱联用(GC-MS)检测方法.同时对22种蔬菜中的多种氨基甲酸酯类农药进行定性及定量分析. 结果 建立一种快速测定蔬菜中6种氨基甲酸酯类农药残留的GC-MS方法,该方法对6种氨基甲酸酯类农药的相对标准偏差为1.06%~3.73%,回收率为86.5%~112.3%,并具有较好的精密度.在应用该方法检测的22种蔬菜中,一份空心菜检测出残杀威,一份香菜中检测出异丙威. 结论 本文建立的快速测定蔬菜中6中氨基甲酸酯类农药的GC-MS方法准确可靠,灵敏度高,可应用于蔬菜中多种氨基甲酸酯农药的同时测定.%Objective To set up a reliable method for determination of six carbamates in vegetables by using GC-MS.. Methods Samples were extracted with acetonitrile and then purified by solid-phase extraction (SPE). A method on rapid detection of six carbamates (Isoprocarb,BPMC,Propoxur,Pirimicarb,MTMC,Carbaryl)in samples by GC-MS has been established. Qualitative and quantitative analysis of pesticide residues in 22 vegetables from local supermarket have been performed by the proposed method. Results The relative standard deviations of the method were between 1.06% and 3.73%,and the method recoveries were in the range of 86.5-112.3% with good precision. Propoxur in water spinach and Isoprocarb in caraway have positive test results in our experiments. Conclusions The method was highly sensitive with satisfied recovery and it could be applied to detect six carbamates residues in vegetables quickly and accurately.

  7. Detection of 20 carbamate pesticides in asparagus by ultra performance liquid chromatography-electrospray ionization-mass spectrometry-mass spectrometry%超高效液相色谱-电喷雾串联四极杆质谱法检测芦笋中20种氨基甲酸酯类农药残留

    赵晓琳; 霍乃蕊; 花锦; 宋欢

    2015-01-01

    目的:建立芦笋及其罐头制品中20种氨基甲酸酯类农药残留的定性定量分析方法。方法采用改进的 QuEchERS 法提取和净化,利用超高效液相色谱-电喷雾串联四极杆质谱仪,在多反应监测正离子扫描模式下对样品进行添加回收率试验。结果分别对绿芦笋、白芦笋、绿芦笋罐头、白芦笋罐头4种空白基质添加0.005~0.050 mg/kg农药样品进行回收率试验,回收率为62.44%~85.99%,定量限均为0.005 mg/kg, RSD均小于9%。结论该方法简单快速,灵敏度高,能够同时满足芦笋及其罐头制品中20种氨基甲酸酯类农药残留的检测要求。%Objective To establish an ultra performance liquid chromatography-electrospray ionization-mass spectrometry-mass spectrometry method for detecting of 20 kinds of carbamate pesticides in asparagus and asparagus products. Methods Samples were extracted by modified QuEchERS method, and the mode of multi-reaction monitoring positive ion scanning was applied for analysis by ultra high performance liquid chromatography-electrospray tandem quadrupole mass spectrometer. Results The blank matrixes (green asparagus, white asparagus, canned white asparagus, canned white asparagus) were added 0.005~0.050 mg/kg carbamate pesticides separately and recovery tests were performed. Results demonstrated that the recovery rates were in the range of 62.44%~85.99% and the limits of quantification were 0.005 mg/kg for all the 20 carbamate pesticides tested with the relative standard deviations (RSDs) below 9%. Conclusion The method, not only simple and fast but also high sensitive, can satisfy the international detection requirement for 20 carbamate pesticides residue in asparagus product simultaneously.

  8. Pesticides

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  9. Carbamate and Organophosphorus Nematicides: Acetylcholinesterase inhibition and Effects on Dispersal.

    Pree, D J; Townshend, J L; Archibald, D E

    1989-10-01

    The sensitivities of acetylcholinesterases (ACHE) from the fungus-feeder Aphelenchus avenae and the plant-parasitic species Helicotylenchus dihystera and Pratylenchus penetrans and the housefly, Musca domestica, were compared using a radiometric assay which utilized H(3) acetylcholine as a substrate. Nematode ACHE were generally less sensitive to inhibition by organophosphorns and carbamate pesticides than were ACHE from the housefly. ACHE from the plant-parasitic species and A. avenae were generally similar in sensitivity. In soil, carbamates were more toxic than the organophosphorus pesticides to A. avenae. All pesticides tested affected nematode movement, but fenamiphos was more inhibitory than others. The effects on dispersal of nematodes may be an important mechanism in control by some nematicides.

  10. Acetylcholinesterase inhibition as an indicator of organophosphate and carbamate poisoning in Kenyan agricultural workers.

    Ohayo-Mitoko, G.J.A.; Heederik, D.; Kromhout, H.; Omondi, B.E.O.; Boleij, J.S.M.

    1997-01-01

    Acetylcholinesterase inhibition was determined for 666 Kenyan agricultural workers; 390 (58.6%) mainly pesticide applicators exposed to organophosphate and carbamate pesticides and 276 (41.4%) unexposed controls from four rural agricultural areas during 1993 and 1994. Baseline levels were depressed

  11. Simultaneous determination of airborne carbamates in workplace by high performance liquid chromatography with fluorescence detection.

    Li, Hong-Ping; Li, Jen-Hou; Li, Gwo-Chen; Jen, Jen-Fon

    2004-06-17

    A high performance liquid chromatography with fluorescence (HPLC-F) detector was examined to simultaneous determination of airborne carbamates in the workplace of manufactory. The OVS-2 air sampling tube filled with glass fiber filter or quartz fiber and combined filter/XAD-2 were evaluated to collect nine commonly used carbamates (Carbofuran, Isoprocarb, Methomyl, Metolcarb, Thiodicarb, Carbaryl, Oxamyl, Methiocarb, and Prpoxur) from the air of manufactory in high humidity country. After being extracted with acetonitrile from sampling tubes, the carbamates were determined by high performance liquid chromatography with fluorescence detection posterior to on-line derivatization. The collection of carbamates and the recovery of extraction from glass wool fiber in several concentration levels, and from quartz filter were evaluated. The storage stability of carbamates was also tested. Results indicated that the HPLC-fluorescence method offers satisfactory resolution and sensitivity in carbamate analysis. With the glass fiber filter and combined filter/XAD-2, the Carbofuran, Isoprocarb, Methomyl, Metolcarb, and Thiodicarb were stable for a 28-day storage test, Carbaryl and Oxamyl for 14 days, and Methiocarb and Prpoxur for 7 days. All of these pesticides were with detection limit of 3mugm(-3). It is suited for environmental monitoring. The airborne carbamates in different areas of the manufactory were measured.

  12. 溶剂浮选-气相色谱/质谱法测定蔬菜中氨基甲酸酯类农药残留%Determination of N-Methyl Carbamate Pesticide Residues in Vegetables by the Method of Solvent Sublation followed by GC/MS

    席艳丽; 董慧茹

    2008-01-01

      建立了一种有效分离富集并检测蔬菜中氨基甲酸酯类农药残留的方法,即采用溶剂浮选法(SS)对蔬菜中的氨基甲酸酯类农药残留进行分离富集,然后用气相色谱/质谱(GC/MS)进行检测.考察了浮选溶剂、试液 pH、通气速度及浮选时间等因素对浮选效果的影响,得到了优化浮选条件;对此条件下的浮选产物进行气相色谱/质谱检测,回收率为81.6%~97.8%,RSD为1.39%~2.65%,定量限(LOQ)为0.39~6.17μg/kg.%  An effective method of solvent sublation followed by GC/MS for separating, enriching and determining of the residue of N-methyl carbamate pesticides in vegetables has been developed. The optimal conditions of the solvent sublation were selected by investigating the effects of organic solvent, pH of the solution, nitrogen flow rate and sublation time on the sublation efficiency of N-methyl carbamate. The recoveries of spiked vegetable samples in the method were from 81.6%to 97.8%, and RSD values were from 1.39%to 2.65%. The limit of quantitation (LOQ) values was in the range of 0.39~6.17μg/kg.

  13. A Quantitative Structure Activity Relationship for acute oral toxicity of pesticides on rats: Validation, domain of application and prediction.

    Hamadache, Mabrouk; Benkortbi, Othmane; Hanini, Salah; Amrane, Abdeltif; Khaouane, Latifa; Si Moussa, Cherif

    2016-02-13

    Quantitative Structure Activity Relationship (QSAR) models are expected to play an important role in the risk assessment of chemicals on humans and the environment. In this study, we developed a validated QSAR model to predict acute oral toxicity of 329 pesticides to rats because a few QSAR models have been devoted to predict the Lethal Dose 50 (LD50) of pesticides on rats. This QSAR model is based on 17 molecular descriptors, and is robust, externally predictive and characterized by a good applicability domain. The best results were obtained with a 17/9/1 Artificial Neural Network model trained with the Quasi Newton back propagation (BFGS) algorithm. The prediction accuracy for the external validation set was estimated by the Q(2)ext and the root mean square error (RMS) which are equal to 0.948 and 0.201, respectively. 98.6% of external validation set is correctly predicted and the present model proved to be superior to models previously published. Accordingly, the model developed in this study provides excellent predictions and can be used to predict the acute oral toxicity of pesticides, particularly for those that have not been tested as well as new pesticides.

  14. Benzimidazole Carbamate Residues in Milk: Detection by SPR Biosensor; using a Modified QuEChERS Method for Extraction

    A surface plasmon resonance (SPR) biosensor screening assay was developed and validated to detect 11 benzimidazole carbamate (BZT) veterinary drug residues in milk. The polyclonal antibody used was raised in sheep against a methyl 5 (6)-[(carboxypentyl)-thio]-2-benzimidazole carbamate protein conjug...

  15. From home range dynamics to population cycles: validation and realism of a common vole population model for pesticide risk assessment.

    Wang, Magnus

    2013-04-01

    Despite various attempts to establish population models as standard tools in pesticide risk assessment, population models still receive limited acceptance by risk assessors and authorities in Europe. A main criticism of risk assessors is that population models are often not, or not sufficiently, validated. Hence the realism of population-level risk assessments conducted with such models remains uncertain. We therefore developed an individual-based population model for the common vole, Microtus arvalis, and demonstrate how population models can be validated in great detail based on published data. The model is developed for application in pesticide risk assessment, therefore, the validation covers all areas of the biology of the common vole that are relevant for the analysis of potential effects and recovery after application of pesticides. Our results indicate that reproduction, survival, age structure, spatial behavior, and population dynamics reproduced from the model are comparable to field observations. Also interannual population cycles, which are frequently observed in field studies of small mammals, emerge from the population model. These cycles were shown to be caused by the home range behavior and dispersal. As observed previously in the field, population cycles in the model were also stronger for longer breeding season length. Our results show how validation can help to evaluate the realism of population models, and we discuss the importance of taking field methodology and resulting bias into account. Our results also demonstrate how population models can help to test or understand biological mechanisms in population ecology.

  16. Analytical Method Validation of Selected Organochlorine Pesticides in Fortified Rice Using Gas Chromatography with Electron Capture Detector

    Mutia Kusuma Wardani

    2014-01-01

    Full Text Available Gas chromatography with electron capture detector (GC-ECD has been validated for simultaneous determination of selected organochlorine pesticides namely heptachlor, endosulfan, dieldrin, dan p,p’-dichlorodiphenyltrichloroethane (p,p’-DDT using aldrin as standard internal. Some parameters for analytical method validation were evaluated, i.e. linearity, precision, sensitivity expressed with limit of detection and limit of quantification, and recovery. GC-ECD was linear for determination of these pesticides with r values ≥ 0.99. The values of LOD obtained were 2.50, 2.97, 1.61, and 2.54 ng/mL for heptachlor, endosulphan, dieldrin, and p,p’-DDT, respectively. Furthermore, the relative standard deviation (RSD values obtained for the assessment of analytical precision were lower than those required by Horwitz. Finally, the used GC-ECD method was accurate for determination of these organochlorine psticides in fortified rice samples which were indicated by the acceptable recovery percentages.

  17. Validation and Uncertainty of the method for multiresidue analysis of 35 pesticides in melon using Gas Chromatography Coupled to Quadrupole Mass Spectrometry (GC-QP/MS)

    Milhome, M. A. L.; Sousa, J. S.; Andrade, G. A.; de Castro, R. C.; Lima, L. K.; Lima, C. G.; Nascimento, R. F.

    2015-01-01

    QuEChERS method and detection in GC/SQ-MS were validated for the analysis of 35 pesticides in melon. Validation parameters (selectivity, linearity, LOD, LOQ, accuracy and precision) were determined according ABNT NBR 14029:2005. The recoveries rates for all the pesticides studied were from 63% to 117% with relative standard deviation (RSD) lower than 15% in the concentration range of 0.05 - 0.20 mg/kg. The limit of quantification (LOQ) for most compounds were below the MRLs established in Brazil. The combined relative uncertainty (Uc) and expanded uncertainty (Ue) was determined using repetitivity, recovery and calibration curves data for each pesticide.

  18. Organic carbamates in drug design and medicinal chemistry.

    Ghosh, Arun K; Brindisi, Margherita

    2015-04-09

    The carbamate group is a key structural motif in many approved drugs and prodrugs. There is an increasing use of carbamates in medicinal chemistry and many derivatives are specifically designed to make drug-target interactions through their carbamate moiety. In this Perspective, we present properties and stabilities of carbamates, reagents and chemical methodologies for the synthesis of carbamates, and recent applications of carbamates in drug design and medicinal chemistry.

  19. Validation of a QuEChERS-based gas chromatographic method for analysis of pesticide residues in Cassia angustifolia (senna).

    Tripathy, Vandana; Saha, Ajoy; Patel, Dilipkumar J; Basak, B B; Shah, Paresh G; Kumar, Jitendra

    2016-08-01

    A simple multi-residue method based on modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) approach was established for the determination of 17 organochlorine (OC), 15 organophosphorous (OP) and 7 synthetic pyrethroid (SP) pesticides in an economically important medicinal plant of India, Senna (Cassia angustifolia), by gas chromatography coupled to electron capture and flame thermionic detectors (GC/ECD/FTD) and confirmation of residues was done on gas chromatograph coupled with mass spectrometry (GC-MS). The developed method was validated by testing the following parameters: linearity, limit of detection (LOD), limit of quantification (LOQ), matrix effect, accuracy-precision and measurement uncertainty; the validation study clearly demonstrated the suitability of the method for its intended application. All pesticides showed good linearity in the range 0.01-1.0 μg mL(-1) for OCs and OPs and 0.05-2.5 μg mL(-1) for SPs with correlation coefficients higher than 0.98. The method gave good recoveries for most of the pesticides (70-120%) with intra-day and inter-day precision < 20% in most of the cases. The limits of detection varied from 0.003 to 0.03 mg kg(-1), and the LOQs were determined as 0.01-0.049 mg kg(-1). The expanded uncertainties were <30%, which was distinctively less than a maximum default value of ±50%. The proposed method was successfully applied to determine pesticide residues in 12 commercial market samples obtained from different locations in India.

  20. [Validation study on a multi-residue analysis of pesticides in agricultural products by using phosphoric acid treatment and GC-MS/MS].

    Makabe, Yuhki; Takahashi, Hiroshi; Enomoto, Tomoko; Aikawa, Takehiko

    2014-01-01

    A rapid method for multi-residue determination of pesticides in agricultural products was validated. The sample was cut into pieces and placed into a mixer cup containing half weight amount of 10% phosphoric acid in order to suppress degradation of easily degraded pesticides, represented by captan, and then homogenized. Pesticides in the phosphoric acid-treated sample were extracted with acetonitrile using a homogenizer, followed by salting out with anhydrous magnesium sulfate and sodium chloride. The extract was cleaned up on a C18 and graphite carbon black/PSA mini-cartridge column. Some pesticides gave tailing peaks, but these peaks became sharp and symmetrical when polyethylene glycol (PEG) 300 was added to the test solution. Recovery tests were performed on nine kinds of agricultural products (brown rice, soybean, spinach, cabbage, potato, orange, apple, strawberry, and Japanese pear) fortified with 170 pesticides at 0.01 and 0.1 μg/g. Each concentration of pesticide residue was extracted from 2 samples on 5 separate days. The trueness of the method for 147-164 pesticides in each sample was 70-120% with satisfactory repeatability and within-run reproducibility. This method is expected to useful for multi-residue analysis of pesticides in agricultural products.

  1. Neurotoxicity of pesticides.

    Keifer, Matthew C; Firestone, Jordan

    2007-01-01

    Several pesticides such as organophosphates, carbamates and the organochlorine pesticides directly target nervous tissue as their mechanism of toxicity. In several others, such as the fumigants, the nervous system is affected by toxicological mechanisms that diffusely affect most or all tissues in the body. Both the central and peripheral nervous system are involved in the acute toxidromes of many pesticides resulting in acute short-term effects. There is strong human epidemiological evidence for persistent nervous system damage following acute intoxication with several important pesticide groups such as organophosphates and certain fumigants. However, whether persistent nervous system damage follows chronic low-level exposure to pesticides in adults (particularly organophosphpates), and whether in utero and/or early childhood exposure leads to persistent nervous system damage, is a subject of study at present. Parkinson's Disease, one of the most common chronic central nervous system diseases, has been linked to pesticide exposure in some studies, but other studies have failed to find an association. Several new pesticidal chemicals such as the neo-nicotinoids and fipronil have central nervous system effects, but only case reports are available to date on acute human intoxications with several of these. Little data are yet available on whether long-term effects result from these chemicals. Several ongoing or recently completed studies should add valuable insight into the effects of pesticides on the human nervous system particularly the effect of low-dose, chronic exposure both in adults and children.

  2. Organophosphorus and carbamates residues in milk and feedstuff supplied to dairy cattle

    Rafael Fagnani; Vanerli Beloti; Ana Paula P. Battaglini; Dunga,Karen da S.; Ronaldo Tamanini

    2011-01-01

    Considering acute and chronic toxicity effects on human and animal health caused by pesticide residues in food, this study aimed to analyze organophosphorate (OP) and carbamate (CB) in feedstuff and water destined for dairy cattle, as well as in the milk produced by these animals, through gas chromatography (GC). In the Agreste region of Pernambuco, Brazil, 30 raw milk samples and all components of the animals' diet were collected from several farms. Out of the 30 milk of milk analyzed, six (...

  3. Guidelines for the validation of qualitative multi-residue methods used to detect pesticides in food

    Mol, J.G.J.; Reynolds, S.L.; Fussell, R.J.; Stajnbaher, D.

    2012-01-01

    There is a current trend for many laboratories to develop and use qualitative gas chromatography–mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS) based multi-residue methods (MRMs) in order to greatly increase the number of pesticides that they can target. Before these q

  4. Diagnosis & Treatment of Poisoning by Pesticides.

    Environmental Protection Agency, Washington, DC. Office of Pesticide Programs.

    This report succinctly discusses the steps necessary to diagnose and treat poisoning from pesticides, especially organophosphates, carbamates and chlorinated hydrocarbons. Immediate and continuing steps in the care of poisoning victims are outlined with supportive information on where to locate emergency assistance. (CS)

  5. Fenugreek hydrogel–agarose composite entrapped gold nanoparticles for acetylcholinesterase based biosensor for carbamates detection

    Kestwal, Rakesh Mohan; Bagal-Kestwal, Dipali; Chiang, Been-Huang, E-mail: bhchiang@ntu.edu.tw

    2015-07-30

    A biosensor was fabricated to detect pesticides in food samples. Acetylcholinesterase was immobilized in a novel fenugreek hydrogel–agarose matrix with gold nanoparticles. Transparent thin films with superior mechanical strength and stability were obtained with 2% fenugreek hydrogel and 2% agarose. Immobilization of acetylcholinesterase on the membrane resulted in high enzyme retention efficiency (92%) and a significantly prolonged shelf life of the enzyme (half-life, 55 days). Transmission electron microscopy revealed that, gold nanoparticles (10–20 nm in diameter) were uniformly dispersed in the fenugreek hydrogel–agarose–acetylcholinesterase membrane. This immobilized enzyme-gold nanoparticle dip-strip system detected various carbamates, including carbofuran, oxamyl, methomyl, and carbaryl, with limits of detection of 2, 21, 113, and 236 nM (S/N = 3), respectively. Furthermore, the fabricated biosensor exhibited good testing capabilities when used to detect carbamates added to various fruit and vegetable samples. - Highlights: • Acetylcholinesterase (AChE) dip-strip biosensor fabricated to detect carbamates. • AChE entrapped in fenugreek hydrogel–agarose matrix with gold nanoparticles (GNPs). • High enzyme retention efficiency (92%) and shelf life (half-life, 55 days). • Detection limits of carbofuran, oxamyl and methomyl: 2, 21 and 113 nM. • The biosensor had good testing capabilities to detect carbamates in food samples.

  6. [Neurotoxicology of pesticides].

    Ichikawa, Hiroo

    2015-01-01

    Pesticides have been used for many years for preventing, destroying, repelling, or mitigating pests such as insects, rodents, and weeds. However, most pesticides are not completely specific for pests and can also induce damage to the human nervous system. In particular, insecticides often directly targets the nervous system by affecting major targets such as the neuro-transmitter metabolism, neuronal receptors, and ion channels; acetylcholine (ACh) esterase for organo-phosphates and carbamates, nicotinic ACh receptor for neonicotinoids, γ-aminobutyric acid receptors/chloride channels for organochlorides and fipronil, and voltage-gated sodium channel for pyrethroids. Additional targets include sites in the sodium channels, glutamate-gated chloride channels, and octopamine and ryanodine receptors. Several pesticides also produce adverse neurological effects indirectly by disrupting the general cellular mechanisms that support the high metabolic activity of the nervous system. Nowadays, more potent pesticides are being developed as replacements for the older, harmful ones. Pesticide neurotoxicity in humans may involve the central or peripheral nervous system or both and may induce typical neuronal damage in case of acute poisoning even by new agents. However, whether effect of exposure to pesticides at below acute-poisoning threshold level remains unclear. Moreover, neurotoxicology for behavioral and higher-brain function remains an unresolved and a challenging problem.

  7. Detection of benzimidazole carbamates and amino metabolites in liver by surface plasmon resonance-biosensor

    Two surface plasmon resonance (SPR) biosensor screening assays were developed and validated to detect 11 benzimidazole carbamate (BZT) and four amino-benzimidazole veterinary drug residues in liver tissue. The assays used polyclonal antibodies, raised in sheep, to detect BZTs and amino-benzimidazole...

  8. Validation of a qualitative screening method for pesticides in fruits and vegetables by gas chromatography quadrupole-time of flight mass spectrometry with atmospheric pressure chemical ionization

    Portolés, T. [Research Institute for Pesticides and Water, University Jaume I, 12071 Castellón (Spain); RIKILT Institute of Food Safety, Wageningen University and Research Centre, Akkermaalsbos 2, 6708 WB Wageningen (Netherlands); Mol, J.G.J. [RIKILT Institute of Food Safety, Wageningen University and Research Centre, Akkermaalsbos 2, 6708 WB Wageningen (Netherlands); Sancho, J.V.; López, Francisco J. [Research Institute for Pesticides and Water, University Jaume I, 12071 Castellón (Spain); Hernández, F., E-mail: hernandf@uji.es [Research Institute for Pesticides and Water, University Jaume I, 12071 Castellón (Spain)

    2014-08-01

    Highlights: • Applicability of GC-(APCI)QTOF MS as new tool for wide-scope screening of pesticides in fruits and vegetables demonstrated. • Validation of screening method according to SANCO/12571/2013. • Detection of the pesticides based on the presence of M+·/MH+ in most cases. • Screening detection limit 0.01 mg kg{sup −1} for 77% of the pesticides investigated. • Successful identification at 0.01 mg kg{sup −1} for 70% of the pesticides/matrix combinations. - Abstract: A wide-scope screening method was developed for the detection of pesticides in fruit and vegetables. The method was based on gas chromatography coupled to a hybrid quadrupole time-of-flight mass spectrometer with an atmospheric pressure chemical ionization source (GC-(APCI)QTOF MS). A non-target acquisition was performed through two alternating scan events: one at low collision energy and another at a higher collision energy ramp (MS{sup E}). In this way, both protonated molecule and/or molecular ion together with fragment ions were obtained in a single run. Validation was performed according to SANCO/12571/2013 by analysing 20 samples (10 different commodities in duplicate), fortified with a test set of 132 pesticides at 0.01, 0.05 and 0.20 mg kg{sup −1}. For screening, the detection was based on one diagnostic ion (in most cases the protonated molecule). Overall, at the 0.01 mg kg{sup −1} level, 89% of the 2620 fortifications made were detected. The screening detection limit for individual pesticides was 0.01 mg kg{sup −1} for 77% of the pesticides investigated. The possibilities for identification according to the SANCO criteria, requiring two ions with a mass accuracy ≤±5 ppm and an ion-ratio deviation ≤±30%, were investigated. At the 0.01 mg kg{sup −1} level, identification was possible for 70% of the pesticides detected during screening. This increased to 87% and 93% at the 0.05 and 0.20 mg kg{sup −1} level, respectively. Insufficient sensitivity for the second

  9. A PHYSIOLOGICALLY BASED PHARMACOKINETIC/PHARMACODYNAMIC (PBPK/PD) MODEL FOR ESTIMATION OF CUMULATIVE RISK FROM EXPOSURE TO THREE N-METHYL CARBAMATES: CARBARYL, ALDICARB, AND CARBOFURAN

    A physiologically-based pharmacokinetic (PBPK) model for a mixture of N-methyl carbamate pesticides was developed based on single chemical models. The model was used to compare urinary metabolite concentrations to levels from National Health and Nutrition Examination Survey (NHA...

  10. 化学发光生物传感器法测定食品中有机磷与氨基甲酸酯类农药残留%Determination of organophosphorus and carbamates pesticide residues in foods by chemiluminescence biosensor

    王晓朋; 曾梅; 万德慧; 唐晗; 赵彬媛; 周雅倩; 刘晓宇

    2014-01-01

    Objective To create a high-sensitivity biosensor for detecting organophosphorus and carbamates pesticides in foods and establish a new method to determine these two kinds of pesticides.Methods Immobilized acetylcholinesterase (AchE) was used as recognition element of the sensor, reacting specifically with the substrate of acetylthiocholine iodide(ATCI), the micro-fluidic chip with CL analyzer was used as detecting element, and luminol-potassium ferricyanide system was used in chemiluminescence system. ResultsWhen the concentration of proximal, dichlorvos, dimethoate ranging from 0.1~10, 0.08~10, and 0.8~15μg/mL, respectively, the correlation coefficients were 0.9923, 0.9903, and 0.9904, and the detection limits were 0.047, 0.054, and 0.388μg/mL, respectively. When the concentrations of carbofuran, carbonyl, and methomyl were ranging from 0.08~15, 0.1~10, and 0.1~10μg/mL, respectively, the correlation coefficients were 0.9926, 0.9972, and 0.9944, and the detection limits were 0.049, 0.051, and 0.080μg/mL, respectively. The evaluation of biosensor performance indicates good precision, when determining all 6 kinds of pesticides under optimal conditions, RSD was below 7%; when the substrate of ATCI was injected into chemiluminescence system 6 times discontinuously, RSD was below 8%, which indicated good stability; immobilized AChE was stored in phosphate buffer(pH=8.0), detecting activity every 10 d, lasting for two months, the relative enzymatic activity decreased only 23%, indicating a good storage stability; the biosensor was used to detect samples of cabbage and apple, fortified recoveries were between 90%~99%.Conclusion This biosensor has a good performance, therefore it can be used to determine pesticides in foods.%目的:构建一种用于检测食品中有机磷与氨基甲酸酯类农药残留的高灵敏度生物传感器,建立一种用于测定食品中两类农药残留的新方法。方法以固定化乙酰胆碱酯酶(AChE

  11. Validation of a flow-through sampler for pesticides and polybrominated diphenyl ethers in air

    Xiao, Hang; Hung, Hayley; Lei, Ying Duan; Wania, Frank

    At locations without access to the electrical grid, a flow-through sampler (FTS) collects large volumes of air for the analysis of semi-volatile organic compounds (SVOCs). To test its performance under field conditions, an FTS and a traditional pumped high volume air sampler, both using polyurethane foam (PUF) as sampling medium, were co-deployed at the campus of the University of Toronto Scarborough from August 2006 to June 2007. Polybrominated diphenyl ethers (PBDEs) and various pesticides were quantified in the samples taken by both samplers to test the FTS's applicability to relatively non-volatile and slightly polar SVOCs. Air concentrations in samples taken with the FTS over five 2-week periods compare favourably with the average of the concentrations in several 24-h active high volume samples taken during the same period. In particular, time trends, temperature dependence relationships, and isomer ratios show a reasonable agreement between the two sampling techniques. An empirical linear solvation energy relationship for predicting the apparent theoretical plate number of the PUF assembly used in the FTS illustrates the effect of chemical properties, as well as temperature and wind speed, on sampling efficiency. In the absence of electrical power, the FTS can collect SVOCs from large air volumes as reliably and quantitatively as traditional HiVol samplers, although without separating gas and particle phase.

  12. Validation and application of a multi-residue method, using accelerated solvent extraction followed by gas chromatography, for pesticides quantification in soil.

    Leyva-Morales, J B; Valdez-Torres, J B; Bastidas-Bastidas, P J; Betancourt-Lozano, M

    2015-01-01

    A multi-residue method was developed to determine different types of pesticides in soils. An extraction with pressure and temperature, through accelerated solvent extraction (dichloromethane:acetone, 50:50, v/v). The pesticides were determined by gas chromatography with several selective detectors: electron capture detector, pulsed flame photometric detector and thermionic specific detector. The following parameters were determined: limit of detection, limit of quantification, equipment linearity (working interval), method linearity as well as, method accuracy and precision. The average recoveries ranged between 76 and 106%, with the exception of chlorothalonil, which had an average recovery of 46%. Additionally, detection limits from 0.9 to 7.6ng g -: (1) and the quantification limits from 3.00 to 25.47ng g -: (1) were estimated. In terms of linearity and precision, the results obtained were in the ranges considered adequate (R(2) ≥ 0.98 and coefficient of variation (CV) ≤ 20%), with the exception of aldrin (R(2) = 0.946, CV = 35.79%), lindane (R(2) = 0.917, CV = 32.91%) and chlorothalonil (R(2) = 0.8184, CV = 81.35%). The proposed method was used to evaluate pesticides in real soil samples, detecting concentrations over 1000ng g -: (1) for some pesticides. The method was correctly validated and provided for the rapid determination of pesticides in soil.

  13. [Validation Study on a Multi-Residue Method for Determination of Pesticide Residues in Vegetables and Fruits by using General Matrix Standard Solutions].

    Fukui, Naoki; Takatori, Satoshi; Yamaguchi, Satoko; Kitagawa, Yoko; Yoshimitsu, Masato; Osakada, Masakazu; Kajimura, Keiji; Obana, Hirotaka

    2015-01-01

    Quantitative methods using the matrix-matched standard solutions approach are widely used for multi-residue pesticide determination by GC-MS/MS to deal with the issue of matrix effects. However, preparing matrix-matched standard solutions in analyses of many kinds of samples is very time-consuming. In order to solve this problem, a method that employs general matrix standard solutions has been developed using polyethylene glycol (PEG), extract of vegetables-fruit juice (VFJm) and triphenyl phosphate (named the PEG-VFJm method). Here, a validation study for 168 pesticides was performed on three kinds of samples [potato, spinach and apple] at concentrations of 0.010 and 0.050 μg/g. In these three commodities, 144 to 158 pesticides satisfied the required criteria using the matrix-matched method and 129 to 149 pesticides satisfied the same criteria using the PEG-VFJm method. Our results suggest that application of general matrix standard solutions would enable rapid and effective analyses of pesticides.

  14. Fluorimetric Determination of Carbamate Pesticides in Host-Guest Complexes

    Alicia Viviana Veglia

    2000-03-01

    Full Text Available From the effect of β-cyclodextrin and hydroxypropyl-β-cyclodextrin on the UVvisible and fluorescence spectra of carbaryl and carbofuran, the values of association constants were determined. The ratio of the fluorescence quantum yields for the bound and free substrates indicated an enhanced fluorimetric method of detection.

  15. Development and Validation of Chronopotentiometric Method for Imidacloprid Determination in Pesticide Formulations and River Water Samples

    Ana Đurović

    2016-01-01

    Full Text Available A new electrochemical method for determination of imidacloprid using chronopotentiometry on thin film mercury and glassy carbon electrode was presented. The most important experimental parameters of chronopotentiometry were examined and optimized with respect to imidacloprid analytical signal. Imidacloprid provided well-defined reduction peak in Britton-Robinson buffer on thin film mercury electrode at −1.0 V (versus Ag/AgCl (KCl, 3.5 mol/L and on glassy carbon electrode at −1.2 V (versus Ag/AgCl (KCl, 3.5 mol/L. The reduction time was linearly proportional to concentrations from 0.8 to 30.0 mg/L on thin film mercury electrode and from 7.0 to 70.0 mg/L on glassy carbon electrode. The detection limits were 0.17 mg/L and 0.93 mg/L for thin film mercury and glassy carbon electrode, respectively. The estimation of method precision as a function of repeatability and reproducibility showed relative standard deviations values lower than 3.73%. Recovery values from 97.3 to 98.1% confirmed the accuracy of the proposed method, while the constancy of the transition time with deliberated small changes in the experimental parameters indicated a very good robustness. A minor influence of possible interfering compounds proved good selectivity of the method. Developed method was applied for imidacloprid determination in commercial pesticide formulations and river water samples.

  16. Validation of a qualitative screening method for pesticides in fruits and vegetables by gas chromatography quadrupole-time of flight mass spectrometry with atmospheric pressure chemical ionization.

    Portolés, T; Mol, J G J; Sancho, J V; López, Francisco J; Hernández, F

    2014-08-01

    A wide-scope screening method was developed for the detection of pesticides in fruit and vegetables. The method was based on gas chromatography coupled to a hybrid quadrupole time-of-flight mass spectrometer with an atmospheric pressure chemical ionization source (GC-(APCI)QTOF MS). A non-target acquisition was performed through two alternating scan events: one at low collision energy and another at a higher collision energy ramp (MS(E)). In this way, both protonated molecule and/or molecular ion together with fragment ions were obtained in a single run. Validation was performed according to SANCO/12571/2013 by analysing 20 samples (10 different commodities in duplicate), fortified with a test set of 132 pesticides at 0.01, 0.05 and 0.20mg kg(-1). For screening, the detection was based on one diagnostic ion (in most cases the protonated molecule). Overall, at the 0.01mg kg(-1) level, 89% of the 2620 fortifications made were detected. The screening detection limit for individual pesticides was 0.01mg kg(-1) for 77% of the pesticides investigated. The possibilities for identification according to the SANCO criteria, requiring two ions with a mass accuracy ≤±5ppm and an ion-ratio deviation ≤±30%, were investigated. At the 0.01mg kg(-1) level, identification was possible for 70% of the pesticides detected during screening. This increased to 87% and 93% at the 0.05 and 0.20mg kg(-1) level, respectively. Insufficient sensitivity for the second ion was the main reason for the inability to identify detected pesticides, followed by deviations in mass accuracy and ion ratios.

  17. Using phylogenetic information and chemical properties to predict species tolerances to pesticides.

    Guénard, Guillaume; Carsten von der Ohe, Peter; Carlisle Walker, Steven; Lek, Sovan; Legendre, Pierre

    2014-08-22

    Direct estimation of species' tolerance to pesticides and other toxic organic substances is a combinatorial problem, because of the large number of species-substance pairs. We propose a statistical modelling approach to predict tolerances associated with untested species-substance pairs, by using models fitted to tested pairs. This approach is based on the phylogeny of species and physico-chemical descriptors of pesticides, with both kinds of information combined in a bilinear model. This bilinear modelling approach predicts tolerance in untested species-compound pairs based on the facts that closely related species often respond similarly to toxic compounds and that chemically similar compounds often have similar toxic effects. The three tolerance models (median lethal concentration after 96 h) used up to 25 aquatic animal species and up to nine pesticides (organochlorines, organophosphates and carbamates). Phylogeny was estimated using DNA sequences, while the pesticides were described by their mode of toxic action and their octanol-water partition coefficients. The models explained 77-84% of the among-species variation in tolerance (log10 LC50). In cross-validation, 84-87% of the predicted tolerances for individual species were within a factor of 10 of the observed values. The approach can also be used to model other species response to multivariate stress factors.

  18. AN ENVIRONMENTAL TECHNOLOGY VERIFICATION (ETV) TESTING OF ENZYMATIC TEST KITS FOR WARFARE AGENTS AND PESTICIDES IN DRINKING WATER

    Enzymatic test kits, generally designed to be handheld and portable, detect the presence of chemical agents, carbamate pesticides, and/or organophosphate pesticides by relying on the reaction of the cholinesterase enzyme. Under normal conditions, the enzyme reacts as expected wi...

  19. Evaluation of the Pollution of surface waters in the basin of west Algeria by Organo chlorine and Organophosphorus pesticides

    Hadjel, M.; Berkok, N.

    2009-07-01

    The pollutants are pesticides which cover a whole range of chemicals designed to protect plants from pests and destroy unwanted plants. There are a very large number of pesticides and we do here that some of the major families (organo chlorine insecticides, organophosphates, carbamates, pyrethroids, phenylcyclohexyl, herbicides. (Author)

  20. Development and validation of multiresidue analytical method in cotton and groundnut oil for 87 pesticides using low temperature and dispersive cleanup on gas chromatography and liquid chromatography-tandem mass spectrometry.

    Chawla, Suchi; Patel, Hemlatta K; Vaghela, Kiran M; Pathan, Firoz Khan; Gor, Hetal N; Patel, Anil R; Shah, Paresh G

    2016-01-01

    A method was developed and validated for the analysis of 87 pesticides in cotton and groundnut oil by GC with ECD and FPD detectors and LC-MS/MS. The extraction procedure based on QuEChERS followed by low-temperature freezing and dispersive cleanup steps was validated in two oil matrices for 87 pesticides of different classes. Linearity, expressed as coefficient of variation, was within the acceptable range. Of those tested, 77-83 and 77-89% pesticides showed recoveries within the acceptable range of 70-120% on LC-MS/MS in cottonseed oil and groundnut oil, respectively, at different spiking levels. In case of GC analysis, 63-65 and 53-82% pesticides showed recoveries within the acceptable range of 70-120% on GC in cottonseed oil and groundnut oil, respectively, at different spiking levels. The exceptions to these recoveries were the few organochlorines which consistently gave lower recoveries. Recovery factors can be employed while analysing these pesticides by this method as the results obtained were consistent in both oils. RSD was less than 20% for most of the pesticides. The calculated limit of quantitation (LOQ) for most of the pesticides satisfies the maximum residue level (MRL) requirements as per European Union (EU) guidelines and Food Safety and Standards Authority of India (FSSAI).

  1. Assessing, mapping and validating site-specific ecotoxicological risk for pesticide mixtures: a case study for small scale hot spots in aquatic and terrestrial environments.

    Vaj, Claudia; Barmaz, Stefania; Sørensen, Peter Borgen; Spurgeon, David; Vighi, Marco

    2011-11-01

    Mixture toxicity is a real world problem and as such requires risk assessment solutions that can be applied within different geographic regions, across different spatial scales and in situations where the quantity of data available for the assessment varies. Moreover, the need for site specific procedures for assessing ecotoxicological risk for non-target species in non-target ecosystems also has to be recognised. The work presented in the paper addresses the real world effects of pesticide mixtures on natural communities. Initially, the location of risk hotspots is theoretically estimated through exposure modelling and the use of available toxicity data to predict potential community effects. The concept of Concentration Addition (CA) is applied to describe responses resulting from exposure of multiple pesticides The developed and refined exposure models are georeferenced (GIS-based) and include environmental and physico-chemical parameters, and site specific information on pesticide usage and land use. As a test of the risk assessment framework, the procedures have been applied on a suitable study areas, notably the River Meolo basin (Northern Italy), a catchment characterised by intensive agriculture, as well as comparative area for some assessments. Within the studied areas, the risks for individual chemicals and complex mixtures have been assessed on aquatic and terrestrial aboveground and belowground communities. Results from ecological surveys have been used to validate these risk assessment model predictions. Value and limitation of the approaches are described and the possibilities for larger scale applications in risk assessment are also discussed.

  2. Multiresidue analysis of 36 pesticides in soil using a modified quick, easy, cheap, effective, rugged, and safe method by liquid chromatography with tandem quadruple linear ion trap mass spectrometry.

    Feng, Xue; He, Zeying; Wang, Lu; Peng, Yi; Luo, Ming; Liu, Xiaowei

    2015-09-01

    A new method for simultaneous determination of 36 pesticides, including 15 organophosphorus, six carbamate, and some other pesticides in soil was developed by liquid chromatography with tandem quadruple linear ion trap mass spectrometry. The extraction and clean-up steps were optimized based on the quick, easy, cheap, effective, rugged, and safe method. The data were acquired in multiple reaction monitoring mode combined with enhanced product ion to increase confidence of the analytical results. Validation experiments were performed in soil samples. The average recoveries of pesticides at four spiking levels (1, 5, 50, and 100 μg/kg) ranged from 63 to 126% with relative standard deviation below 20%. The limits of detection of pesticides were 0.04-0.8 μg/kg, and the limits of quantification were 0.1-2.6 μg/kg. The correlation coefficients (r(2) ) were higher than 0.990 in the linearity range of 0.5-200 μg/L for most of the pesticides. The method allowed for the analysis of the target pesticides in the lower μg/kg concentration range. The optimized method was then applied to the test of real soil samples obtained from several areas in China, confirming the feasibility of the method.

  3. Method validation for the analysis of 169 pesticides in soya grain, without clean up, by liquid chromatography-tandem mass spectrometry using positive and negative electrospray ionization.

    Pizzutti, Ionara R; de Kok, André; Zanella, Renato; Adaime, Martha B; Hiemstra, Maurice; Wickert, Cristine; Prestes, Osmar D

    2007-02-23

    Part of a comprehensive study on the comparison of different extraction methods, GC-MS(/MS) and LC-MS/MS detection methods and modes, for the analysis of soya samples is described in this paper. The validation of an acetone-based extraction method for analysis of 169 pesticides in soya, using LC-MS/MS positive and negative electrospray ionisation (ESI) mode, is reported. Samples (5 g) were soaked with 10 g water and subsequently extracted with 100 mL of a mixture of acetone, dichloromethane and light petroleum (1:1:1), in the presence of 15 g anhydrous sodium sulphate. After centrifugation, aliquots of the extract were evaporated and reconstituted in 1.0 mL of methanol, before direct injection of the final extract (corresponding with 0.05 g soya mL(-1)) into the LC-MS/MS system. Linearity, r(2) of calibration curves, instrument limit of detection/quantitation (LOD/LOQ) and matrix effect were evaluated, based on seven concentrations measured in 6-fold. Good linearity (at least r(2)> or =0.99) of the calibration curves was obtained over the range from 0.1 or 0.25 to 10.0 ng mL(-1), corresponding with pesticide concentrations in soya bean extract of 2 or 5-200 microg kg(-1). Instrument LOD values generally were 0.1 or 0.25 ng mL(-1). Matrix effects were negligible for approximately 90% of the pesticides. The accuracy, precision and method LOQ were determined via recovery experiments, spiking soya at 10, 50, 100 microg kg(-1), six replicates per level. In both ESI modes, method LOQ values were mostly 10 or 50 microg kg(-1) and more than 70% of pesticides analysed by each mode met the acceptability criteria of recovery (70-120%) and RSD (soya, without cleanup.

  4. Organophosphorus and carbamates residues in milk and feedstuff supplied to dairy cattle

    Rafael Fagnani

    2011-07-01

    Full Text Available Considering acute and chronic toxicity effects on human and animal health caused by pesticide residues in food, this study aimed to analyze organophosphorate (OP and carbamate (CB in feedstuff and water destined for dairy cattle, as well as in the milk produced by these animals, through gas chromatography (GC. In the Agreste region of Pernambuco, Brazil, 30 raw milk samples and all components of the animals' diet were collected from several farms. Out of the 30 milk of milk analyzed, six (20% were contaminated with OP, five (16.7% with CB, and one sample with both pesticides. From 48 analyzed feed samples, 15 (31.25% were contaminated with residues of OP, six (12.50% with CB, and one sample was contaminated with both pesticides. Out of 16 water samples analyzed, six (37.50% were contaminated with OP residues, but non with CB. In four dairy farms the pesticides detected in milk were compatible with the active principles found in water and/or foodstuff, suggesting them to be the source of contamination.

  5. Modification and re-validation of the ethyl acetate-based multi-residue method for pesticides in produce

    Mol, H.G.J.; Rooseboom, A.; Dam, R. van; Roding, M.; Arondeus, K.; Sunarto, S.

    2007-01-01

    The ethyl acetate-based multi-residue method for determination of pesticide residues in produce has been modified for gas chromatographic (GC) analysis by implementation of dispersive solid-phase extraction (using primary-secondary amine and graphitized carbon black) and large-volume (20 μL) injecti

  6. Modification and re-validation of the ethyl acetate-based multi-residue method for pesticides in produce

    Mol, J.G.J.; Rooseboom, A.; Dam, van R.; Roding, M.; Arondeus, K.; Sunarto, S.

    2007-01-01

    The ethyl acetate-based multi-residue method for determination of pesticide residues in produce has been modified for gas chromatographic (GC) analysis by implementation of dispersive solid-phase extraction (using primary¿secondary amine and graphitized carbon black) and large-volume (20 ¿L) injecti

  7. Vortex-assisted surfactant-enhanced emulsification liquid-liquid microextraction for the determination of carbamates in juices by micellar electrokinetic chromatography tandem mass spectrometry.

    Moreno-González, David; Huertas-Pérez, José F; García-Campaña, Ana M; Gámiz-Gracia, Laura

    2015-07-01

    A new method based on vortex-assisted surfactant-enhanced-emulsification liquid-liquid microextraction has been developed for the extraction of carbamate pesticides in juice samples prior to their determination by micellar electrokinetic chromatography coupled to tandem mass spectrometry. This sample treatment allowed the satisfactory extraction and the extract clean-up of 25 carbamates from different fruit and vegetal juices (banana, tomato, and peach). In this study, the addition of ammonium perfluorooctanoate in the aqueous sample in combination with vortex agitation, provided very clean extracts with short extraction times. Under optimized conditions, recoveries of the proposed method for these pesticides from fortified juice samples ranged from 81% to 104%, with relative standard deviations lower than 15%. Limits of quantification were between 2.3µgkg(-)(1) and 4.7µgkg(-)(1), showing the high sensitivity of this fast and simple method.

  8. Pesticide use and self-reported symptoms of acute pesticide poisoning among aquatic farmers in Phnom Penh, Cambodia

    Jensen, Hanne Klith; Konradsen, Flemming; Jørs, Erik

    2011-01-01

    Organophosphates and carbamates (OPs/CMs) are known for their acetylcholinesterase inhibiting character. A cross-sectional study of pesticide handling practices and self-perceived symptoms of acute pesticide poisoning was conducted using questionnaire-based interviews with 89 pesticide sprayers...... in Boeung Cheung Ek (BCE) Lake, Phnom Penh, Cambodia. The study showed that 50% of the pesticides used belonged to WHO class I + II and personal protection among the farmers were inadequate. A majority of the farmers (88%) had experienced symptoms of acute pesticide poisoning, and this was significantly...... associated with the number of hours spent spraying with OPs/CMs (OR = 1.14, CI 95%: 1.02-1.28). The higher educated farmers reduced their risk of poisoning by 55% for each extra personal protective measure they adapted (OR = 0.45, CI 95%: 0.22-0.91). These findings suggest that improving safe pesticide...

  9. Select small core structure carbamates exhibit high contact toxicity to "carbamate-resistant" strain malaria mosquitoes, Anopheles gambiae (Akron.

    Dawn M Wong

    Full Text Available Acetylcholinesterase (AChE is a proven target for control of the malaria mosquito (Anopheles gambiae. Unfortunately, a single amino acid mutation (G119S in An. gambiae AChE-1 (AgAChE confers resistance to the AChE inhibitors currently approved by the World Health Organization for indoor residual spraying. In this report, we describe several carbamate inhibitors that potently inhibit G119S AgAChE and that are contact-toxic to carbamate-resistant An. gambiae. PCR-RFLP analysis was used to confirm that carbamate-susceptible G3 and carbamate-resistant Akron strains of An. gambiae carry wild-type (WT and G119S AChE, respectively. G119S AgAChE was expressed and purified for the first time, and was shown to have only 3% of the turnover number (k(cat of the WT enzyme. Twelve carbamates were then assayed for inhibition of these enzymes. High resistance ratios (>2,500-fold were observed for carbamates bearing a benzene ring core, consistent with the carbamate-resistant phenotype of the G119S enzyme. Interestingly, resistance ratios for two oxime methylcarbamates, and for five pyrazol-4-yl methylcarbamates were found to be much lower (4- to 65-fold. The toxicities of these carbamates to live G3 and Akron strain An. gambiae were determined. As expected from the enzyme resistance ratios, carbamates bearing a benzene ring core showed low toxicity to Akron strain An. gambiae (LC(50>5,000 μg/mL. However, one oxime methylcarbamate (aldicarb and five pyrazol-4-yl methylcarbamates (4a-e showed good to excellent toxicity to the Akron strain (LC(50 = 32-650 μg/mL. These results suggest that appropriately functionalized "small-core" carbamates could function as a resistance-breaking anticholinesterase insecticides against the malaria mosquito.

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

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

    2005-01-01

    5 classical tracer pesticides but also for other chemical classes of herbicides (sulfonylurea, aryloxyalcanoic acids, chloroacetanilides), insecticides (pyrethroids, carbamates) and fungicides (dicarboximides, phenylamides, triazoles and strobilurines). To monitor these pesticides in elutes and substrates, two analytical methods were developed, optimised and validated : the first one by Gas Chromatography with Mass Spectrometry Detection (GC-MS), and the second one by High Performance Liquid Chromatography with UV Diode Array Detection (HPLC-DAD). The micro-organisms activity in the substrate was also measured in some situations.

  11. Pesticide burial grounds in Poland: a review.

    Gałuszka, Agnieszka; Migaszewski, Zdzisław M; Manecki, Piotr

    2011-10-01

    Obsolete pesticides were stored in Poland from the middle sixties until the late eighties of the 20th century mostly in underground disposal sites, called "pesticide burial grounds" or "pesticide tombs". The total amount of pesticide waste and packaging materials disposed of in these landfills exceeded 20000 Mg. Typically, the content of a pesticide tomb was dominated by organochlorine pesticides (comprising 10-100% of the total waste volume) with DDT as the prevailing compound. Other pesticide types, such as phosphoroorganic, carbamate insecticides, dinitrophenols, phenoxyacids, and inorganic compounds were stored in smaller quantities, usually not exceeding 10-20% of the total waste volume. With the growing awareness of the threats that these landfills posed to the environment, the first inventory for the whole country was made in 1993 and remediation was initiated in 1999. The total amount of waste, which had to be removed from the known pesticide tombs (hazardous substances, contaminated soils, construction materials etc.) was about 100000 Mg. According to the National Waste Management Plan, the reclamation of pesticide tombs was assumed to have been finished by the end of 2010, however, this goal has not been achieved. The aim of this review is to present a historical perspective of pesticide burial grounds in Poland with an emphasis on their creation, function, inventory, and remediation. Based on unpublished reports, and other published materials of limited availability written in Polish, this review may serve as a source of information for representatives of other countries, where remediation of pesticide burial grounds is still in progress. The experience gained over a ten-year period, when restoration of pesticide tombs was implemented in Poland, reveals that there are many obstacles to this action arising not only from technical, but also from economic and social issues.

  12. Method validation for 243 pesticides and environmental contaminants in meats and poultry by tandem mass spectrometry coupled to low-pressure gas chromatography and ultra high-performance liquid chromatography

    An easy and reliable high-throughput analysis method was developed and validated for 192 diverse pesticides and 51 environmental contaminants (13 PCB congeners, 14 PAHs, 7 PBDE congeners, and 17 novel flame retardants) in cattle, swine, and poultry muscle. Sample preparation was based on the “quick,...

  13. High lethality and minimal variation after acute self-poisoning with carbamate insecticides in Sri Lanka – implications for global suicide prevention

    Lamb, Thomas; Selvarajah, Liza R.; Mohamed, Fahim; Jayamanne, Shaluka; Gawarammana, Indika; Mostafa, Ahmed; Buckley, Nicholas A.; Roberts, Michael S.; Eddleston, Michael

    2016-01-01

    Abstract Background: Highly hazardous organophosphorus (OP) insecticides are responsible for most pesticide poisoning deaths. As they are removed from agricultural practice, they are often replaced by carbamate insecticides of perceived lower toxicity. However, relatively little is known about poisoning with these insecticides. Methods: We prospectively studied 1288 patients self-poisoned with carbamate insecticides admitted to six Sri Lankan hospitals. Clinical outcomes were recorded for each patient and plasma carbamate concentration measured in a sample to confirm the carbamate ingested. Findings: Patients had ingested 3% carbofuran powder (719), carbosulfan EC25 liquid (25% w/v, 389), or fenobucarb EC50 liquid (50% w/v, 127) formulations, carbamate insecticides of WHO Toxicity Classes Ib, II, and II, respectively. Intubation and ventilation was required for 183 (14.2%) patients while 71 (5.5%) died. Compared with carbofuran, poisoning with carbosulfan or fenobucarb was associated with significantly higher risk of death [carbofuran 2.2%; carbosulfan 11.1%, OR 5.5 (95% CI 3.0–9.8); fenobucarb 6.3%, OR 3.0 (1.2–7.1)] and intubation [carbofuran 6.1%; carbosulfan 27.0%, OR 5.7 (3.9–8.3); fenobucarb 18.9%, OR 3.6 (2.1–6.1)]. The clinical presentation and cause of death did not differ markedly between carbamates. Median time to death was similar: carbofuran 42.3 h (IQR 5.5–67.3), carbosulfan 21.3 h (11.5–71.3), and fenobucarb 25.3 h (17.3–72.1) (p = 0.99); no patients showed delayed onset of toxicity akin to the intermediate syndrome seen after OP insecticide poisoning. For survivors, median duration of intubation was 67.8 h (IQR 27.5–118.8) with no difference in duration between carbamates. Reduced GCS at presentation was associated with worse outcome although some patients with carbosulfan died after presentation with normal GCS. Conclusions: We did not find carbamate insecticide self-poisoning to vary markedly according to the carbamate

  14. Increasing pesticide-resistant ectoparasitic infections may increase pesticide poisoning risks in children.

    Diaz, James H

    2008-01-01

    Head louse and scabies mite infestations are common among pre-school and school-age children, and topical pesticides are frequently prescribed to treat such conditions. Ectoparasite resistance to the safest and most commonly prescribed pyrethrin/pyrethroid pesticides for ectoparasitic infections has, however, been increasing since the 1980s. The increasing resistance of these arthropods to the safest pesticides may lead to greater use of more toxic, alternative pesticides to control infestations and to prevent institutional outbreaks. MEDLINE and Cochrane searches, 1966-2008, were conducted to assess the impact of increasing pesticide resistance on prescribing practices for ectoparasitic infections and to describe the evolving global epidemiology of pediatric poisonings by more toxic pediculicides and miticides, including carbamates, organochlorines, and organophosphates. Pharmacists, physicians, and poison control personnel should be fully informed about increasing pesticide resistance among the most commonly encountered ectoparasites of children and the institutionalized and be prepared to prevent and to treat accidental home and institutional pesticide poisonings with more toxic pesticides.

  15. Comparative in vitro-in vivo percutaneous absorption of the pesticide propoxur

    Sandt, J.J.M. van de; Meuling, W.J.A.; Elliott, G.R.; Cnubben, N.H.P.; Hakkert, B.C.

    2000-01-01

    In vitro and in vivo skin absorption of the pesticide propoxur (2-isopropoxyphenyl N-methyl carbamate, commercially Baygon(TM) and Unden(TM); log Po/w 1.56, MW 209.2) was investigated. In vivo studies were performed in rats and human volunteers, applying the test compound to the dorsal skin and the

  16. Antimicrobial Pesticides

    Jump to main content US EPA United States Environmental Protection Agency Search Search Pesticides Share Facebook Twitter Google+ ... of antimicrobial pesticides (Part 158W) Antimicrobials play an important role in public health and safety. While providing ...

  17. Tolerance to the carbamate insecticide propoxur.

    Costa, L G; Hand, H; Schwab, B W; Murphy, S D

    1981-01-01

    Male mice were given the carbamate insecticide propoxur (2-isopropoxy phenyl methylcarbamate; Baygon) in the drinking water at weekly increasing concentrations (from 50 to 2000 ppm), for a period of 6 weeks. At the end of the treatment the LD50 for propoxur was significantly higher in the treated animals as compared with controls. Propoxur-treated animals were also resistant to the hypothermic effect of an acute administration of the same compound. Groups of mice were challenged with the cholinergic agonist carbachol at intervals during the drinking water dosing and at its end. No differences in sensitivity to carbachol acute toxicity were found between control and treated animals. Propoxur-tolerant animals were also not resistant to the hypothermic effect of oxotremorine, another cholinergic agonist. [3H]Quinuclidinyl benzilate ([3H]QNB) binding (a measure of muscarinic receptor density and affinity) in forebrain, hindbrain and ileum never differed in control and treated mice. The possibility that repeated administrations of propoxur induced increased metabolic inactivation was tested by measuring hexobarbital sleeping time and carboxylesterase activity in treated and control mice. No changes in tissue carboxylesterase activities occurred but hexobarbital sleeping time was significantly reduced in propoxur treated animals suggesting an induction of hepatic microsomal enzymes. These results suggest that tolerance to propoxur is not mediated by a decrease of cholinergic receptors, as reported for other acetylcholinesterase inhibitors, but possibly by an enhancement of its metabolism.

  18. 40 CFR 721.7200 - Perfluoroalkyl aromatic carbamate modified alkyl methacrylate copolymer.

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Perfluoroalkyl aromatic carbamate... Significant New Uses for Specific Chemical Substances § 721.7200 Perfluoroalkyl aromatic carbamate modified...) The chemical substance identified generically as perfluoroalkyl aromatic carbamate modified...

  19. Synthesis and decreasing Aβ content evaluation of arctigenin-4-yl carbamate derivatives.

    Xu, Xingyu; Li, Cong; Lei, Min; Zhu, Zhiyuan; Yan, Jianming; Shen, Xu; Hu, Lihong

    2016-07-01

    A series of arctigenin-4-yl carbamate derivatives were synthesized and evaluated for potency in reducing β-amyloid (Aβ) content in HEK293-APPswe cells. Most of the arctigenin-4-yl aralkyl or aryl carbamate derivatives showed improved potency in reducing Aβ content. Among the synthesized compounds, arctigenin-4-yl (3-chlorophenyl)carbamate (20) exhibited the strongest potency with 78.7% Aβ content reduction at 20μM. Furthermore, the effect of arctigenin-4-yl (4-chlorophenyl)carbamate (19) and arctigenin-4-yl (3-chlorophenyl)carbamate (20) on lowing Aβ content was better than arctigenin under the concentrations of 1, 10 and 20μM.

  20. A computational quantitative structure-activity relationship study of carbamate anticonvulsants using quantum pharmacological methods.

    Knight, J L; Weaver, D F

    1998-10-01

    A pattern recognition quantitative structure-activity relationship (QSAR) study has been performed to determine the molecular features of carbamate anticonvulsants which influence biological activity. Although carbamates, such as felbamate, have been used to treat epilepsy, their mechanisms of efficacy and toxicity are not completely understood. Quantum and classical mechanics calculations have been exploited to describe 46 carbamate drugs. Employing a principal component analysis and multiple linear regression calculations, five crucial structural descriptors were identified which directly relate to the bioactivity of the carbamate family. With the resulting mathematical model, the biological activity of carbamate analogues can be predicted with 85-90% accuracy.

  1. (1)H NMR-based metabonomic profiling of rat serum and urine to characterize the subacute effects of carbamate insecticide propoxur.

    Liang, Yu-Jie; Wang, Hui-Ping; Long, Ding-Xin; Wu, Yi-Jun

    2012-09-01

    Carbamate insecticide propoxur is widely used in agriculture and public health programs. To prevent adverse health effects arising from exposure to this insecticide, sensitive methods for detection of early stage organismal changes are necessary. We present here an integrative metabonomic approach to investigate toxic effects of pesticide in experimental animals. Results showed that propoxur even at low dose levels can induce oxidative stress, impair liver function, enhance ketogenesis and fatty acid β-oxidation, and increase glycolysis, which contribute to the hepatotoxocity. These findings highlight the applicability of (1)H NMR spectroscopy and multivariate statistics in elucidating the toxic effects of propoxur.

  2. Pesticide Use and Self-Reported Symptoms of Acute Pesticide Poisoning among Aquatic Farmers in Phnom Penh, Cambodia

    Hanne Klith Jensen

    2011-01-01

    Full Text Available Organophosphates and carbamates (OPs/CMs are known for their acetylcholinesterase inhibiting character. A cross-sectional study of pesticide handling practices and self-perceived symptoms of acute pesticide poisoning was conducted using questionnaire-based interviews with 89 pesticide sprayers in Boeung Cheung Ek (BCE Lake, Phnom Penh, Cambodia. The study showed that 50% of the pesticides used belonged to WHO class I + II and personal protection among the farmers were inadequate. A majority of the farmers (88% had experienced symptoms of acute pesticide poisoning, and this was significantly associated with the number of hours spent spraying with OPs/CMs (OR = 1.14, CI 95%: 1.02–1.28. The higher educated farmers reduced their risk of poisoning by 55% for each extra personal protective measure they adapted (OR = 0.45, CI 95%: 0.22–0.91. These findings suggest that improving safe pesticide management practices among the farmers and enforcing the effective banning of the most toxic pesticides will considerably reduce the number of acute pesticide poisoning episodes.

  3. 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.

  4. Measurement of pyrethroid, organophosphorus, and carbamate insecticides in human plasma using isotope dilution gas chromatography-high resolution mass spectrometry.

    Pérez, José J; Williams, Megan K; Weerasekera, Gayanga; Smith, Kimberly; Whyatt, Robin M; Needham, Larry L; Barr, Dana Boyd

    2010-10-01

    We have developed a gas chromatography-high resolution mass spectrometry method for measuring pyrethroid, organophosphorus, carbamate and fipronil pesticides and the synergist piperonyl butoxide in human plasma. Plasma samples were extracted using solid phase extraction and were then concentrated for injection and analysis using isotope dilution gas chromatography-high resolution mass spectrometry. The limits of detection ranged from 10 to 158 pg/mL with relative recoveries at concentrations near the LODs (e.g., 25 or 250 pg/mL) ranging from 87% to 156% (9 of the 16 compounds were within ±15% of 100%). The extraction recoveries ranged from 20% to 98% and the overall method relative standard deviations were typically less than 20% with some exceptions. Analytical characteristics were determined at 25, 250, and 1000 pg/mL.

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

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

    2014-08-01

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

  6. Pesticides and oil and grease in selected streams and lakes in northeastern Louisiana, 2001

    McGee, Benton D.

    2003-01-01

    A 6-month study was begun in April 2001 to determine the concentrations of pesticides or oil and grease in selected stream reaches and lakes within the Ouachita, Tensas, and Black River Basins in northeastern Louisiana. During April through September 2001, six monthly water samples for analysis of pesticides were collected from 22 sites: 17 sites were on 11 streams, and 5 sites were on 5 lakes. During Apirl through July 2001, four monthly samples for analysis of oil and grease were collected from 5 sites: 4 sites were on three streams, and 1 site was on a lake. A total of 131 water samples were analyzed for 17 pesticides (15 insecticides and 2 herbicides). The following classes of pesticides, as classified from the Pesticide Analysis (U.S. Environmental Protection Agency Region 6 Laboratory), are reported: organochlorine, nitrogen-phosphorus, and carbamate. The 8 pesticides detected in samples, in decreasing frequency, were as follow: atrazine, molinate, methyl parathion, 4,4'-DDT, carbofuran, diazinon, toxaphene, and 4,4'DDE. Organochlorine pesticides (insecticides) represented the majority (12 out of 17) of the pesticides analyzed. Of those 12 organochlorine pesticides, only 3 (4,4'-DDT, 4,4'-DDE, and toxaphene) were detected in the 131 samples. Of the organochlorine pesticides, 4,4'-DDT was detected most frequently (in 11 percent of the samples), and concentrations ranged from 1.22 to 4.70 ng/L (nanograms per liter). Nitrogen-phosphorus pesticides were the most frequently detected and abundant pesticides. Of all the pesticides analyzed, atrazine and molinate (nitrogen-phosphorus herbicides) were the pesticides most frequently detected (in 93 and 21 percent of the samples), had the highest and most wide-ranging concentrations (10.8 to 15,100 ng/L and 10.0 to 11,600 ng/L), and were most widely distributed throughout the study area. Carbofuran, a carbamate insecticide, was detected at 8 of the 22 pesticide data-collection sites and in 9.2 percent of the 131 samples

  7. Potential developmental neurotoxicity of pesticides used in Europe

    Grandjean Philippe

    2008-10-01

    Full Text Available Abstract Pesticides used in agriculture are designed to protect crops against unwanted species, such as weeds, insects, and fungus. Many compounds target the nervous system of insect pests. Because of the similarity in brain biochemistry, such pesticides may also be neurotoxic to humans. Concerns have been raised that the developing brain may be particularly vulnerable to adverse effects of neurotoxic pesticides. Current requirements for safety testing do not include developmental neurotoxicity. We therefore undertook a systematic evaluation of published evidence on neurotoxicity of pesticides in current use, with specific emphasis on risks during early development. Epidemiologic studies show associations with neurodevelopmental deficits, but mainly deal with mixed exposures to pesticides. Laboratory experimental studies using model compounds suggest that many pesticides currently used in Europe – including organophosphates, carbamates, pyrethroids, ethylenebisdithiocarbamates, and chlorophenoxy herbicides – can cause neurodevelopmental toxicity. Adverse effects on brain development can be severe and irreversible. Prevention should therefore be a public health priority. The occurrence of residues in food and other types of human exposures should be prevented with regard to the pesticide groups that are known to be neurotoxic. For other substances, given their widespread use and the unique vulnerability of the developing brain, the general lack of data on developmental neurotoxicity calls for investment in targeted research. While awaiting more definite evidence, existing uncertainties should be considered in light of the need for precautionary action to protect brain development.

  8. Pesticide contamination of the coastline of Martinique.

    Bocquené, Gilles; Franco, Alain

    2005-01-01

    In January and February 2002, the presence of certain agricultural pesticides throughout the coastline of the Caribbean island of Martinique was investigated. The tropical climate of the French West Indies is suitable for banana production, which requires intensive use of pesticides. An inventory of all pesticides used on the island (compounds and tonnage) was compiled. Surveys and analyses revealed the presence of pesticides in the plumes of seven rivers. The organochlorine chlordecone and metabolites of aldicarb were detected at nearly all of the monitored sites, even though the use of chlordecone has been prohibited since 1993. Two triazines (ametryn and simazine) were also identified. The concentrations of carbamates and triazines detected in the water and sediment samples from Martinique are comparable to those reported for mainland France. Chlordecone concentrations in the sediment and particulate matter samples were, however, particularly high in the samples from Martinique. Toxicological implications are discussed. Of particular concern are the high levels of chlordecone (which is bioaccumulating and carcinogenic) and further monitoring of this compound is recommended, especially in fish and other sea-food products.

  9. Correlation between Cholinesterase and Paraoxonase 1 Activities: Case Series of Pesticide Poisoning Subjects

    S Austin Richard

    2013-08-01

    Full Text Available Introduction: Acute exposure to pesticide due to suicidal poisoning is the most extensive cause of pesticide exposure, compared with all other causes including agricultural or industrial exposure. Organophosphate (OP and carbamate group of pesticides can inhibit acetylcholinesterase; on the other hand, paraoxonase1 can detoxify organophosphate poisoning by hydrolyzing organophosphate metabolites. Methods: We have compared the serum paraoxonase1 status and cholinesterase activity of subjects who attempted to commit suicide by consuming OP pesticide. Cholinesterase and paraoxonase1 activity were measured spectrophotometrically using butyrylthiocholine and phenyl acetate as substrates, respectively. Results: A positive correlation was found between serum paraoxonase1 activity and cholinesterase activity among pesticide consumed subjects. Conclusion: Our results suggest that subjects with higher paraoxonase1 activity may have a better chance of detoxifying the lethal effect of acute organophosphate poisoning.

  10. The Target of Benzimidazole Carbamate Against Cysticerci cellulosae

    LI Qing-zhang; HAO Yan-hong; GAO Xue-jun; GAO Wen-xue; ZHAO Bing

    2007-01-01

    To study the target of benzimidazole carbamate drugs against Cysticerci cellulosae and give a theoretical basis for type evolution and new drug design, the changes of key enzyme activities and metabolite contents in the pathway of energy metabolism in C. cellulosae in vitro and in vivo were tested with albendazole and oxfendazole, respectively. Both albendazole and oxfendazole inhibited the pathways of anaerobic glycolysis, partial inversed tricarboxylic acid cycle of Taenia Solium oncosphere, immature and mature Cysticerci in vitro, and immature and mature Cysticerci in vivo to a certain degree, and enhanced fat decomposing, amino acid decomposing, xanthine decomposing metabolism, and on the other hand, the absorption of glucose was hindered; furthermore, both albendazole and oxfendazole inhibited the activities of the fumaric reductase (FR) complex noncompetently in vitro. Benzimidazole carbamate drugs could inhibit the activities of FR complex noncompetently and hinder the absorption of glucose.

  11. Rapid determination of residues of pesticides in honey by µGC-ECD and GC-MS/MS: Method validation and estimation of measurement uncertainty according to document No. SANCO/12571/2013.

    Paoloni, Angela; Alunni, Sabrina; Pelliccia, Alessandro; Pecorelli, Ivan

    2016-01-01

    A simple and straightforward method for simultaneous determination of residues of 13 pesticides in honey samples (acrinathrin, bifenthrin, bromopropylate, cyhalothrin-lambda, cypermethrin, chlorfenvinphos, chlorpyrifos, coumaphos, deltamethrin, fluvalinate-tau, malathion, permethrin and tetradifon) from different pesticide classes has been developed and validated. The analytical method provides dissolution of honey in water and an extraction of pesticide residues by n-Hexane followed by clean-up on a Florisil SPE column. The extract was evaporated and taken up by a solution of an injection internal standard (I-IS), ethion, and finally analyzed by capillary gas chromatography with electron capture detection (GC-µECD). Identification for qualitative purpose was conducted by gas chromatography with triple quadrupole mass spectrometer (GC-MS/MS). A matrix-matched calibration curve was performed for quantitative purposes by plotting the area ratio (analyte/I-IS) against concentration using a GC-µECD instrument. According to document No. SANCO/12571/2013, the method was validated by testing the following parameters: linearity, matrix effect, specificity, precision, trueness (bias) and measurement uncertainty. The analytical process was validated analyzing blank honey samples spiked at levels equal to and greater than 0.010 mg/kg (limit of quantification). All parameters were satisfactorily compared with the values established by document No. SANCO/12571/2013. The analytical performance was verified by participating in eight multi-residue proficiency tests organized by BIPEA, obtaining satisfactory z-scores in all 70 determinations. Measurement uncertainty was estimated according to the top-down approaches described in Appendix C of the SANCO document using the within-laboratory reproducibility relative standard deviation combined with laboratory bias using the proficiency test data.

  12. Herbicide and pesticide occurrence in the soils of children's playgrounds in Sarajevo, Bosnia and Herzegovina.

    Sapcanin, Aida; Cakal, Mirsada; Imamovic, Belma; Salihovic, Mirsada; Pehlic, Ekrem; Jacimovic, Zeljko; Jancan, Gordan

    2016-08-01

    Pesticide pollution in Sarajevo public playgrounds is an important health and environmental issue, and the lack of information about it is causing concerns amongst the general population as well as researchers. Since children are in direct contact with surface soils on children's playgrounds, such soils should be much more carefully examined. Furthermore, herbicides and pesticides get transmitted from soil surfaces brought from outside the urban areas, or they get dispersed following their direct applications in urban areas. Infants' and children's health can be directly affected by polluted soils because of the inherent toxicity and widespread use of the different pesticides in urban environments such as playgrounds. In addition to that, the presence of chromated copper arsenate (CCA) wood preservative pesticide found as soil pollutant in playing equipment was also documented. Soil samples from playgrounds were collected and analyzed for triazines, carbamates, dithiocarbamates, phenolic herbicides and organochlorine pesticides. Samples for the determination of heavy metals Cu, Cr and As were prepared by microwave-assisted acid digestion, and the findings were determined by using an inductively coupled plasma optical emission spectrometer. Triazines, carbamates, dithiocarbamates, chlorphenoxy compounds, phenolic herbicides, organochlorine pesticides and organotin compounds were detected in playground soils and their determined concentrations (mg/kg) were respectively found as follows: playground soils.

  13. Effect of pesticide exposure on acetylcholinesterase activity in subsistence farmers from Campeche, Mexico.

    Rendón von Osten, Jaime; Epomex, Centro; Tinoco-Ojanguren, Rolando; Soares, Amadeu M V M; Guilhermino, Lucia

    2004-08-01

    The authors surveyed agricultural production methods and pesticide use among subsistence farmers (campesinos) in 4 rural communities of Campeche, Mexico. Self-reports of symptoms of poisoning resulting from occupational pesticide exposure were elicited by questionnaire (N = 121), and acetylcholinesterase (AChE) activity during insecticide use was evaluated from blood samples (N = 127). In individuals from 2 of the 4 communities, AChE activity was significantly lower (p < 0.05) than the mean of activity determined for individuals in a reference group. Results of this study show that erythrocyte AChE inhibition provides a good biomarker of exposure to organophosphate pesticides in field studies with human populations. Carbamates, particularly carbofuran, seem to be more associated with exuberant and diversified symptomatology of pesticide exposure than organophosphates. Studies in field communities where both carbamates and organophosphates are suspected to exist should include blood AChE determinations, symptomatology surveys, and socioeconomic questionnaires. The authors recommend that the Mexican National Health Ministry authorities specify additional provisions regarding the use of protective equipment and the adoption of other safety practices during field work, increase information campaigns about the risks of pesticide use and the value of safety practices, and increase programs of medical monitoring and assistance for rural communities dealing with pesticides.

  14. National Pesticide Information Center

    ... any pest." Herbicides Disinfectants Fungicides Insecticides Natural and Biological Pesticides Repellents Rodenticides Other types of pesticides Local Contacts Find local pesticide & pest control information Pesticide Information and Resources: Frequently Asked Questions: ...

  15. Introduction to Pesticide Labels

    Pesticide product labels provide critical information about how to safely and legally handle and use pesticide products. Unlike most other types of product labels, pesticide labels are legally enforceable. Learn about pesticide product labels.

  16. Pesticides in the propolis at São Saulo State, Brazil - doi: 10.4025/actascianimsci.v34i4.15859 Pesticides in the propolis at São Saulo State, Brazil - doi: 10.4025/actascianimsci.v34i4.15859

    Samir Moura Kadri

    2012-10-01

    Full Text Available The increasing demand for propolis has caused a raise in its production. However, an increasingly pesticide-dependent agriculture is a great concern with regard to bees, their produce and environmental contamination. Current analysis evaluates the presence of pesticides (organochlorines, organophosphates, pyrethroids, carbamates, herbicides, fungicides and acaricides in samples of propolis from the state of São Paulo, Brazil. Beekeepers from several localities in the state provided samples of propolis (50, which were collected, stored in non-toxic plastic bags and maintained in a freezer for analyses. Possible pesticide residues were examined by gas chromatography method but no pesticide residues were detected in the examined propolis samples. Propolis analyzed in the state of São Paulo did not show any pesticide contamination. The increasing demand for propolis has caused a raise in its production. However, an increasingly pesticide-dependent agriculture is a great concern with regard to bees, their produce and environmental contamination. Current analysis evaluates the presence of pesticides (organochlorines, organophosphates, pyrethroids, carbamates, herbicides, fungicides and acaricides in samples of propolis from the state of São Paulo, Brazil. Beekeepers from several localities in the state provided samples of propolis (50, which were collected, stored in non-toxic plastic bags and maintained in a freezer for analyses. Possible pesticide residues were examined by gas chromatography method but no pesticide residues were detected in the examined propolis samples. Propolis analyzed in the state of São Paulo did not show any pesticide contamination.

  17. Validation of method for determination of different classes of pesticides in aqueous samples by dispersive liquid-liquid microextraction with liquid chromatography-tandem mass spectrometric detection.

    Caldas, Sergiane Souza; Costa, Fabiane Pinho; Primel, Ednei Gilberto

    2010-04-14

    In this study, a simple, rapid and efficient method has been developed for the extraction and preconcentration of different classes of pesticides, carbofuran (insecticide), clomazone (herbicide) and tebuconazole (fungicide) in aqueous samples by dispersive liquid-liquid microextraction (DLLME) coupled with liquid chromatography-tandem mass spectrometric detection. Some experimental parameters that influence the extraction efficiency, such as the type and volume of the disperser solvents and extraction solvents, extraction time, speed of centrifugation, pH and addition of salt were examined and optimized. Under the optimum conditions, the recoveries of pesticides in water at spiking levels between 0.02 and 2.0 microg L(-1) ranged from 62.7% to 120.0%. The relative standard deviations varied between 1.9% and 9.1% (n=3). The limits of quantification of the method considering a 50-fold preconcentration step were 0.02 microg L(-1). The linearity of the method ranged from 1.0 to 1000 microg L(-1) for all compounds, with correlation coefficients varying from 0.9982 to 0.9992. Results show that the method we propose can meet the requirements for the determination of pesticides in water samples. The comparison of this method with solid-phase extraction indicates that DLLME is a simple, fast, and low-cost method for the determination of pesticides in natural waters.

  18. Validation of a qualitative screening method for pesticides in fruits and vegetables by gas chromatography quadrupole-time of flight mass spectrometry with atmospheric pressure chemical ionization

    Portoles, T.; Mol, J.G.J.; Sancho, J.V.; Lopez, F.J.; Hernandez, F.

    2014-01-01

    A wide-scope screening method was developed for the detection of pesticides in fruit and vegetables. The method was based on gas chromatography coupled to a hybrid quadrupole time-of-flight mass spectrometer with an atmospheric pressure chemical ionization source (GC-(APCI)QTOF MS). A non-target acq

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

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

    2012-01-01

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

  20. Total Pesticide Exposure Calculation among Vegetable Farmers in Benguet, Philippines

    Jinky Leilanie Lu

    2009-01-01

    Full Text Available This was a cross-sectional study that investigated pesticide exposure and its risk factors targeting vegetable farmers selected through cluster sampling. The sampling size calculated with =.05 was 211 vegetable farmers and 37 farms. The mean usage of pesticide was 21.35 liters. Risk factors included damaged backpack sprayer (34.7%, spills on hands (31.8%, and spraying against the wind (58%. The top 3 pesticides used were pyrethroid (46.4%, organophosphates (24.2%, and carbamates (21.3%. Those who were exposed to fungicides and insecticides also had higher total pesticide exposure. Furthermore, a farmer who was a pesticide applicator, mixer, loader, and who had not been given instructions through training was at risk of having higher pesticide exposure. The most prevalent symptoms were headache (64.1%, muscle pain (61.1%, cough (45.5%, weakness (42.4%, eye pain (39.9%, chest pain (37.4%, and eye redness (33.8%. The data can be used for the formulation of an integrated program on safety and health in the vegetable industry.

  1. Obsolete pesticides

    Showstack, Randy

    Several hundred tons of obsolete pesticide stocks worldwide will pose a threat to humans and the environment until the year 2030 in some regions, unless funding for waste disposal is significantly increased, the United Nations Food and Agriculture Organization (FAO) said in a message directed to donor governments and industry on May 24.“Deadly chemicals are contaminating the soils, groundwater, irrigation, and drinking water,” said Amemayehu Wodageneh, senior expert on obsolete pesticides for FAO. “These ‘forgotten’ stocks are a serious risk, [and] they could cause an environmental tragedy in rural areas and big cities. There is hardly any developing country that is not affected by the hazards of obsolete pesticides.”

  2. Highly selective biomarkers for pesticides developed in Eisenia fetida using SELDI-TOF MS.

    Park, Doo-San; Jeon, Hwang-Ju; Park, Eun-Sil; Bae, In Kyung; Kim, Yong-Eun; Lee, Sung-Eun

    2015-03-01

    The repeated use of pesticides, and their subsequent residues, has contributed to severe adverse effects on the environment, including risks to human health. Therefore, it is important to assess the quality of the environment to ensure it remains free from pesticide residues. The six pesticides tested in this study showed high mortality on Eisenia fetida with LC50 values ranging from 7.7 to 37.9 g L(-1). The strongest lethal effect resulted from the organochlorine insecticide endosulfan (LC50=7.7 g L(-1)). Following exposure to the carbamate pesticides, acetylcholinesterase activity in E. fetida decreased dramatically in comparison to the control. Carboxylesterase activity was only lowered in E. fetida exposed to propoxur, when compared to the control. The remaining five pesticides had no significant effect on carboxylesterase activity in E. fetida. In order to discover pesticide-specific biomarkers with differentially expressed proteins after exposure to pesticides, protein patterns of pesticide-treated E. fetida were analyzed using SELDI-TOF MS with Q10 ProteinChips. Protein patterns were compared with their intensities at the same mass-to-charge ratios (m/z). All 42 peaks had intensities with associated p-values less than 0.089, and 40 of these peaks had associated p-values of 0.05. Using SELDI-TOF MS technology, selective biomarkers for the six pesticides tested were found in E. fetida; four proteins with 5425, 5697, 9523, and 9868 m/z were consistently observed in the earthworms following exposure to the carbamates.

  3. Generalisering og validering af model for afdrift af pesticider til læhegn og andre marknære biotoper

    Bruus, Marianne; Løfstrøm, Per; Andersen, Helle Vibeke;

    mængden af pesticider, der lander i læhegnene og dermed reducerer blomstring og frugtsætning. Samtidig viser såvel målinger som modelberegninger, at der ikke er den store effekt af sprøjtefrie bufferzoner på afdriften til læhegn, specielt ikke i den øverste del af læhegnene, hvor frugterne ofte er mest...

  4. Occupational allergic contact dermatitis from xanthates and carbamates in mining processes.

    Sasseville, Denis; Muhn, Channy Y; Al-Sowaidi, Mowza

    2003-09-01

    The objective of this article is to describe allergic contact dermatitis from sodium isopropyl xanthate, potassium amyl xanthate, and carbamates in a geotechnician, to discuss possible cross-reactions, and to report the widespread use of carbamates and mercaptobenzothiazole in mining processes.

  5. 40 CFR 268.39 - Waste specific prohibitions-spent aluminum potliners; reactive; and carbamate wastes.

    2010-07-01

    ... aluminum potliners; reactive; and carbamate wastes. 268.39 Section 268.39 Protection of Environment... Land Disposal § 268.39 Waste specific prohibitions—spent aluminum potliners; reactive; and carbamate...-U411 are prohibited from land disposal. In addition, soil and debris contaminated with these wastes...

  6. Subchronic Toxicity Study in Rats of Two New Ethyl-Carbamates with Ixodicidal Activity

    María Guadalupe Prado-Ochoa

    2014-01-01

    Full Text Available Female and male Wistar rats were used to determine the subchronic oral toxicities of two new ethyl-carbamates with ixodicidal activities (ethyl-4-bromphenyl-carbamate and ethyl-4-chlorphenyl-carbamate. The evaluated carbamates were administered in the drinking water (12.5, 25 and 50 mg/kg/day for 90 days. Exposure to the evaluated carbamates did not cause mortality or clinical signs and did not affect food consumption or weight gain. However, exposure to these carbamates produced alterations in water consumption, hematocrit, percentages of reticulocytes, plasma proteins, some biochemical parameters (aspartate aminotransferase, gamma-glutamyl transpeptidase, cholinesterase, and creatinine activities, thiobarbituric acid reactive substances, and the relative weight of the spleen. Histologically, slight pathological alterations were found in the liver that were consistent with the observed biochemical alterations. The nonobserved adverse effect levels (NOAELs of the evaluated carbamates were 12.5 mg/kg/day for both the female and male rats. The low severity and reversibility of the majority of the observed alterations suggest that the evaluated carbamates have low subchronic toxicity.

  7. Evaluation of carbamate insecticides as chemotherapeutic agents for cancer

    Mohd. Amanullah

    2011-01-01

    Full Text Available Background: Cancer chemotherapy has already been in practice by the use of toxins and some of the specific poisonous compounds of cyanide derivatives. Carbamate insecticides inhibit cellular metabolism including energy, protein, and nucleic acid metabolism, thereby, causing cell regression and death. Aim: Preliminary evaluation of three carbamate insecticides, namely, baygon, carbaryl, and carbofuran as chemotherapeutic agents for cancer is undertaken in the present study. Materials and Methods: The toxicity of carbamates on squamous cell carcinoma was assessed in-vitro using dye binding tests. Cells were grown in microtitration ELISA plates, as adherent cultures, for six hours, and then exposed to the drugs for 2, 4, 8, and 12 hours, and finally stained with neutral red, to assess the viable cell number, and with methylene blue for the determination of protein in the monolayer. Optical density was read in an ELISA reader. Statistical Analysis: The data obtained during the experiment was subjected to statistical analysis by using the student ′t′ test. Results: The results indicated that the percentage of the viable cell number reduced with an increase in the time of exposure of the drugs. Exposure of the tumor cells to the drugs for 12 hours detached them completely from the wells, and hence, all the cells were washed out. Exposure of the drugs prior to the establishment of the culture in-vitro resulted in the non-formation of the monolayer in the wells. Conclusions: Among the three drugs studied, the survival percent was least with carbaryl treatment followed by baygon, and with carbofuran treatment it was almost near to control group.

  8. Brazilian vodkas have undetectable levels of ethyl carbamate

    Elainy V. S. Pereira

    2013-01-01

    Full Text Available While in Europe vodka is mainly derived from potatoes or cereals, a large proportion of Brazilian vodka is likely obtained from sugarcane, which contains ethyl carbamate (EC precursors. EC, in addition to several other contaminants and congeners, were investigated in 32 samples of Brazilian vodka. All samples complied with the Brazilian regulations for congeners and contaminants, having EC content below 0.01 mg/L (detection limit. These results are probably related to the processing of vodka, in particular the use of extractive and rectifying stainless steel distillation columns, which allow the production of high strength spirits with low levels of congeners and contaminants.

  9. [Survey of pesticide residues in imported spices and herbs (1997.4-2011.3)].

    Kobayashi, Maki; Ohtsuka, Kenji; Tamura, Yasuhiro; Tomizawa, Sanae; Kinoshita, Teruaki; Kamijo, Kyoko; Iwakoshi, Keiko; Sato, Chizuko; Nagayama, Toshihiro; Takano, Ichiro

    2013-01-01

    A survey of pesticide residues in 313 samples of imported spices and herbs on the Tokyo market from April 1997 to March 2011 was carried out. Thirty-seven kinds of pesticides, including organophosphorus, organochlorine, pyrethroid, carbamate and others, were detected between levels of trace (below 0.01 ppm) and 3.3 ppm from 64 samples. The rate of detection was highest in peel (100%) followed by stem (66.7%), fruit (34.5%), bark (33.3%), flower (31.3%) and leaf (14.7%). No residues were detected in root, seed or whole grass. Organochlorine pesticides were detected in all plant parts. The insecticides were detected in products from all production areas, suggesting that their use is common. Residue levels of these pesticides were calculated as less than 1% of their ADI values, based on the daily intake of spices and herbs. Therefore, these spices and herbs should be safe when consumed in customary amounts.

  10. Detection and quantification of dithiocarbamate pesticides by Surface Enhanced Raman Spectroscopy (SERS)

    Saute, Benjamin Calvin

    Dithiocarbamates are a subclass of carbamate pesticides that are widely used as insecticidal agents on food crops in the US and abroad. Quantitative determination of trace quantities of dithiocarbamates is necessary in order to mitigate potential human exposure via pesticide residues left on inadequately washed food items as well as groundwater contamination from agricultural runoff. The focus of this research is on the development and optimization of a Surface Enhanced Raman Spectroscopy (SERS) based analytical technique for the quantitative determination of trace amounts of dithiocarbamate pesticides in different matrices. Gold nanoparticles of different shapes and sizes will be investigated to determine the suitability of these materials as SERS active substrates for the trace analysis of dithiocarbamate pesticides. Analytical sensitivity will be evaluated by determining the limits of detection using established statistical methods.

  11. Ultra-Trace Determination of Methyl Carbamate and Ethyl Carbamate in Local Wines by GC-FID Following Pre concentration with C18-SPE

    Supawadee Sarawan

    2014-09-01

    Full Text Available An analytical method is described for ultra-trace determination of methyl carbamate and ethyl carbamate in locally produced fruit wines. The quantitative analysis involves with dichloromethane extraction followed by 30-fold preconcentration using C18 SPE prior to measurement by capillary GC-FID. Under the optimized conditions, a good linearity of their calibration curves was obtained in the range of 0.1-50.0 mg/L with r2 > 0.994. LOD and LOQ were 3.3-16.7 µg/L and 11.1-55.6 µg/L, respectively. The averaged recovery of these carbamates was ranged of 82.2-95.2% with RSD < 8.76%. The procedure was applied to determine both carbamate residues in various local wine samples. It was found that the concentration range of methyl carbamate (6.9-24.1 µg/L was rather fluctuated and higher than that of ethyl carbamate (2.6-4.3 µg/L, suggesting that is a certain residual background contamination naturally occurring in the wine fermentation.

  12. Development, validation and application of a methodology based on solid-phase micro extraction followed by gas chromatography coupled to mass spectrometry (SPME/GC-MS) for the determination of pesticide residues in mangoes.

    Menezes Filho, Adalberto; dos Santos, Fábio Neves; Pereira, Pedro Afonso de Paula

    2010-04-15

    A method was developed for the simultaneous analysis of 14 pesticide residues (clofentezine, carbofuran, diazinon, methyl parathion, malathion, fenthion, thiabendazole, imazalil, bifenthrin, permethrin, prochloraz, pyraclostrobin, difenoconazole and azoxystrobin) in mango fruit, based on solid-phase micro extraction (SPME) coupled to gas chromatography-mass spectrometry (GC-MS). Different parameters of the method were evaluated, such as fiber type, extraction mode (direct immersion and headspace), temperature, extraction and desorption times, stirring velocities and ionic strength. The best results were obtained using polyacrylate fiber and direct immersion mode at 50 degrees C for 30 min, along with stirring at 250 rpm and desorption for 5 min at 280 degrees C. The method was validated using mango samples spiked with pesticides at concentration levels ranging from 33.3 to 333.3 microg kg(-1). The average recoveries (n=3) for the lowest concentration level ranged from 71.6 to 117.5%, with relative standard deviations between 3.1 and 12.3%, respectively. Detection and quantification limits ranged from 1.0 to 3.3 microg kg(-1) and from 3.33 to 33.33 microg kg(-1), respectively. The optimized method was then applied to 16 locally purchased mango samples, all of them containing the pesticides bifenthrin and azoxystrobin in concentrations of 18.3-57.4 and 12.7-55.8 microg kg(-1), respectively, although these values were below the MRL established by Brazilian legislation. The method proved to be selective, sensitive, and with good precision and recovery rates, presenting LOQ below the MRL admitted by Brazilian legislation.

  13. Validation and use of a QuEChERS-based gas chromatographic-tandem mass spectrometric method for multiresidue pesticide analysis in blackcurrants including studies of matrix effects and estimation of measurement uncertainty.

    Walorczyk, Stanisław

    2014-03-01

    A triple quadrupole GC-QqQ-MS/MS method was optimized for multiresidue analysis of over 180 pesticides in blackcurrants. The samples were prepared by using a modified quick, easy, cheap, effective, rugged and safe (QuEChERS) analytical protocol. To reduce matrix co-extractives in the final extract, the supernatant was cleaned up by dispersive-solid phase extraction (dispersive-SPE) with a mixture of sorbents: primary secondary amine (PSA), octadecyl (C18) and graphitized carbon black (GCB). The validation results demonstrated fitness for purpose of the streamlined method. The overall recoveries at the three spiking levels of 0.01, 0.05 and 0.2 mg kg(-1) spanned between 70% and 116% (102% on average) with relative standard deviation (RSD) values between 3% and 19% except for chlorothalonil (23%). Response linearity was studied in the range between 0.005 and 0.5 mg kg(-1). The matrix effect for each individual compound was evaluated through the study of ratios of the slopes obtained in solvent and blackcurrant matrix. The optimized method provided small matrix effect (30%, respectively. Following the application of "top-down" approach, the expanded measurement uncertainty was estimated as being 21% on average (coverage factor k=2, confidence level 95%). If compared with samples of other crops, the analyses of blackcurrants revealed a high percentage of exceedance of the legislative maximum residue levels (MRLs), as well as some instances of the detection of pesticides unapproved on this crop.

  14. Pesticides residues in the Prochilodus costatus (Valenciennes, 1850) fish caught in the São Francisco River, Brazil.

    Oliveira, Fabiano A; Reis, Lilian P G; Soto-Blanco, Benito; Melo, Marília M

    2015-01-01

    The objective of this study was to determine the levels of pesticides in the fish Prochilodus costatus caught in São Francisco River, one of most important rivers in Brazil. Thirty-six fish were captured in three different areas, and samples of the dorsal muscle and pooled viscera were collected for toxicological analysis. We evaluated the presence of 150 different classes of insecticides, fungicides, herbicides and acaricides by multiresidue analysis technique using liquid chromatography-tandem mass spectrometry (LC-MS/MS), with the limit of detection of 5 ppb. In this study, organophosphorus and carbamate pesticides were detected at the highest levels in the caught fish. Among the 41 organophosphorus pesticides surveyed, nine types were detected (chlorpyrifos, diazinon, dichlorvos, disulfoton, ethion, etrimfos, phosalone, phosmet and pyrazophos) in the muscle, viscera pool, or both in 22 (61.1%) fish. Sampled tissues of 20 (55.6%) fish exhibited at least one of the eight evaluated carbamate pesticides and their metabolites: aldicarb, aldicarb sulfoxide, carbaryl, carbofuran, carbosulfan, furathiocarb, methomyl and propoxur. Fungicides (carbendazim, benalaxyl, kresoxim-methyl, trifloxystrobin, pyraclostrobin and its metabolite BF 500 pyraclostrobin), herbicides (pyridate and fluasifop p-butyl), acaricide (propargite) and pyrethroid (flumethrin) were also detected. In conclusion, P. costatus fish caught in the São Francisco River contained residues of 17 different pesticides, in both muscles and the viscera pool, indicating heavy environmental contamination by pesticides in the study area.

  15. Pesticides in the Ebro River basin: Occurrence and risk assessment.

    Ccanccapa, Alexander; Masiá, Ana; Navarro-Ortega, Alícia; Picó, Yolanda; Barceló, Damià

    2016-04-01

    In this study, 50 pesticides were analyzed in the Ebro River basin in 2010 and 2011 to assess their impact in water, sediment and biota. A special emphasis was placed on the potential effects of both, individual pesticides and their mixtures, in three trophic levels (algae, daphnia and fish) using Risk Quotients (RQs) and Toxic Units (TUs) for water and sediments. Chlorpyrifos, diazinon and carbendazim were the most frequent in water (95, 95 and 70% of the samples, respectively). Imazalil (409.73 ng/L) and diuron (150 ng/L) were at the highest concentrations. Sediment and biota were less contaminated. Chlorpyrifos, diazinon and diclofenthion were the most frequent in sediments (82, 45 and 21% of the samples, respectively). The only pesticide detected in biota was chlorpyrifos (up to 840.2 ng g(-1)). Ecotoxicological risk assessment through RQs showed that organophosphorus and azol presented high risk for algae; organophosphorus, benzimidazoles, carbamates, juvenile hormone mimic and other pesticides for daphnia, and organophosphorus, azol and juvenile hormone mimics for fish. The sum TUsite for water and sediments showed values pesticide residues present.

  16. Comparative effect of pesticides on brain acetylcholinesterase in tropical fish.

    Assis, Caio Rodrigo Dias; Linhares, Amanda Guedes; Oliveira, Vagne Melo; França, Renata Cristina Penha; Carvalho, Elba Veronica Matoso Maciel; Bezerra, Ranilson Souza; de Carvalho, Luiz Bezerra

    2012-12-15

    Monitoring of pesticides based on acetylcholinesterase (AChE; EC 3.1.1.7) inhibition in vitro avoids interference of detoxification defenses and bioactivation of some of those compounds in non-target tissues. Moreover, environmental temperature, age and stress are able to affect specific enzyme activities when performing in vivo studies. Few comparative studies have investigated the inter-specific differences in AChE activity in fish. Screening studies allow choosing the suitable species as source of AChE to detect pesticides in a given situation. Brain AChE from the tropical fish: pirarucu (Arapaima gigas), cobia (Rachycentron canadum) and Nile tilapia (Oreochromis niloticus) were characterized and their activities were assayed in the presence of pesticides (the organophosphates: dichlorvos, diazinon, chlorpyrifos, temephos, tetraethyl pyrophosphate- TEPP and the carbamates: carbaryl and carbofuran). Inhibition parameters (IC₅₀ and Ki) for each species were found and compared with commercial AChE from electric eel (Electrophorus electricus). Optimal pH and temperature were found to be 8.0 and 35-45 °C, respectively. A. gigas AChE retained 81% of the activity after incubation at 50 °C for 30 min. The electric eel enzyme was more sensitive to the compounds (mainly carbofuran, IC₅₀ of 5 nM), excepting the one from A. gigas (IC₅₀ of 9 nM) under TEPP inhibition. These results show comparable sensitivity between purified and non-purified enzymes suggesting them as biomarkers for organophosphorus and carbamate detection in routine environmental and food monitoring programs for pesticides.

  17. Multiresidue Analysis of 86 Pesticides Using Gas Chromatography Mass Spectrometry: II-Nonleafy Vegetables

    M. H. EL-Saeid

    2013-01-01

    Full Text Available A total of 1057 samples of fresh vegetables from import and domestic production were analyzed (cold pepper, egg plant, carrot, cucumber, potato, hot pepper, cultivation tomato, squash, beans, okra, onions, cauliflower, and green house tomato. The aim of this study was to investigate pesticide residues in market foods in Riyadh, which have been collected from Riyadh Development Company (Al-Tamer Vegetables Market. Pesticide residues were determined by gas chromatography with mass selective detector (GC-MSD. A multiresidue method was developed and described for simultaneous determination of 86 pesticides commonly used in crop protection. This method used to determine 86 pesticide residues with a broad range of physicochemical properties in fresh vegetables related to organophosphorus (OPP, organochlorines (OCP, pyrethroids, and carbamates mainly used in agriculture. Sample extract was cleaned up by using AOAC method. Pesticide residues above the maximum residue limits (MRL were detected in 15.89% of the total samples (168 from 1057 samples, but 83.90% of the total samples (887 from 1057 samples has no residues or contained pesticide residues at or below MRL. The detected and most frequently found pesticide residues were permethrin (45 times and endosulfan (34 times followed by deltamethrin (27 times. The findings of this study pointed to the following recommendations: the need for a monitoring program for pesticide residues in imported food crops.

  18. Vortex-Assisted Dispersive Micro-Solid Phase Extraction Using CTAB-Modified Zeolite NaY Sorbent Coupled with HPLC for the Determination of Carbamate Insecticides.

    Salisaeng, Pawina; Arnnok, Prapha; Patdhanagul, Nopbhasinthu; Burakham, Rodjana

    2016-03-16

    A vortex-assisted dispersive micro-solid phase extraction (VA-D-μ-SPE) based on cetyltrimethylammonium bromide (CTAB)-modified zeolite NaY was developed for preconcentration of carbamate pesticides in fruits, vegetables, and natural surface water prior to analysis by high performance liquid chromatography with photodiode array detection. The small amounts of solid sorbent were dispersed in a sample solution, and extraction occurred by adsorption in a short time, which was accelerated by vortex agitation. Finally, the sorbents were filtered from the solution, and the analytes were subsequently desorbed using an appropriate solvent. Parameters affecting the VA-D-μ-SPE performance including sorbent amount, sample volume, desorption solvent ,and vortex time were optimized. Under the optimum condition, linear dynamic ranges were achieved between 0.004-24.000 mg kg(-1) (R(2) > 0.9946). The limits of detection (LODs) ranged from 0.004-4.000 mg kg(-1). The applicability of the developed procedure was successfully evaluated by the determination of the carbamate residues in fruits (dragon fruit, rambutan, and watermelon), vegetables (cabbage, cauliflower, and cucumber), and natural surface water.

  19. Hydrogels for osteochondral repair based on photocrosslinkable carbamate dendrimers.

    Degoricija, Lovorka; Bansal, Prashant N; Söntjens, Serge H M; Joshi, Neel S; Takahashi, Masaya; Snyder, Brian; Grinstaff, Mark W

    2008-10-01

    First generation, photocrosslinkable dendrimers consisting of natural metabolites (i.e., succinic acid, glycerol, and beta-alanine) and nonimmunogenic poly(ethylene glycol) (PEG) were synthesized divergently in high yields using ester and carbamate forming reactions. Aqueous solutions of these dendrimers were photocrosslinked with an eosin-based photoinitiator to afford hydrogels. The hydrogels displayed a range of mechanical properties based on their structure, generation size, and concentration in solution. All of the hydrogels showed minimal swelling characteristics. The dendrimer solutions were then photocrosslinked in situ in an ex vivo rabbit osteochondral defect (3 mm diameter and 10 mm depth), and the resulting hydrogels were subjected to physiologically relevant dynamic loads. Magnetic resonance imaging (MRI) showed the hydrogels to be fixated in the defect site after the repetitive loading regimen. The ([G1]-PGLBA-MA) 2-PEG hydrogel was chosen for the 6 month pilot in vivo rabbit study because this hydrogel scaffold could be prepared at low polymer weight (10 wt %) and possessed the largest compressive modulus of the 10% formulations, a low swelling ratio, and contained carbamate linkages, which are more hydrolytically stable than the ester linkages. The hydrogel-treated osteochondral defects showed good attachment in the defect site and histological analysis showed the presence of collagen II and glycosaminoglycans (GAGs) in the treated defects. By contrast, the contralateral unfilled defects showed poor healing and negligible GAG or collagen II production. Good mechanical properties, low swelling, good attachment to the defect site, and positive in vivo results illustrate the potential of these dendrimer-based hydrogels as scaffolds for osteochondral defect repair.

  20. B-type esterases in the snail Xeropicta derbentina: An enzymological analysis to evaluate their use as biomarkers of pesticide exposure

    Laguerre, Christel [Universite d' Avignon et des Pays de Vaucluse, UMR 406 UAPV/INRA, F-84914 Avignon (France); INRA, Laboratoire de Toxicologie Environnementale, UMR 406 UAPV/INRA, F-84914 Avignon (France); Sanchez-Hernandez, Juan C. [Laboratory of Ecotoxicology, Faculty of Environmental Science, University of Castilla-La Mancha, Avda. Carlos III s/n, 45071 Toledo (Spain); Koehler, Heinz R. [Animal Physiological Ecology, University of Tuebingen, Konrad-Adenauer-Strasse 20, D-72072 Tuebingen (Germany); Triebskorn, Rita [Animal Physiological Ecology, University of Tuebingen, Konrad-Adenauer-Strasse 20, D-72072 Tuebingen (Germany); Steinbeis-Transfer Center for Ecotoxicology and Ecophysiology, Blumenstrasse 13, D-72108 Rottenburg (Germany); Capowiez, Yvan [INRA, Unite PSH, F- 84914 Avignon (France); Rault, Magali [Universite d' Avignon et des Pays de Vaucluse, UMR 406 UAPV/INRA, F-84914 Avignon (France); INRA, Laboratoire de Toxicologie Environnementale, UMR 406 UAPV/INRA, F-84914 Avignon (France); Mazzia, Christophe [Universite d' Avignon et des Pays de Vaucluse, UMR 406 UAPV/INRA, F-84914 Avignon (France); INRA, Laboratoire de Toxicologie Environnementale, UMR 406 UAPV/INRA, F-84914 Avignon (France)], E-mail: mazzia@avignon.inra.fr

    2009-01-15

    The study was prompted to characterize the B-type esterase activities in the terrestrial snail Xeropicta derbentina and to evaluate its sensitivity to organophosphorus and carbamate pesticides. Specific cholinesterase and carboxylesterase activities were mainly obtained with acetylthiocholine (K{sub m} = 77.2 mM; V{sub max} = 38.2 mU/mg protein) and 1-naphthyl acetate (K{sub m} = 222 mM, V{sub max} = 1095 mU/mg protein) substrates, respectively. Acetylcholinesterase activity was concentration-dependently inhibited by chlorpyrifos-oxon, dichlorvos, carbaryl and carbofuran (IC50 = 1.35 x 10{sup -5}-3.80 x 10{sup -8} M). The organophosphate-inhibited acetylcholinesterase activity was reactivated in the presence of pyridine-2-aldoxime methochloride. Carboxylesterase activity was inhibited by organophosphorus insecticides (IC50 = 1.20 x 10{sup -5}-2.98 x 10{sup -8} M) but not by carbamates. B-esterase-specific differences in the inhibition by organophosphates and carbamates are discussed with respect to the buffering capacity of the carboxylesterase to reduce pesticide toxicity. These results suggest that B-type esterases in X. derbentina are suitable biomarkers of pesticide exposure and that this snail could be used as sentinel species in field monitoring of Mediterranean climate regions. - Characterization of the B-type esterases in the terrestrial snail Xeropicta derbentina in order to evaluate pesticide exposure.

  1. Comparative Evaluation of Carbamates as Prophylactic Agents against Organophosphate Intoxication Rats

    A. K. Chatterjee

    1992-04-01

    Full Text Available Investigates the effects of two well-known carbamates, physostigmine and pyridostigmine against organophosphorous compound and nerve gas toxicity. Physostigmine pretreatment for 30 min enhanced the survival time of rats against DFP intoxication whereas it did not have any effect with sarin poisoning. However, pyridostigmine pretreatment did not produce any significant effect on survival time either against DFP or sarin intoxication. Treatment with atropine along with carbamates further enhanced significantly the survival time against DFP poisoning.

  2. Pesticides (Environmental Health Student Portal)

    ... pesticides are and commonly used ones around the house. Pesticides (Tox Town - National Library of Medicine) - Introduction to the health effects associated with exposure to pesticides and where ...

  3. Transdermal carbamate poisoning – a case of misuse

    Lalit Kumar Rajbanshi

    2017-01-01

    Full Text Available Acute pesticide poisoning is a common mode of intentional self harm. Oral ingestion is the usual mode of poisoning. However, inhalation, accidental or occupational transdermal exposure leading to acute or chronic poisoning can be the other route of poisoning. It has been seen that the purpose of poising is suicidal intensity in most of the cases. We report an unusual case where the victim had acute pesticide poisoning through transdermal route that was intended for non suicidal purpose. The patient was managed successfully with immediate decontamination and adequate antidote.

  4. Increased Risk of Dementia in Patients With Acute Organophosphate and Carbamate Poisoning: A Nationwide Population-Based Cohort Study.

    Lin, Jiun-Nong; Lin, Cheng-Li; Lin, Ming-Chia; Lai, Chung-Hsu; Lin, Hsi-Hsun; Yang, Chih-Hui; Kao, Chia-Hung

    2015-07-01

    Organophosphate (OP) and carbamate (CM) are the most commonly used pesticides against insects. Little is known regarding the relationship between dementia and acute OP and CM poisoning. A nationwide population-based cohort study was conducted from the National Health Insurance Research Database in Taiwan. The incidence and relative risk of dementia were assessed in patients hospitalized for acute OP and CM poisoning from 2000 to 2011. The comparison cohort was matched with the poisoned cohort at a 4:1 ratio based on age, sex, and the year of hospitalization. During the follow-up period, the incidence of dementia was 29.4 per 10,000 person-years in the poisoned group, and represented a 1.98-fold increased risk of dementia compared with the control cohort (95% confidence interval, 1.59-2.47). This study provides evidence on the association between dementia and acute OP and CM poisoning. Regular follow-up of poisoned patients for dementia is suggested.

  5. Use of an ionic liquid-based surfactant as pseudostationary phase in the analysis of carbamates by micellar electrokinetic chromatography.

    Tejada-Casado, Carmen; Moreno-González, David; García-Campaña, Ana M; del Olmo-Iruela, Monsalud

    2015-03-01

    The applicability of an ionic liquid-based cationic surfactant 1-dodecyl-3-methyl-imidazolium tetrafluoroborate (C12 MImBF4 ) as pseudostationary phase in MEKC has been evaluated for the analysis of 11 carbamate pesticides (promecarb, carbofuran, metolcarb, fenobucarb, aldicarb, propoxur, asulam, benomyl, carbendazim, ethiofencarb, isoprocarb) in juice samples. Under optimum conditions (separation buffer, 35 mM NaHCO3 and 20 mM C12 MImBF4 , pH 9.0; capillary temperature 25°C; voltage -22 kV) the analysis was carried out in less than 12 min, using hydrodynamic injection (50 mbar for 7.5 s) and detection at 200 nm. For the extraction of these CRBs from juice samples, a dispersive liquid-liquid microextraction (DLLME) procedure has been proposed, by optimization of variables affecting the efficiency of the extraction. Following this treatment, sample throughput was approximately 12 samples per hour, obtaining a preconcentration factor of 20. Matrix-matched calibration curves were established using tomato juice as representative matrix (from 5 to 250 μg/L for CBZ, BY, PX, CF, FEN, ETH, ISP, and 25-250 μg/L for ASL, ALD, PRC, MTL), obtaining quantification limits ranging from 1 to 18 μg/L and recoveries from 70 to 96%, with RSDs lower than 9%.

  6. Development, validation and application of a SDME/GC-FID methodology for the multiresidue determination of organophosphate and pyrethroid pesticides in water.

    Pinheiro, Anselmo de Souza; de Andrade, Jailson B

    2009-10-15

    A single-drop microextraction (SDME) procedure was developed for the analysis of organophosphorus and pyrethroid pesticides in water by gas chromatography (GC) with flame ionization detection (GC-FID). The significant parameters that affect SDME performance, such as the selection of microextraction solvent, solvent volume, extraction time, and stirring rate, were studied and optimized using a tool screening factorial design. The limits of detection (LODs) in water for the four investigated compounds were between 0.3 and 3.0 microgL(-1), with relative standard deviations ranging from 7.7 to 18.8%. Linear response data were obtained in the concentration range of 0.9-6.0 microg L(-1) (lambda-cyhalothrin), 3.0-60.0 microg L(-1) (methyl parathion), 9.0-60.0 microg L(-1) (ethion), and 9.0-30.0 microg L(-1) (permethrin), with correlation coefficients ranging from 0.9337 to 0.9977. The relative recoveries for the spiked water ranged from 73.0 to 104%. Environmental water samples (n=26) were successfully analyzed using the proposed method and methyl parathion presented concentration up to 2.74 microg L(-1). The SDME method, coupled with GC-FID analysis, provided good precision, accuracy, and reproducibility over a wide linear range. Other highlights of the method include its ease of use and its requirement of only small volumes of both organic solvent and sample.

  7. Study of Inhibition, Reactivation and Aging Processes of Pesticides Using Graphene Nanosheets/Gold Nanoparticles-Based Acetylcholinesterase Biosensor

    Zhang, Lin; Long, Linjuan; Zhang, Weiying; Du, Dan; Lin, Yuehe

    2012-09-10

    Organophosphate (OP) and carbamate pesticides exert their toxicity via attacking the hydroxyl moiety of serine in the 'active site' of acetylcholinesterase (AChE). In this paper we developed a stable AChE biosensor based on self-assembling AChE to graphene nanosheet (GN)-gold nanoparticles (AuNPs) nanocomposite electrode for investigation of inhibition, reactivation and aging processes of different pesticides. It is confirmed that pesticides can inhibit AChE in a short time. OPs poisoning is treatable with oximes while carbarmates exposure is insensitive to oximes. The proposed electrochemical approach thus provides a new simple tool for comparison of pesticide sensitivity and guide of therapeutic intervention.

  8. Postcolumn photolysis of pesticides for fluorometric determination by high-performance liquid chromatography

    Miles, C.J.; Moye, H.A.

    1988-02-01

    A high-performance liquid chromatography postcolumn reaction detector that employs UV photolysis with an optional reaction by using o-phthalaldehyde-2-mercaptoethanol (OPA-MERC) followed by fluorescence detection was found to be useful for several classes of pesticides. In the presence of the OPA-MERC reagent, most carbamates, carbamoyl oximes, carbamothioic acids, and substituted ureas gave a sensitive response while the response of dithiocarbamates, phenylamides, and phenylcarbamates varied. The response of most of the pesticides tested was significantly affected by the solvent used. Method detection limits for aldicarb sulfoxide, aldicarb, propoxur, thiram, and neburon in ground water were 2.5, 2.3, 3.3, 3.8, and 2.0 ..mu..g/L, respectively. In the absence of OPA-MERC reagent, several of the substituted aromatic compounds also gave strong fluorescence after photolysis. This detector is applicable to a broad range of nitrogenous pesticides.

  9. Comparison of Current-Use Pesticide and Other Toxicant Urinary Metabolite Levels among Pregnant Women in the CHAMACOS Cohort and NHANES

    2010-01-01

    Background We measured 34 metabolites of current-use pesticides and other precursor compounds in urine samples collected twice during pregnancy from 538 women living in the Salinas Valley of California, a highly agricultural area (1999–2001). Precursors of these metabolites included fungicides, carbamate, organochlorine, organophosphorus (OP), and pyrethroid insecticides, and triazine and chloroacetanilide herbicides. We also measured ethylenethiourea, a metabolite of the ethylene-bisdithioca...

  10. Household Products Database: Pesticides

    ... Glossary Contact Us More Resources Browse Pesticides Category Pesticides activator algaecide ants ants & roaches ants, roaches aphids ... snakes sow bugs spiders termites termites, carpenter ants/bees ticks tomatoes total vegetation control tree trees trees, ...

  11. Pesticide Product Label System

    U.S. Environmental Protection Agency — The Pesticide Product Label System (PPLS) provides a collection of pesticide product labels (Adobe PDF format) that have been approved by EPA under Section 3 of the...

  12. Pesticides and honey bees

    Amaro, Pedro; Godinho, Joana

    2012-01-01

    After the analysis of the criterion of toxicological classification (TC) of pesticides to honeybees and of the evolution of TC and of legislation related to the theme, in Portugal, it is demonstrated how the absence of rigor of the Portuguese Pesticide Regulation Authority (AFN) and of the pesticides suppliers contribute to the very high probability of mortality of honeybees by pesticides and finally are presented proposals for the optimization of perspectives to...

  13. Health Risk Assessment of Pesticide Residues via Dietary Intake of Market Vegetables from Dhaka, Bangladesh

    Md. Shakhaoat Hossain

    2013-02-01

    Full Text Available The present study was designed to assess the health risk of pesticide residues via dietary intake of vegetables collected from four top agro-based markets of Dhaka, Bangladesh. High performance liquid chromatography with a photo diode array detector (HPLC-PDA was used to determine six organophosphorus (chlorpyrifos, fenitrothion, parathion, ethion, acephate, fenthion, two carbamate (carbaryl and carbofuran and one pyrethroid (cypermethrin pesticide residues in twelve samples of three common vegetables (tomato, lady’s finger and brinjal. Pesticide residues ranged from below detectable limit (<0.01 to 0.36 mg/kg. Acephate, chlorpyrifos, ethion, carbaryl and cypermethrin were detected in only one sample, while co-occurrence occurred twice for fenitrothion and parathion. Apart from chlorpyrifos in tomato and cypermethrin in brinjal, all pesticide residues exceeded the maximum residue limit (MRL. Hazard risk index (HRI for ethion (10.12 and carbaryl (1.09 was found in lady’s finger and tomato, respectively. Rest of the pesticide residues were classified as not a health risk. A continuous monitoring and strict regulation should be enforced regarding control of pesticide residues in vegetables and other food commodities.

  14. Determination of biocides and pesticides by on-line solid phase extraction coupled with mass spectrometry and their behaviour in wastewater and surface water

    Singer, Heinz; Jaus, Sylvia; Hanke, Irene; Lueck, Alfred; Hollender, Juliane [Eawag, Swiss Federal Institute of Aquatic Science and Technology, Ueberlandstrasse 133, CH-8600 Duebendorf (Switzerland); Alder, Alfredo C., E-mail: alfredo.alder@eawag.c [Eawag, Swiss Federal Institute of Aquatic Science and Technology, Ueberlandstrasse 133, CH-8600 Duebendorf (Switzerland)

    2010-10-15

    This study focused on the input of hydrophilic biocides into the aquatic environment and on the efficiency of their removal in conventional wastewater treatment by a mass flux analysis. A fully automated method consisting of on-line solid phase extraction coupled to LC-ESI-MS/MS was developed and validated for the simultaneous trace determination of different biocidal compounds (1,2-benzisothiazoline-3-one (BIT), 3-Iodo-2-propynylbutyl-carbamate (IPBC), irgarol 1051 and 2-N-octyl-4-isothiazolinone (octhilinone, OIT), carbendazim, diazinon, diuron, isoproturon, mecoprop, terbutryn and terbutylazine) and pharmaceuticals (diclofenac and sulfamethoxazole) in wastewater and surface water. In the tertiary effluent, the highest average concentrations were determined for mecoprop (1010 ng/L) which was at comparable levels as the pharmaceuticals diclofenac (690 ng/L) and sulfamethoxazole (140 ng/L) but 1-2 orders of magnitude higher than the other biocidal compounds. Average eliminations for all compounds were usually below 50%. During rain events, increased residual amounts of biocidal contaminants are discharged to receiving surface waters. - Incomplete removal of biocides and pesticides during wastewater treatment.

  15. Synthesis of methyl N-phenyl carbamate from dimethyl carbonate and 1,3-diphenyl urea under mild conditions

    Jun Jie Gao; Hui Quan Li; Yi Zhang

    2007-01-01

    Synthesis of methyl N-phenyl carbamate from dimethyl carbonate and 1,3-diphenyl urea was investigated under atmospheric pressure. The results showed that homogenous catalyst sodium methoxide had the excellent activity to efficiently catalyze the synthesis of methyl N-phenyl carbamate under atmospheric pressure.

  16. Assessment of Acute Oral and Dermal Toxicity of 2 Ethyl-Carbamates with Activity against Rhipicephalus microplus in Rats

    María Guadalupe Prado-Ochoa

    2014-01-01

    Full Text Available The acute oral and dermal toxicity of two new ethyl-carbamates (ethyl-4-bromophenyl-carbamate and ethyl-4-chlorophenyl-carbamate with ixodicide activity was determined in rats. The oral LD50 of each carbamate was 300 to 2000 mg/kg, and the dermal LD50 of each carbamate was >5000 mg/kg. Clinically, the surviving rats that had received oral doses of each carbamate showed decreased weight gain (P<0.05 and had slight nervous system manifestations. These clinical signs were evident from the 300 mg/kg dose and were reversible, whereas the 2000 mg/kg dose caused severe damage and either caused their death or was motive for euthanasia. At necropsy, these rats had dilated stomachs and cecums with diffuse congestion, as well as moderate congestion of the liver. Histologically, the liver showed slight degenerative lesions, binucleated hepatocytes, focal coagulative necrosis, and congestion areas; the severity of the lesions increased with dosage. Furthermore, an slight increase in gamma-glutamyltransferase, lactate dehydrogenase, and creatinine was observed in the plasma. The dermal application of the maximum dose (5000 mg/kg of each carbamate did not cause clinical manifestations or liver and skin alterations. This finding demonstrates that the carbamates under study have a low oral hazard and low acute dermal toxicity.

  17. Influence of pretreatment of carbamates on dynamic pulmonary mechanics in rats exposed to sarin aerosols.

    Husain, K; Kumar, P; Vijayaraghavan, R; Singh, R; Das Gupta, S

    1993-07-01

    The effect of pretreatment of two carbamates, pyridostigmine and physostigmine on dynamic pulmonary mechanics has been studied in rats exposed to sarin aerosols. Sign-free dose of pyridostigmine (0.075 mg/kg, i.m.) or physostigmine (0.1 mg/kg, i.m.) did not significantly alter the parameters of the dynamic pulmonary mechanics 20 min after treatment. However, sarin (51.2 mg/m3, for 15 min) depressed the respiratory rate, air flow and minute volume and enhanced the transthoracic pressure and tidal volume. Pretreatment with carbamates 20 min prior to sarin exposure significantly modified or counteracted the above induced changes. It is concluded that the protective effect of carbamates is mainly due to the correction of respiratory changes caused by sarin aerosols in rats.

  18. Carbamate stabilities of sterically hindered amines from quantum chemical methods: relevance for CO2 capture.

    Gangarapu, Satesh; Marcelis, Antonius T M; Zuilhof, Han

    2013-12-02

    The influence of electronic and steric effects on the stabilities of carbamates formed from the reaction of CO2 with a wide range of alkanolamines was investigated by quantum chemical methods. For the calculations, B3LYP, M11-L, MP2, and spin-component-scaled MP2 (SCS-MP2) methods were used, coupled with SMD and SM8 solvation models. A reduction in carbamate stability leads to an increased CO2 absorption capacity of the amine and a reduction of the energy required for solvent regeneration. Important factors for the reduction of the carbamate stability were an increase in steric hindrance around the nitrogen atom, charge on the N atom and intramolecular hydrogen bond strength. The present study indicates that secondary ethanolamines with sterically hindering groups near the N atom show significant potential as candidates for industrial CO2-capture solvents.

  19. Biofilters to treat the pesticides wastes from spraying applications: results after 4 years of study.

    Pigeon, O; De Vleeschouwer, C; Cors, F; Weickmans, B; Huyghebaert, B; Planchon, V; Pussemier, L; Culot, M

    2006-01-01

    Biofilters were developed in order to eliminate or reduce the quantity of pesticides from rinsing and cleaning waters of sprayers. Biofilters consist in 1, 2 or 3 plastic containers of 1 m3 placed in a vertical pile and containing a substrate elaborated from a homogenised mixture of local soil, chopped straw and compost able to absorb and degrade the pesticides. Biofilters are installed near the area for cleaning and rinsing the sprayer and the waste waters are pumped into the system. Since 2002, a pilot study is carried out in Belgium in order to evaluate the efficacy of these systems. Twenty pilot systems were installed since 2002 until 2004 in several farms, agricultural technical centres or schools and in a municipal maintenance service. The efficacy of the biofilters was studied for several chemical classes of herbicides (sulfonylurea, aryloxyalcanoic acids, chloroacetanilides), insecticides (pyrethroids, carbamates) and fungicides (dicarboximides, phenylamides, triazoles and strobilurines). The balance of the inputs and the outputs of the pesticides was determined by monitoring the elutes. The degradation kinetic of pesticides into the substrate was evaluated by analysing the pesticides into the substrate. The microbiological activity of the substrate was also evaluated by measuring respiration and some indirect parameters like dry matter content, Kjeldahl nitrogen content, organic carbon content and biological oxygen demand (BOD). Results obtained until now after four years of experiments have showed an overall good efficacy (retention) of pesticides by the biofilter and a high degradation rate for the majority of pesticides. Biofilters permit to reduce highly the quantity of pesticides from rinsing and cleaning waters of sprayers and contribute significantly to the reduction of the contamination of surface water. Biofilters are now registered by the Ministry of Agriculture and Environment of the Walloon Region in Belgium and are recommended to pesticides

  20. Plant-parasitic Nematode Acetylcholinesterase Inhibition by Carbamate and Organophosphate Nematicides.

    Opperman, C H; Chang, S

    1990-10-01

    The sensitivity of acetylcholinesterases (ACHE) isolated from the plant-parasitic nematodes Meloidogyne arenaria, M. incognita, and Heterodera glycines and the free-living nematode Caenorhabditis elegans to carbamate and organophosphate nematicides was examined. The AChE from plant-parasitic nematode species were more sensitive to carbamate inhibitors than was AChE from C. elegans, but response to the organophosphates was approximately equivalent. The sulfur-containing phosphate nematicides were poor inhibitors of nematode acetylcholinesterase, but treatment with an oxidizing agent greatly improved inhibition. Behavioral bioassays with living nematodes revealed a poor relationship between enzyme inhibition and expression of symptoms in live nematodes.

  1. Distribution of pesticides in n-hexane/water and n-hexane/acetonitrile systems and estimation of possibilities of their extraction isolation and preconcentration from various matrices.

    Zayats, M F; Leschev, S M; Petrashkevich, N V; Zayats, M A; Kadenczki, L; Szitás, R; Szemán Dobrik, H; Keresztény, N

    2013-04-24

    Distribution of 150 most widely used pesticides of different chemical classes (amides, anilinopirimidines, aromatics, benzenesulfonates, carbamates, dicarboximides, organophosphorus compounds, phenyl esters, phenylureas, pyrazoles, pyrethroids, pyrimidines, strobilurins, sulfamides, triazines, triazoles, etc.) in n-hexane/water and n-hexane/acetonitrile systems was investigated at 25°C. Distribution constants of pesticides (P) have been calculated as ratio of pesticide concentration in n-hexane to its concentration in water or acetonitrile phase. HPLC and GC methods were used for pesticides determination in phases. It was found that the overwhelming majority of pesticides are hydrophobic, i.e. in n-hexane/water system LgP≫0, and the difference in LgP values can reach 9.1 units. Replacement of water for acetonitrile leads to dramatic fall of LgP values reaching 9.5 units. The majority of LgP values in this case are negative and their differences is strongly leveled in comparison with a hexane/water system. Thus, maximal difference in pesticides LgP values for n-hexane/acetonitrile system is 3.2 units. It is shown that n-hexane can be used for selective and efficient extraction and preconcentration of pesticides from water matrices. On the other hand, acetonitrile is effective for the isolation and preconcentration of pesticides from hydrocarbon and vegetable oil matrices. The distribution constants described in the paper may be effectively used for the estimation of possibilities of extraction isolation, preconcentration and separation of pesticides.

  2. Comparison of solid phase- and liquid/liquid-extraction for the purification of hair extract prior to multi-class pesticides analysis.

    Duca, Radu-Corneliu; Salquebre, Guillaume; Hardy, Emilie; Appenzeller, Brice M R

    2014-04-01

    The present study focuses on the influence of a purification step - after extraction of pesticides from hair and before analysis of the extract - on the sensitivity of analytical methods including compounds from different chemical classes (both parent and metabolites). Sixty-seven pesticides and metabolites from different chemical classes were tested here: organochlorines, organophosphates, carbamates, pyrethroids, ureas, azoles, phenylpyrazoles and neonicotinoids. Two gas chromatography-negative chemical ionization-tandem mass spectrometry methods and one based on ultra-performance liquid chromatography-electrospray tandem mass spectrometry were used. Seven solid-phase extraction cartridges: C18, S-DVB, PS-DVB, GCB, GCB/PSA, SAX/PSA and Florisil/PSA were tested and compared to more classical liquid-liquid extraction procedures using ethyl acetate, hexane and dichloromethane. Although LLE allowed obtaining good results for some compounds, on the whole, SPE clearly provided better recovery for the majority of the pesticide residues tested in the present study. GCB/PSA was clearly the best suited to non-polar compounds such as organochlorines, pyrethroids and organophosphates, with recovery ranging from 45.9% (diflufenican) to 117.1% (parathion methyl). For hydrophilic metabolites (e.g. dialkyl phosphates and other organophosphate metabolites, pyrethroid metabolites, phenols and carbamate metabolites), the best results were obtained with PS-DVB, with recovery ranged from 10.3% (malathion monocarboxylic acid) to 93.1% (para-nitrophenol). For hydrophilic parent pesticides (e.g. neonicotinoids, carbamates, azoles) and metabolites without nucleophilic functions, the best recovery was obtained with SAX/PSA, with recovery ranging from 52.1% (3-hydroxycarbofuran) to 100.9% (3,4-dichloroaniline). Solid phase extraction was found to be more suitable than the liquid-liquid extraction for pesticides and their metabolites determination in terms of number of extracted compounds

  3. Efficient preparation of carbamates by Rh-catalysed oxidative carbonylation: unveiling the role of the oxidant.

    Iturmendi, Amaia; Iglesias, Manuel; Munárriz, Julen; Polo, Victor; Pérez-Torrente, Jesús J; Oro, Luis A

    2016-12-22

    The synthesis of a wide variety of carbamates from amines, alcohols and carbon monoxide has been achieved by means of a Rh-catalysed oxidative carbonylation reaction that uses Oxone as a stoichiometric oxidant. In-depth studies on the reaction mechanism shed light on the intimate role of Oxone in the catalytic cycle.

  4. The Use and Effect of Carbamate Insecticide on Animal Health and Products

    Indraningsih

    2008-06-01

    Full Text Available The use of carbamate in Indonesia is relatively new, in particular after prohibition on the use of most organochlorines (OC. Carbamates that commonly used for agricultural activities are carbofuran (Furadan, aldicarb (Temik and carbaryl (Sevin. When properly used, they will provide benefit, but misuse of insecticides would affect productivity, poisoning, public health problems, environmental contamination and residues in foods. A monitoring result of carbamate used in Java indicates that carbofurans were detected in soils (0,8 – 56,3 ppb; water (0,1 – 5,0 ppb; rice (nd – 5,0 ppb; soybeans (1,2 – 610 ppb; animal feed (12 – 102 ppb; beef (110 – 269 ppb; and sera of beef cattle (167 – 721 ppb. The residue level was above the maximum residue limits (MRL released by Indonesian Standardization Agency (Badan Standardisasi Nasional in some samples. The presence of carbofuran in foods should be taken into account since the carbofuran is regarded highly toxic for public and animal health. This paper describes the toxicity of carbamate, clinical signs of poisoning, residue in foods and environment, handling of poisoning and residue control.

  5. Design, synthesis, and evaluation of carbamate-substituted analogues of (+)-discodermolide.

    Smith, Amos B; Freeze, B Scott; Lamarche, Matthew J; Hirose, Tomoyasu; Brouard, Ignacio; Rucker, Paul V; Xian, Ming; Sundermann, Kurt F; Shaw, Simon J; Burlingame, Mark A; Horwitz, Susan Band; Myles, David C

    2005-01-20

    [Structure: see text] The design, syntheses, and biological evaluation of 22 totally synthetic analogues of the potent microtubule-stabilizing agent (+)-discodermolide (1) have been achieved. Structure-activity relationships of the C(19) carbamate were defined, exploiting two synthetically simplified scaffolds, as well as the parent (+)-discodermolide framework.

  6. Baygon-A New Carbamate Insecticide and its Evaluation Against Cockroaches by a Simple New Technique

    R. N. Varma

    1969-10-01

    Full Text Available Baygon a new carbamate insecticide has been tested for its efficacy against cockroaches, Periplanta americana Linn. in relation to Sumithion and Malathion by a simple technique developed by the authors. It has been found to be much superior in producing Knock-down and kill of the insects as compared to Sumithion and Malathion.

  7. Carbamate Stabilities of Sterically Hindered Amines from Quantum Chemical Methods: Relevance ofr CO2 Capture

    Gangarapu, S.; Marcelis, A.T.M.; Zuilhof, H.

    2013-01-01

    The influence of electronic and steric effects on the stabilities of carbamates formed from the reaction of CO2 with a wide range of alkanolamines was investigated by quantum chemical methods. For the calculations, B3LYP, M11-L, MP2, and spin-component-scaled MP2 (SCS-MP2) methods were used, coupled

  8. Discovery and optimization of adamantyl carbamate inhibitors of 11β-HSD1.

    Tice, Colin M; Zhao, Wei; Krosky, Paula M; Kruk, Barbara A; Berbaum, Jennifer; Johnson, Judith A; Bukhtiyarov, Yuri; Panemangalore, Reshma; Scott, Boyd B; Zhao, Yi; Bruno, Joseph G; Howard, Lamont; Togias, Jennifer; Ye, Yuan-Jie; Singh, Suresh B; McKeever, Brian M; Lindblom, Peter R; Guo, Joan; Guo, Rong; Nar, Herbert; Schuler-Metz, Annette; Gregg, Richard E; Leftheris, Katerina; Harrison, Richard K; McGeehan, Gerard M; Zhuang, Linghang; Claremon, David A

    2010-11-15

    Synthesis of 2-adamantyl carbamate derivatives of piperidines and pyrrolidines led to the discovery of 9a with an IC(50) of 15.2 nM against human 11β-HSD1 in adipocytes. Optimization for increased adipocyte potency, metabolic stability and selectivity afforded 11k and 11l, both of which were >25% orally bioavailable in rat.

  9. Pesticides and oncogenic modulation.

    Vakonaki, Elena; Androutsopoulos, Vasilis P; Liesivuori, Jyrki; Tsatsakis, Aristidis M; Spandidos, Demetrios A

    2013-05-10

    Pesticides constitute a diverse class of chemicals used for the protection of agricultural products. Several lines of evidence demonstrate that organochlorine and organophosphate pesticides can cause malignant transformation of cells in in vitro and in vivo models. In the current minireview a comprehensive summary of recent in vitro findings is presented along with data reported from human population studies, regarding the impact of pesticide exposure on activation or dysregulation of oncogenes and tumor suppressor genes. Substantial mechanistic work suggests that pesticides are capable of inducing mutations in oncogenes and increase their transcriptional expression in vitro, whereas human population studies indicate associations between pesticide exposure levels and mutation occurrence in cancer-related genes. Further work is required to fully explore the exact mechanisms by which pesticide exposure affects the integrity and normal function of oncogenes and tumor suppressor genes in human populations.

  10. Comparative toxicity of the pesticides carbofuran and malathion to the freshwater flagellate Euglena gracilis.

    Azizullah, Azizullah; Richter, Peter; Häder, Donat-Peter

    2011-08-01

    Pesticides are toxic chemicals used for agricultural as well as non-agricultural purposes. The toxicity of pesticides does not remain limited to the site of application but they also cause toxicity to non-target organisms in terrestrial as well as in aquatic environments. This study discusses the comparative toxicity of a carbamate (carbofuran) and an organophosphorus (malathion) pesticide to the freshwater flagellate Euglena gracilis during short- and long-term exposures. To evaluate the toxicity of the pesticides, different parameters of the flagellate, like cell density, motility, swimming velocity, cell shape, gravitactic orientation, photosynthetic efficiency, and concentration of light harvesting pigments, were used as end points. Carbofuran was found to be more toxic to E. gracilis than malathion and adversely affected almost all the tested parameters in short- and long-term experiments. The only significant adverse effect by malathion could be demonstrated on the swimming velocity of cells in short-term experiments. The adverse effects of the pesticides were more pronounced during short-term than during long-term exposure.

  11. Identification and quantification of pesticide residues in water samples of Dhamrai Upazila, Bangladesh

    Hasanuzzaman, M.; Rahman, M. A.; Salam, M. A.

    2016-10-01

    Being agricultural country, different types of pesticides are widely used in Bangladesh to prevent the crop losses due to pest attack which are ultimately drain to the water bodies. The present study was conducted to identify and quantify the organochlorine (DDT, DDE and DDD), organophosphorus (malathion, diazinon and chloropyrifos) and carbamate (carbaryl) residues in water samples of different sources from Dhamrai upazila of Bangladesh using high performance liquid chromatography (HPLC) equipped with ultra violate (UV) detector. Thirty water samples from fish pond, cultivated land and tube-well were collected in winter season to analyze the pesticide residues. Among the organophosphorus pesticides, malathion was present in seven water samples ranging from 42.58 to 922.8 μg/L, whereas diazinon was detected in water sample-8 (WS-8) and the concentration was 31.5 μg/L. None of the tested water samples was found to be contaminated with chlorpyrifos, carbaryl or DDT and its metabolites (DDE and DDD). Except for a tube-well water sample, concentrations of the detected residues are above the acceptable limit for human body as assigned by different organizations. To avoid the possible health hazards, the indiscriminate application of pesticides should be restricted and various substitute products like bio-pesticide should be introduced in a broad scale as soon as possible.

  12. Collateral damage: rapid exposure-induced evolution of pesticide resistance leads to increased susceptibility to parasites.

    Jansen, Mieke; Stoks, Robby; Coors, Anja; van Doorslaer, Wendy; de Meester, Luc

    2011-09-01

    Although natural populations may evolve resistance to anthropogenic stressors such as pollutants, this evolved resistance may carry costs. Using an experimental evolution approach, we exposed different Daphnia magna populations in outdoor containers to the carbamate pesticide carbaryl and control conditions, and assessed the resulting populations for both their resistance to carbaryl as well as their susceptibility to infection by the widespread bacterial microparasite Pasteuria ramosa. Our results show that carbaryl selection led to rapid evolution of carbaryl resistance with seemingly no cost when assessed in a benign environment. However, carbaryl-resistant populations were more susceptible to parasite infection than control populations. Exposure to both stressors reveals a synergistic effect on sterilization rate by P. ramosa, but this synergism did not evolve under pesticide selection. Assessing costs of rapid adaptive evolution to anthropogenic stress in a semi-natural context may be crucial to avoid too optimistic predictions for the fitness of the evolving populations.

  13. [Pesticide detection in Costarican vegetables based on the inhibition of serum and erythrocytic human cholinesterases].

    Nevermann, Karl Schosinsky; Guzmán, Eugenia Quintana

    2004-12-01

    A simple and low cost method able to detect the presence of pesticides, organophosphates and carbamates based on the inhibition of serum and erythrocytic cholinesterases, was used in lettuce (Lactuca sativa), cilantro (Coriandum santivum) and celery (Apium graveolens) obtained from the Ferias del Agricultor from Valle Central of Costa Rica. The percentage inhibition of cholinesterases is related to the presence of plaguicide in the vegetable. Thirteen percent of the analyzed samples were positive for plaguicides using serum cholinesterase and 33% for erythrocytic cholinesterase. Washing and cooking the vegetables does not eliminate the presence of plaguicides but they lower slightly the concentration. Statistical evidence (p = 0.0001) indicates that erythrocytic cholinesterase has higher analytical sensitivity than serum cholinesterase. It is very important to establish the degree of contamination with pesticides in these agricultural products because they are exposed to direct contamination by fumigation, soil contamination and irrigation water, and are products that are often consumed without adequate cooking and washing.

  14. Optical Biosensor with Multienzyme System Immobilized onto Hybrid Membrane for Pesticides Determination

    Lyubov Yotova

    2011-12-01

    Full Text Available A construction of optical biosensor based on simultaneous immobilization of acetylcholinesterase and choline oxidase enzymes for the detection of pesticides residues is described. Different kinds of novel SiO2 hybrid membranes were synthesized to be suitable for optical biosensors using sol-gel techniques. The bioactive component of the sensor consists of a multi-enzyme system including acetylcholinesterase and choline oxidase covalently immobilized on new hybrid membranes. The sensor exhibited a linear response to acetylcholine in a concentration range of 2.5 - 30 mM. Inhibition plots obtained from testing carbamate (carbofuran pesticides exhibited concentration dependent behaviour and showed linear profiles in concentration ranges between 5x10-8 - 5x10-7 M for carbofuran. The factors affecting the constructed optical biosensors were investigated.

  15. Characterizing pesticide sorption and degradation in macro scale biopurification systems using column displacement experiments

    Wilde, Tineke de [Laboratory of Crop Protection Chemistry, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, B-9000 Ghent (Belgium)], E-mail: Tineke.DeWilde@UGent.be; Spanoghe, Pieter [Laboratory of Crop Protection Chemistry, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, B-9000 Ghent (Belgium); Mertens, Jan; Sniegowksi, Kristel; Ryckeboer, Jaak [Division of Soil and Water Management, Faculty of Bioscience Engineering, K.U. Leuven, Kasteelpark Arenberg 20, B-3001 Heverlee (Belgium); Jaeken, Peter [PCF-Royal Research Station of Gorsem, De Brede Akker 13, 3800 Sint-Truiden (Belgium); Springael, Dirk [Division of Soil and Water Management, Faculty of Bioscience Engineering, K.U. Leuven, Kasteelpark Arenberg 20, B-3001 Heverlee (Belgium)

    2009-04-15

    The efficiency of biopurification systems to treat pesticide-contaminated water was previously studied in microcosms. To validate the obtained results, macrocosm systems were set-up. Four pesticides (linuron, isoproturon, bentazone, and metalaxyl) were continuously applied to ten different organic substrate mixes. Retention of the pesticides was similar and in some cases slightly lower in the macrocosms compared to the microcosms. Differences in retention between the different mixes were however minimal. Moreover, the classification of the retention strength of the pesticides was identical to that observed in microcosms: linuron > isoproturon > metalaxyl > bentazone. Monod kinetics were used to describe delayed degradation, which occurred for isoproturon, metalaxyl and bentazone. No breakthrough of linuron was observed, thus, this pesticide was appointed as the most retained and/or degraded pesticide, followed by isoproturon, metalaxyl and bentazone. Finally, most of the matrix mixes efficient in degrading or retaining pesticides were mixes containing dried cow manure. - Transport of pesticides in macrocosm containing organic substrates.

  16. Control of Pesticides 2000

    Krongaard, T.; Petersen, K. K.; Christoffersen, C.

    Three different groups of products covered by the pesticide regulation have been included in the 2000 analytical chemical authority control: 1) herbicides containing aclonifen, clopyralid, dicamba, quinoclamine, bromoxynil, ioxynil, simazine, and terbuthylazine. 2) Fungicides containing fenpropidin......, fluazinam, and kresoxim-methyl, and among insecticides containing fenazaquin. Thus, all the eighteen analysed samples of these pesticides complied with the accepted tolerances with respect to content of active ingredients set by the Danish regulation of pesticides. The only product containing buprofezin...

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

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

    2013-05-01

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

  18. Improved indicators and monitoring of pesticide use

    Sørensen, Peter Borgen; Kjær, Christian; Kudsk, Per

      The goal for the new improved indicator, PestNaB (Pesticiders NaturBelastning), was to develop a valid indicator reflecting the potential risk for nature due to application of pesticides and based on available data set for Danish conditions. The focus is on risk in relation the nature close to......, and directly inside, the agricultural areas so this excludes the risk for contamination of groundwater and the human risk. Elements from existing indicators are combined in a way that can make optimal use of the available data, where the level of complexity is adjusted to fit the conditions of uncertainty...

  19. Pesticide Product Information System (PPIS)

    U.S. Environmental Protection Agency — The Pesticide Product Information System contains information concerning all pesticide products registered in the United States. It includes registrant name and...

  20. Exposure to Pesticides in Residents or the Banks of the Río Bogotá (Suesca and the Capitan Fish

    Rodríguez-Forero Adriana

    2012-03-01

    Full Text Available Objective: Considering the high use of pesticides in Colombia and the harmful effects resulting fromexposure to these substances on human health and the environment, a study for the determinationof biomarkers of exposure and effect of pesticides in population of the banks of the Río Bogotáin Suesca, the levels of pesticides in river water samples taken in the same city and in samples offish, “Capitán de la Sabana” (Eremophylus mutisii caught in this area. Materials and methods:We measured for organophosphates, carbamates, dithiocarbamates and organochlorines. We alsoexplored through a survey of occupational exposure to pesticides in the population and knowledgeand use of personal protective measures in their work. Additionally, we explored the habit offishing for captain and consumption in the diet of the inhabitants of the riverbank. Results: Theresults show the presence of organochlorine and organophosphorus pesticides in the river and infish tissue and organochlorine and ethylene thiourea in human biological samples. Participated inthe study workers directly exposed to pesticides, highly toxic handlers, most know and use personalprotective measures and industrial hygiene. Conclusions: Pollution such as pesticides in the upperbasin of Bogotá that affects wildlife and coastal populations. Best action is necessary to promoteenvironmental care, protection and self-care of persons using pesticides in the area.

  1. [Analysis of pesticide multiresidues in rice by gas chromatography-mass spectrometry coupled with solid phase extraction].

    Liu, Pengyan; Liu, Qingxue; Ma, Yusong; Liu, Jinwei; Jia, Xuan

    2006-05-01

    A new analytical method was developed to simultaneously determine multiple pesticide residues in rice including organophosphorus, organochlorine, carbamate and pyrethroid. First, the solvents for pesticide extraction were selected for optimization. Eight solvents were screened to find that the extraction efficiency with dichloromethane was the best. Second, clean-up was performed by solid phase extraction using a Florisil cartridge. Various mixtures of hexane and acetone were tested to show that the mixture of hexane-acetone (4:1, v/v) had the best performance. The clean-up helped the sample purification significantly. The prepared sample was analyzed using gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring (SIM) mode. The pesticides were identified with retention time and selected ions and their relative abundances, and they were quantified based on extract of spiking standards in a blank sample. The limits of detection (LODs) were evaluated on the values of the lower concentration fortified sample under the signal-to-noise ratio of 3:1. The recoveries and relative standard deviations (RSDs) were checked by adding pesticide standard solution at two levels to untreated samples, and the triplicate analysis of the samples were carried out for each spiked level. The LODs were at microg/kg level. The average recoveries of most pesticides were from 75% to 120 %. The RSDs were less than 10.4% (n = 3). These results indicated that this method is simple, rapid, sensitive for the simultaneous determination requirements of multiple pesticide residues in rice.

  2. Pesticide Sector Performed Well

    Wang Lvxian

    2007-01-01

    @@ 1 Further output growth in the first half of 2007 According to data from the National Bureau of Statistics of China, the output of pesticides (usually refering to pure pesticide technical) in China was 856 thousand tons in the first half of 2007, an increase of 25.6% over the same period of 2006.

  3. Food and Pesticides

    EPA sets limits on how much of a pesticide may be used on food during growing and processing, and how much can remain on the food you buy. Learn about regulation of pesticides on food and how you can limit exposure.

  4. Pesticides in Ground Water

    Bjerg, Poul Løgstrup

    1996-01-01

    Review af: Jack E. Barbash & Elizabeth A. Resek (1996). Pesticides in Ground Water. Distribution trends and governing factors. Ann Arbor Press, Inc. Chelsea, Michigan. pp 588.......Review af: Jack E. Barbash & Elizabeth A. Resek (1996). Pesticides in Ground Water. Distribution trends and governing factors. Ann Arbor Press, Inc. Chelsea, Michigan. pp 588....

  5. Control of Pesticides 2001

    Krongaard, T.; Petersen, K. K.; Christoffersen, C.

    The analytical chemical authority control on pesticide products on the Danish market performed in 2001 is reported. Samples of selected groups of pesticides have been collected from the market and analysed to verify whether the actual contents of the respective active ingredients in the products...... comply with the label-claimed content. The tolerance of deviation from the label-claimed content of active ingredient is set by the Danish pesticide regulation. Three different groups of products covered by the pesticide regulation have been included in the 2001 analytical chemical authority control: 1....... Satisfactory results were found among herbicides containing pendimethalin and methabenzthiazuron, among fungicides containing azaconazole, tolylfluanid, propamocarb and cyprodinil, and among insecticides containing amitraz, phosalone and diflubenzuron. Thus, the twelve analysed samples of these pesticides...

  6. Pesticide content of infant formulae and weaning foods available in New Zealand.

    Cressey, P J; Vannoort, R W

    2003-01-01

    A survey of the pesticide content of 25 commercially available infant formulae and 30 weaning foods available in New Zealand was undertaken in 1996. It included a representative mixture of imported and New Zealand manufactured infant foods. Three different pesticide screening techniques were used: a high-sensitivity organochlorine screen was carried out on all infant formulae, while a multiresidue screen (organochlorine and organophosphorus pesticides, synthetic pyrethroids, carbamate pesticides, fungicides and herbicides), and a specific screen for dithiocarbamate fungicides were both carried out on all weaning foods and on soy-based infant formulae. All results are expressed on a ready-to-feed basis. Extremely low levels of residues of three organochlorine compounds (p,p'-DDE, p,p'-DDT and dieldrin) were detected in infant formulae samples. Residues of p,p'-DDE were found in seven of 20 milk-based infant formulae at concentrations ranging from 0.03 to 0.5 microgram kg(-1). Residues of p,p'-DDT were found in one imported milk-based infant formula at 0.7 microgram kg(-1), and dieldrin residues were detected in four of five soy-based infant formulae at concentrations ranging from 0.05 to 0.08 microgram kg(-1). The multiresidue pesticide screen detected low levels of residues of two organophosphorus pesticides; azinphos-methyl in one soy-based infant formula at a level of 22 microgram kg(-1) and pirimiphos-methyl in two cereal-based weaning foods at concentrations of 5 and 14 microgram kg(-1). None of the other approximately 140 pesticides (including fungicides and herbicides) included in the multiresidue screen were detected in any weaning foods or soy-based infant formulae, at a detection limit of 10 microgram kg(-1). No residues of dithiocarbamate fungicides were detected in any product analysed, at a detection limit of 100 microgram kg(-1).

  7. Health Risk Assessment of Pesticide Usage in Menia El-Kamh Province of Sharkia Governorate in Egypt

    Jean-Claude Assad

    2002-10-01

    Full Text Available Abstract: Menia El-Kamh province of the Sharkia Governorate constitutes one of the largest agricultural areas in Egypt. About 88% of the nearly 472,000 people living in this province rely on agricultural activities for subsistence. Several pesticides including organochloride, organophosphorus, carbamate, and pyrethroid insecticides, fungicides, and herbicides are commonly used in citrus, vegetable and other crop-growing areas to increase agricultural productivity. However, their use has also been associated with several cases of pesticide poisoning. In this research, we conducted a field survey to assess the knowledge, attitudes, and practices of the farmer’s community regarding the safe use of pesticides. We also evaluated the residual concentrations of selected pesticides in water, soil, milk, fish, and orange samples, and estimated the potential health risks associated with the exposure to these pesticides. Data obtained from the field survey indicate that more than 95% of farm workers do not practice safety precautions during pesticide formulation and application; leading to a considerable prevalence of pesticide-related illnesses in this agricultural community. Pesticide residues in various environmental samples varied greatly; from below detection levels (3-5 ng to as high as 325 ppb depending on the matrix of interest, and the specific pesticide of concern. The analysis of health risk estimates indicated that chlorpyrifos, DDT, dimethoate, methomyl, and larvin did not pose a direct hazard to human health, although present in water, milk, orange, and/or fish. However, aldicarb, and carbosulfan levels exceeded the reference doses, indicating a great potential for systemic toxicity, especially in children who are considered to be the most vulnerable population subgroup. The upper-bound values of cancer risk from DDT exposure were estimated to be about 8 (adults, and 55 (children excess cancers in a population of one million.

  8. Intensification of degradation of methomyl (carbamate group pesticide) by using the combination of ultrasonic cavitation and process intensifying additives.

    Raut-Jadhav, Sunita; Pinjari, Dipak V; Saini, Daulat R; Sonawane, Shirish H; Pandit, Aniruddha B

    2016-07-01

    In the present work, the degradation of methomyl has been carried out by using the ultrasound cavitation (US) and its combination with H2O2, Fenton and photo-Fenton process. The study of effect of operating pH and ultrasound power density has indicated that maximum extent of degradation of 28.57% could be obtained at the optimal pH of 2.5 and power density of 0.155 W/mL. Application of US in combination with H2O2, Fenton and photo-Fenton process has further accelerated the rate of degradation of methomyl with complete degradation of methomyl in 27 min, 18 min and 9 min respectively. Mineralization study has proved that a combination of US and photo-Fenton process is the most effective process with maximum extent of mineralization of 78.8%. Comparison of energy efficiency and cost effectiveness of various processes has indicated that the electrical cost of 79892.34Rs./m(3) for ultrasonic degradation of methomyl has drastically reduced to 2277.00Rs./m(3), 1518.00Rs./m(3) and 807.58Rs./m(3) by using US in combination with H2O2, Fenton and photo-Fenton process respectively. The cost analysis has also indicated that the combination of US and photo-Fenton process is the most energy efficient and cost effective process.

  9. A study on the effects of golf course organophosphate and carbamate pesticides on endangered, cave-dwelling arthropods Kauai, Hawaii

    US Fish and Wildlife Service, Department of the Interior — Three endemic species, two arthropods and one isopod, are present in the Kauai caves. These species are critical components of the cave ecosystems and are possibly...

  10. The effects of some carbamate local anaesthetics on the guinea-pig ileum.

    Bezeková, M; Bauer, V

    1986-01-01

    The action of some carbamate local anaesthetics, pentacaine, BK-52 and heptacaine, was compared in the guinea-pig ileum with that of classic local anaesthetics, procaine and trimecaine. Contractions of the ileum were evoked by transmural stimulation, nicotine, acetylcholine, noradrenaline, histamine, K+ and Ba++. Although the evoked contractions were inhibited by all the local anaesthetics, there was a marked difference in their ability to influence the smooth muscle activation induced by different stimuli. The differences among the IC50 values were slight in the case of pentacaine, moderate in the case of trimecaine and BK-52 and large in the case of procaine and heptacaine. It is suggested that besides their effects on the unmyelinated autonomic nerves, the carbamate local anaesthetics studied can also affect the smooth muscle membrane, similarly to the classic agents. The mechanism of their direct effect is discussed.

  11. Sulfonamide and carbamate derivatives of 6-chloropurine: synthesis, characterization and antimicrobial activity evaluation

    K. Venkata Narayana

    2016-07-01

    Full Text Available A series of new sulfonamide derivatives, 9-(substitutedbenzenesulfonyl-6-chloro-9H-purines 7(a-e and carbamate derivatives, 6-chloro-purine-9-carboxylic acid substituted alkyl/arylester 9(a-d, have been synthesized through an intermediate, sodium salt of 6-chloro-9(H-purine (6 which was prepared by the treatment of 6-chloro-9(H-purine (4 with sodium hydride. Structures of the newly synthesized compounds were elucidated by IR, NMR ( 1H and 13C, mass spectra and elemental analysis. Antimicrobial activity against three bacterial strains and three fungal strains at two different concentrations, 100 and 200 µg/mL including MIC values was investigated. Bio-screening data disclosed that most of the sulfonamide derivatives, 7a, 7c and 7d, and one carbamate derivative 9a showed promising antimicrobial activity having MIC values in the range of 18.0-25.0 µg/mL.

  12. Quantitative analysis of ethyl carbamate in Korean alcoholic beverages by chromatography with mass selective detection

    Park, G.B.; Lee, S.G. [Korea Research Institute of Chemical Technology, Taejon (Korea)

    2002-02-01

    In order to determine the contents of ethyl carbamate in Korean traditional alcoholic beverages and general beverages, GC/MS-SIM method was used after extraction of beverages with dichloromethane. The contents of ethyl carbamate in Korean traditional alcoholic beverages, non-distilled alcohol, and whisky were detected in the rage of 4.6-50.2 {mu}g/L, 27.8-45.4 {mu}g/L, and 24.8-55.1 {mu}g/L, respectively. The recoveries were ranged from 83.3 to 104.8 %. The values of relative standard deviation were ranged from 1.8 to 14.8% and the detection limit was 0.3 {mu}g/L. (author). 13 refs., 2 tabs., 4 figs.

  13. The Danish Pesticide Tax

    Pedersen, Anders Branth; Nielsen, Helle Ørsted; Andersen, Mikael Skou

    2015-01-01

    This case study analyses the effects of the Danish pesticide tax (1996-2013) on agriculture which was introduced as an ad valorem tax in 1996, doubled in 1998, and redesigned in 2013 as a tax based on the toxicity of the pesticides. The Danish pesticide taxes probably represent the world’s highes...... individuals in the target group necessarily react to the economic incentives as predicted by economic modeling. It also demonstrates that a small first green-tax-step over time might develop into a better tax design.......This case study analyses the effects of the Danish pesticide tax (1996-2013) on agriculture which was introduced as an ad valorem tax in 1996, doubled in 1998, and redesigned in 2013 as a tax based on the toxicity of the pesticides. The Danish pesticide taxes probably represent the world’s highest...... pesticide taxes on agriculture, which makes it interesting to analyze how effective they have been. Here the effects of the ad valorem tax (1996-2013) are analyzed. The case study demonstrates the challenges of choosing an optimal tax design in a complex political setting where, additionally, not all...

  14. A study of neurologic symptoms on exposure to organophosphate pesticides in the children of agricultural workers

    Rastogi S

    2010-01-01

    Full Text Available Pesticides are used extensively throughout the world in agriculture and in pest control as well as for community health purposes. Organophosphate (OP pesticide self-poisoning is an important clinical problem in rural regions of the developing world that kills an estimated 200,000 people every year. Unintentional poisoning kills far fewer people but is an apparent problem in places where highly toxic OP pesticides are available. Neurologic dysfunction is the best documented health effect of pesticide exposure. High-level exposure has both acute and long-term neurologic signs and symptoms, and adverse effects have been reported in most type of pesticides, including organophosphate (OP, carbamate, organochlorine, and pyrethroid insecticides, herbicides, fungicides, and fumigants. Acute OP pesticide exposure can involve in wide range of both central and peripheral neurologic symptoms. Increased neurologic symptom prevalence may provide early evidence of neurologic dysfunctions, before clinically measurable signs are evident. In this study, we analyzed the cross-sectional data on neurologic signs and symptoms from 225 rural children, both males (n = 132 and females (n = 93 who were occupationally and paraoccupationally exposed to methyl OPs (dichlorvos, fenthion, malathion, methyl parathion and ethyl OPs (chlorpyrifos, diazinon, ethyl parathion as they belonged to agricultural families handling, mixing, and spraying the OP pesticides. The children completed a specially designed questionnaire (Q16 on neurologic symptoms associated with pesticide exposure with their parental help. A suitable reference group consisting of rural children (n = 50 never involved in pesticide handling (neither outdoor nor indoor belonging to similar socioeconomic strata included in the study to compare the prevalence of various neurologic symptoms between the two groups. Among all the neurologic self-reported symptoms, headache, watering in eyes, and burning sensation in

  15. Efficient Lewis Acids Catalyzed Aza-Michael Reactions of Enones with Carbamates

    XIA Chun-Gu; XU Li-Wen

    2004-01-01

    The a-amino carbonyl functionality is not only a segment of biologically important natural products but also a versatile intermediate for the synthesis of nitrogen-containing compounds.1 The development of novel synthetic methods leading to a-amino ketone, a-amino acids or their derivatives has attracted much attention in organic synthesis.2 Among the traditional methods for generating a-amino carbonyl compounds, Mannich-type reaction is one of the classical and powerful methods.3 However, the classic Mannich reaction presents serious disadvantages, for example, there is still a drawback in that the silyl enolates have to be prepared from the corresponding carbonyl compounds. Alternatively, aza-Michael additions can be used to create carbon-heteroatom bonds by reaction of a,a-unsaturated carbonyl compounds with amines. Although recent advances have made this route more attractive, development of cheaper, simpler, and more efficient metal catalyst, especially which can be applied to chalcone, is highly desirable.In this paper, we demonstrated that the first aza-Michael reaction of chalcone with a less nucleophilic carbamates can be accomplished on Me3SiCFFeCl3 catalyst system under very mild conditions. Apart from experimental simplicity, the advantages of this methodology are the use of a very cheap Lewis acid catalyst and the insensitivity of the reaction mixture towards air and moisture.catalyst for aza-Michael reaction of chalcone and cyclic enones with carbamates. And with the cyclic enones with carbamates in dichloromethane at room temperature were also investigated. In this conjugate addition reaction, good to excellent yields of a-amino ketones were obtained with system could also mediates aza-Michael addition of carbamates to chalcone and derivatives.These new strategies opened efficient procedures for the synthesis of a-amino ketones under mild conditions.

  16. Management of exogenous intoxication by carbamates and organophosphates at an emergency unit

    Sydney Correia Leão

    2015-10-01

    Full Text Available Summary Objectives: to evaluate and indicate the procedure to be followed in the health unit, both for diagnosis and the treatment of acute exogenous intoxications by carbamates or organophosphates. Methods: a descriptive study based on retrospective analysis of the clinical history of patients diagnosed with intoxication by carbamates or organophosphates admitted at the emergency unit of the Hospital de Urgências de Sergipe Governador João Alves (HUSE between January and December of 2012. Some criteria were evaluated, such as: intoxicating agent; patient's age and gender; place of event, cause, circumstances and severity of the intoxication; as well as signs and symptoms of the muscarinic, nicotinic and neurological effects. Results: seventy patients (average age: 25±19.97 formed the study's population. It was observed that 77.14% of them suffered carbamate intoxication. However, organophosphate intoxications were more severe, with 68.75% of patients presenting moderate to severe forms. Suicide attempt was the leading cause of poisoning, with 62 cases (88.57% of total. Atropine administration was an effective therapeutic approach for treating signs and symptoms, which included sialorrhea (p=0.0006, nausea (p=0. 0029 and emesis (p lt0.0001. The use of activated charcoal was shown effective, both in combating the signs and symptoms presented by both patient groups (p <0.0001. Conclusion: it is concluded that the use of atropine and activated charcoal is highly effective to treat the signs and symptoms developed by patients presenting acute exogenous intoxication by carbamates or organophosphates.

  17. Deconvolution Method for Determination of the Nitrogen Content in Cellulose Carbamates

    2001-01-01

    Cellulose carbamates (CC) were synthesized with microcrystalline cellulose as raw materials. The Fourier transform infrared spectra of CC with different nitrogen content were recorded. The accurate results of the nitrogen content for CC can be obtained by using the deconvolution method when the nitrogen content is less than 3.5%. The relationship between the nitrogen content and the absorption intensity ratio of the corresponding separated absorption peaks in FTIR spectra has been expressed by an equation precisely.

  18. [Thermal test of reactive hyperemia: a propos of an objective study of pyridinol carbamate].

    Lauliac, M

    1978-01-01

    The thermal test of reactive hyperhemia (TTHR) gives a global and reliable appreciation of the cutaneous microcirculation, the importance of which is well known. In this study, sixty-one subjects were treated for from one month to one year with pyridinol-carbamate. The TTHR was modified in seventy-nine per cent of the cases, showing a considerable and lasting improvement. The clinical symptoms followed a comparable evolution.

  19. Preparation of sintered silver nanosheets by coating technique using silver carbamate complex

    Ahn, Hee-Yong; Cha, Jae-Ryung; Gong, Myoung-Seon, E-mail: msgong@dankook.ac.kr

    2015-03-01

    This study describes a coating technique approach for large-scale preparation of sintered silver nanosheets whose lateral dimensions were controlled in the thickness range of 50–65 nm. These procedures involved coating water-soluble poly (vinyl alcohol) (PVA) and silver 2-ethylhexylcarbamate (Ag-EHC), as well as thermal reduction of a silver precursor by heating at 150 °C, followed by dissolving away the PVA layer with alcoholic water. When the silver carbamate layer on the PVA layer was heated to 150 °C, the silver carbamate layer was thermally reduced and directed to grow into uniform sintered nanosheets with aspect ratios as high as 1000. The multi-stacked PVA/Ag structures and sintered silver nanosheets were confirmed by scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffraction. Measurements of the conductive property at room temperature indicated that these nanosheets were electrically continuous with a resistivity of approximately 7.3 × 10{sup −6} Ω cm. - Highlights: • A coating technique is used to make sintered Ag nanosheets. • PVA and silver carbamate act as a separation layer and a silver precursor. • The Ag nanosheets have thickness width 50–60 nm and width up to hundred μm. • The Ag nanosheets showed a resistivity of ca. 7.3 × 10{sup −6} Ω cm.

  20. Novel cinchona carbamate selectors with complementary enantioseparation characteristics for N-acylated amino acids.

    Krawinkler, Karl Heinz; Maier, Norbert M; Ungaro, Rocco; Sansone, Francesco; Casnati, Alessandro; Lindner, Wolfgang

    2003-01-01

    The synthesis and chromatographic evaluation of the enantiomer separation capabilities of covalently immobilized calix[4]arene-cinchona carbamate hybrid type receptors derived from quinine (QN) and its corresponding C9-epimer (eQN) in different solvents are reported. The receptors display complementary enantiomer separation profiles in terms of elution order, chiral substrate specificity, and mobile phase characteristics, indicating the existence of two distinct chiral recognition mechanisms. The QN-derived receptor binds the (S)-enantiomers of N-acylated amino acids more strongly, shows preferential recognition of open-chained amino acids, and superior enantioselectivity in polar media such as methanol/acetic acid. In contrast, the eQN congener preferentially recognizes the corresponding (R)-enantiomers, displays good enantioselectivity (alpha up to 1.74) for cyclic amino acids, and enhanced stereodiscriminating properties in apolar mobile phases, e.g., chloroform/acetic acid. A comparison of the enantiomer separation profiles with those of the corresponding QN and eQN tert-butyl carbamate congeners indicates no significant level of cooperativity between the calix[4]arene module and the cinchona units in terms of overall chiral recognition, most probably as a consequence of residual conformational flexibility of the calixarene module and the carbamate linkage.

  1. Watershed scale influence of pesticide reduction practices on pesticides and fishes within channelized agricultural headwater streams

    Implementation of pesticide reduction practices to reduce pesticide usage within agricultural watersheds has the potential to reduce pesticide concentrations within agricultural streams. The watershed scale influence of pesticide reduction practices on pesticides and the biota within agricultural he...

  2. Characterizing pesticide sorption and degradation in macro scale biopurification systems using column displacement experiments.

    De Wilde, Tineke; Spanoghe, Pieter; Mertens, Jan; Sniegowksi, Kristel; Ryckeboer, Jaak; Jaeken, Peter; Springael, Dirk

    2009-04-01

    The efficiency of biopurification systems to treat pesticide-contaminated water was previously studied in microcosms. To validate the obtained results, macrocosm systems were set-up. Four pesticides (linuron, isoproturon, bentazone, and metalaxyl) were continuously applied to ten different organic substrate mixes. Retention of the pesticides was similar and in some cases slightly lower in the macrocosms compared to the microcosms. Differences in retention between the different mixes were however minimal. Moreover, the classification of the retention strength of the pesticides was identical to that observed in microcosms: linuron>isoproturon>metalaxyl>bentazone. Monod kinetics were used to describe delayed degradation, which occurred for isoproturon, metalaxyl and bentazone. No breakthrough of linuron was observed, thus, this pesticide was appointed as the most retained and/or degraded pesticide, followed by isoproturon, metalaxyl and bentazone. Finally, most of the matrix mixes efficient in degrading or retaining pesticides were mixes containing dried cow manure.

  3. Acute oral and percutaneous toxicity of pesticides to mallards: Correlations with mammalian toxicity data

    Hudson, R.H.; Haegele, M.A.; Tucker, R.K.

    1979-01-01

    Acute oral (po) and 24-hr percutaneous (perc) LD50 values for 21 common pesticides (19 anticholinesterases, of which 18 were organophosphates, and one was a carbamate; one was an organochlorine central nervous system stimulant; and one was an organonitrogen pneumotoxicant) were determined in mallards (Anas platyrhynchos). Three of the pesticides tested were more toxic percutaneously than orally. An index to the percutaneous hazard of a pesticide, the dermal toxicity index (DTI = po LD50/perc LD50 ? 100), was also calculated for each pesticide. These toxicity values in mallards were compared with toxicity data for rats from the literature. Significant positive correlations were found between log po and log percutaneous LD50 values in mallards (r = 0.65, p 0.10). Variations in percutaneous methodologies are discussed with reference to interspecies variation in toxicity values. It is recommended that a mammalian DTI value approaching 30 be used as a guideline for the initiation of percutaneous toxicity studies in birds, when the po LD50 and/or projected percutaneous LD50 are less than expected field exposure levels.

  4. Health risks of employees working in pesticide retail shops: An exploratory study

    Kesavachandran C

    2009-01-01

    Full Text Available Background: Shop keepers dealing with pesticides are exposed to multiple pesticides that include organophosphates, organochlorines, carbamates, pyrethroids. Hence an exploratory health study was conducted on shopkeepers selling pesticides in urban areas of Lucknow and Barabanki District, Uttar Pradesh, India. Materials and Methods: Detailed information regarding socio-economic status, family history, personal habits and work practices were recorded for 20 subjects and controls by the investigator on a pre-tested questionnaire. Clinical examination including neurological studies of the shopkeepers and control subjects was done. Results: The study revealed significant slowing of motor nerve conduction velocity and low peak expiratory flow rate among shopkeepers as compared to control subjects. Prevalence of significantly higher gastro-intestinal problems was also observed among exposed subjects. Neurological, ocular, cardiovascular and musculo-skeletal symptoms were also found to be higher among shopkeepers. This was not statistically significant. Significantly higher relative risk for sickness related to systems viz., cardio-vasular, genito-urinary, respiratory, nervous and dermal was observed among exposed subjects compared to controls. Conclusions: These findings provide a prima facie evidence of clinical manifestations because of multiple exposures to pesticides and poor safety culture at work place.

  5. Pesticide-Exposure Matrix

    The "Pesticide-exposure Matrix" was developed to help epidemiologists and other researchers identify the active ingredients to which people were likely exposed when their homes and gardens were treated for pests in past years.

  6. Control of Pesticides 2006

    Krongaard, Teddy; Petersen, Kitty Kastalag; Christoffersen, Christel

    The analytical chemical authority control of pesticide products on the Danish market in 2006 is described in this report. Samples of selected groups of pesticides have been collected from the market and analysed to verify whether the actual contents of the respective active ingredients in the pro......The analytical chemical authority control of pesticide products on the Danish market in 2006 is described in this report. Samples of selected groups of pesticides have been collected from the market and analysed to verify whether the actual contents of the respective active ingredients...... analytical chemical authority control: Herbicides containing metamitron, propaquizafop and haloxyfop-ethoxyethyl. Fungicides containing azoxystrobin, propiconazole, cyprodinil, picoxystrobin and fenpropidin. Insecticides containing pirimicarb. Plant growth regulators containing chlormequat chloride, mepiquat...

  7. Control of Pesticides 2004

    Krongaard, T.; Petersen, K. K.; Christoffersen, C.

    Four different groups of products covered by the pesticide regulation were included in the 2004 analytical chemical authority control: 1) Herbicides containing bentazone, dicamba, dichlorprop-P, mecoprop-P, MCPA, foramsulfuron, iodosulfuron-methylsodium, rimsulfuron and triasulfuron. 2) Fungicides...

  8. Pesticide Registration Information System

    U.S. Environmental Protection Agency — PRISM provides an integrated, web portal for all pesticide related data, communications, registrations and transactions for OPP and its stakeholders, partners and...

  9. Respiratory Protection against Pesticides

    Kurt, Burak; Akbaba, Muhsin

    2015-01-01

    Although the respiratory (breathing) system tolerates exposure to a limited degree, some chemicals can impair or destroy portions of it. For many pesticides, the respiratory system is the quickest and most direct route into the circulatory system, allowing rapid transport throughout the body. Thus, it is important to follow the pesticide label and follow directions for control of exposure, especially when respiratory protection is specified. A respirator is a safety device covering at least t...

  10. Development of an analytical strategy based on LC-MS/MS for the measurement of different classes of pesticides and theirs metabolites in meconium: application and characterisation of foetal exposure in France.

    Berton, Thierry; Mayhoub, Flora; Chardon, Karen; Duca, Radu-Corneliu; Lestremau, Francois; Bach, Véronique; Tack, Karine

    2014-07-01

    It is important to evaluate the impact of pesticides on human health because exposure to these compounds has been linked to harmful effects in many research studies. This exposure may be particularly harmful during the early stages of development (e.g. the prenatal period). The aim of the present study was to develop an analytical strategy for quantifying a number of pesticides and their metabolites in meconium (the neonate's first faeces), in order to characterize the extent of foetal exposure. The meconium sample was dried and grinded in order to homogenize the sample, prior to solid-liquid extraction and a purification by solid-phase extraction using a weak anion mixed-mode polymeric sorbent. Analyte separation and quantification was performed by liquid chromatography coupled to electrospray-triple quadrupole mass spectrometry. Five pesticide families (carbamates, organophosphates, pyrethroids, phenylureas and phenoxy herbicides) and their metabolites could be quantified in meconium with limits of quantification ranging between 0.2 ng/g and 200 ng/g. This method was applied to a set of 171 meconium samples collected in the Picardie region of northern France. The highest prevalence was observed for metabolites of organophosphates and carbamates (57.9% and 22.8%, respectively). The parent pesticides were rarely present and were only found at very low concentrations, except for the pyrethroids cyfluthrin and cypermethrin, which were found in 7.6% of meconium samples at concentrations of between 43.8 and 480 ng/g. The most frequently detected contaminant was the organophosphate metabolite dimethyl thiophosphate detected in 49.1% of the samples and quantified with a median concentration of 344 ng/g. These data evidence significant foetal exposure to organophosphate pesticides, pyrethroids and carbamates.

  11. A meta-analysis of the effects of pesticides and fertilizers on survival and growth of amphibians.

    Baker, Nick J; Bancroft, Betsy A; Garcia, Tiffany S

    2013-04-01

    The input of agrochemicals has contributed to alteration of community composition in managed and associated natural systems, including amphibian biodiversity. Pesticides and fertilizers negatively affect many amphibian species and can cause mortality and sublethal effects, such as reduced growth and increased susceptibility to disease. However, the effect of pesticides and fertilizers varies among amphibian species. We used meta-analytic techniques to quantify the lethal and sublethal effects of pesticides and fertilizers on amphibians in an effort to review the published work to date and produce generalized conclusions. We found that pesticides and fertilizers had a negative effect on survival of -0.9027 and growth of -0.0737 across all reported amphibian species. We also observed differences between chemical classes in their impact on amphibians: inorganic fertilizers, organophosphates, chloropyridinyl, phosphonoglycines, carbamates, and triazines negatively affected amphibian survival, while organophosphates and phosphonoglycines negatively affected amphibian growth. Our results suggest that pesticides and fertilizers are an important stressor for amphibians in agriculturally dominated systems. Furthermore, certain chemical classes are more likely to harm amphibians. Best management practices in agroecosystems should incorporate amphibian species-specific response to agrochemicals as well as life stage dependent susceptibility to best conserve amphibian biodiversity in these landscapes.

  12. Effects of pesticides on songbird productivity in conjunction with pecan cultivation in southern Georgia: A multiple-exposure experimental design

    Patnode, K.A.; White, D.H.

    1991-01-01

    A prototypic experimental design was used to assess sublethal effects of multiple and varied organophosphates and carbamates on reproduction in birds. The design allowed for classification of pesticide exposure according to toxicity of applied compounds and type and frequency of applications. Daily survival rates (DSRs) of nests, eggs, and nestlings were determined for northern mockingbirds (Mimus polyglottos), brown thrashers (Toxostoma rufum), and northern cardinals (Cardinalis cardinalis) nesting along edges of pecan orchards and row crops in southern Georgia [USA]. Egg and nestling DSRs for all species combined varied inversely (P 0.05) among three exposure levels. Brain cholinesterase activities were age-dependent and substantiated adult, but not nestling, exposure. Results suggest that increasing exposure to pesticides may reduce songbird productivity.

  13. Comparing regulatory regimens for pesticide control in 22 countries: toward a new generation of pesticide regulation.

    Schmidt-Bleek, F; Marchal, M M

    1993-06-01

    Some historical developments of chemical control legislation are being traced, from specialized laws, such as pesticide acts, to the 1970/1980 generation of generalized legal instruments involving all commercial chemicals. It is then argued that from an environmental protection point of view, a "cradle-to-grave" assessment will henceforth be necessary. Ecological guidelines and indicators for the assessment of the life-cyclewide environmental impact intensity of economic outputs are presented. The international implications of the worldwide trade in pesticides are being considered. As the use of pesticides has invariably transfrontier effects and since unilateral import restrictions due to environmental quality requirements constitute nontariff barriers to trade, a high degree of international harmonization is desirable. This point is also of some importance with a view to the GATT negotiations and the chances for exporting chemicals from developing and postsocialist countries into industrialized hard currency areas in the future. The results of a comprehensive review in 1990/1991 of the regulatory pesticide management regime in 22 countries are presented, comprising countries from Central and Eastern Europe as well as the industrialized Western countries. The review is based upon the returns to a questionnaire which had been designed jointly by the International Institute of Applied Systems Analysis (IIASA) and the Regional Office of the WHO in Copenhagen. The information received was subsequently validated by the competent authorities. Taking all observations into consideration, the framework of an advanced prototype legislative framework for pesticides management is proposed.

  14. Pesticide residues screening in wine by mass spectrometry

    Machado Andrea F.

    2016-01-01

    Full Text Available Recently, a study (from PAN Europe covered 40 bottles of wine – 34 conventional and six organic ones – purchased inside the EU. According to the results, the 34 bottles of conventional wine together contained 148 pesticide residues. All 34 bottles contained from one to ten pesticides, bringing the average per bottle to more than four. Of the six bottles of organic wine tested, one sample contained a low concentration of a possibly carcinogenic pesticide. According to PAN Europe, the “contamination of wines is a direct result of over-reliance on pesticides in grape production”. This study, between others, to prove the importance of develop methods sensivity and confident for pesticide detection in wine. A multi-residue method was developed for the determination ca of 250 pesticide residues in wine using Quechers extraction, gas chromatography-tandem mass spectrometry (GC-MS-MS and liquid chromatography-tandem mass spectrometry (LC-MS-MS. The method was validated with the evaluation of follow parameters: Linearity, Precision, Accuracy, Matrix effect, Limit of detection and Limit of Quantification. The method was approved and was able to quantify pesticide residues in more than 60 samples of wine.

  15. Discovery of Highly Selective and Nanomolar Carbamate-Based Butyrylcholinesterase Inhibitors by Rational Investigation into Their Inhibition Mode.

    Sawatzky, Edgar; Wehle, Sarah; Kling, Beata; Wendrich, Jan; Bringmann, Gerhard; Sotriffer, Christoph A; Heilmann, Jörg; Decker, Michael

    2016-03-10

    Butyrylcholinesterase (BChE) is a promising target for the treatment of later stage cognitive decline in Alzheimer's disease. A set of pseudo-irreversible BChE inhibitors with high selectivity over hAChE was synthesized based on carbamates attached to tetrahydroquinazoline scaffolds with the 2-thiophenyl compound 2p as the most potent inhibitor of eqBChE (KC = 14.3 nM) and also of hBChE (KC = 19.7 nM). The inhibitors transfer the carbamate moiety onto the active site under release of the phenolic tetrahydroquinazoline scaffolds that themselves act as neuroprotectants. By combination of kinetic data with molecular docking studies, a plausible binding model was probed describing how the tetrahydroquinazoline scaffold guides the carbamate into a close position to the active site. The model explains the influence of the carrier scaffold onto the affinity of an inhibitor just before carbamate transfer. This strategy can be used to utilize the binding mode of other carbamate-based inhibitors.

  16. Human Health Benchmarks for Pesticides

    U.S. Environmental Protection Agency — Advanced testing methods now allow pesticides to be detected in water at very low levels. These small amounts of pesticides detected in drinking water or source...

  17. Shanghai Pesticide Research Institute (SPRI)

    2007-01-01

    @@ Shanghai Pesticide Research Institute (SPRI), established in 1963, is the first professional pesticide institute in China. After being approved by the Science & Technology Committee of PRC, it became the base for Shanghai Branch of National Pesticide R&D South center.

  18. Combating highly resistant emerging pathogen Mycobacterium abscessus and Mycobacterium tuberculosis with novel salicylanilide esters and carbamates.

    Baranyai, Zsuzsa; Krátký, Martin; Vinšová, Jarmila; Szabó, Nóra; Senoner, Zsuzsanna; Horváti, Kata; Stolaříková, Jiřina; Dávid, Sándor; Bősze, Szilvia

    2015-08-28

    In the Mycobacterium genus over one hundred species are already described and new ones are periodically reported. Species that form colonies in a week are classified as rapid growers, those requiring longer periods (up to three months) are the mostly pathogenic slow growers. More recently, new emerging species have been identified to lengthen the list, all rapid growers. Of these, Mycobacterium abscessus is also an intracellular pathogen and it is the most chemotherapy-resistant rapid-growing mycobacterium. In addition, the cases of multidrug-resistant Mycobacterium tuberculosis infection are also increasing. Therefore there is an urgent need to find new active molecules against these threatening strains. Based on previous results, a series of salicylanilides, salicylanilide 5-chloropyrazinoates and carbamates was designed, synthesized and characterised. The compounds were evaluated for their in vitro activity on M. abscessus, susceptible M. tuberculosis H37Rv, multidrug-resistant (MDR) M. tuberculosis MDR A8, M. tuberculosis MDR 9449/2006 and on the extremely-resistant Praha 131 (XDR) strains. All derivatives exhibited a significant activity with minimum inhibitory concentrations (MICs) in the low micromolar range. Eight salicylanilide carbamates and two salicylanilide esters exhibited an excellent in vitro activity on M. abscessus with MICs from 0.2 to 2.1 μM, thus being more effective than ciprofloxacin and gentamicin. This finding is potentially promising, particularly, as M. abscessus is a threateningly chemotherapy-resistant species. M. tuberculosis H37Rv was inhibited with MICs from 0.2 μM, and eleven compounds have lower MICs than isoniazid. Salicylanilide esters and carbamates were found that they were effective also on MDR and XDR M. tuberculosis strains with MICs ≥1.0 μM. The in vitro cytotoxicity (IC50) was also determined on human MonoMac-6 cells, and selectivity index (SI) of the compounds was established. In general, salicylanilide

  19. Synthesis and evaluation of benzimidazole carbamates bearing indole moieties for antiproliferative and antitubulin activities.

    Guan, Qi; Han, Chunming; Zuo, Daiying; Zhai, Min'an; Li, Zengqiang; Zhang, Qian; Zhai, Yanpeng; Jiang, Xuewei; Bao, Kai; Wu, Yingliang; Zhang, Weige

    2014-11-24

    A series of novel benzimidazole carbamates bearing indole moieties with sulphur or selenium atoms connecting the aromatic rings were synthesised and evaluated for their antiproliferative activities against three human cancer cell lines (SGC-7901, A-549 and HT-1080) using an MTT assay. Compounds 10a, 10b, 7a, 7b and 7f showed significant activities against these cell lines. The most potent compound in this series, 10a, was selected to investigate its antitumour mechanism. In addition, molecular docking studies suggested that compound 10a interacts very closely with the nocodazole docking pose through hydrogen bonds at the colchicine binding site of tubulin.

  20. 76 FR 34147 - Land Disposal Restrictions: Revision of the Treatment Standards for Carbamate Wastes

    2011-06-13

    ... production of carbamates and carbamoyl oximes. Acetophenone...... 98-86-2 0.010 9.7 Aniline 62-53-3 0.81 14...-3 0.059 5.6 Phenol 108-95-2 0.039 6.2 Pyridine 110-86-1 0.014 16 Toluene 108-88-3 0.080 10... CARBN Methylene chloride 75-09-2 0.089 30 Methylethyl ketone 78-93-3 0.28 36 Pyridine 110-86-1 0.014...

  1. Equilibrium constant for carbamate formation from monoethanolamine and its relationship with temperature

    Aroua, M.K.; Benamor, A.; Haji-Sulaiman, M.Z. [Univ. of Malaya, Kuala Lumpur (Malaysia). Dept. of Chemical Engineering

    1999-09-01

    Removal of acid gases such as CO{sub 2} and H{sub 2}S using aqueous solutions of alkanolamines is an industrially important process. The equilibrium constant for the formation of carbamate from monoethanolamine was evaluated at various temperatures of 298, 308, 318, and 328 K and ionic strengths up to 1.7 M. From the plot of log{sub 10} K versus I{sup 0.5}, the variation of the thermodynamical constant with temperature follows the relationship log{sub 10} K{sub 1} = {minus}0.934 + (0.671 {times} 10{sup 3})K/T.

  2. Exposure to pesticides and metal contaminants of fertilizer among tree planters.

    Gorman Ng, Melanie; Stjernberg, Ernst; Koehoorn, Mieke; Demers, Paul A; Davies, Hugh W

    2011-08-01

    In British Columbia, Canada, harvested forests are manually replanted by seasonal workers. The work is known to be physically demanding and ergonomically difficult, and recently, there have been concerns over chemical exposures due to pesticide residues on seedlings, fertilizers (often applied alongside seedlings), and potential metal contamination of these fertilizers. This study aimed to characterize metal and pesticide exposure among a sample of British Columbia tree planters. Between May 2006 and April 2007, exposure measurements were taken from 54 tree planters at five geographically disperse worksites throughout British Columbia. Four worksites were using fertilizer and one was not. Metal concentrations were measured by inductively coupled plasma mass spectrometry on post-shift hand wipes, full-shift personal air sample, bulk soil, seedling root balls, and fertilizer samples. Pesticides were measured on post-shift hand wipes and on bulk seedling samples. Seedling nursery pesticide application records were used to focus pesticide analyses on pesticides known to have been applied to the seedlings used at the study sites. Carbamate pesticides were analyzed by high-performance liquid chromatography/mass spectroscopy and all other pesticides by gas chromatography mass spectrometry. No evidence was found that tree planters who worked with fertilizer were at an elevated risk of exposure to arsenic, lead, cadmium, chromium, and nickel relative to tree planters who did not. Pesticide residues were found on seedlings taken from work sites early in the tree planting season in April 2007. At these worksites, the fungicides chlorothalonil and iprodione were found on the skin of workers at low levels (range 0.37-106.3 ng cm(-2) and 0.48-15.9 ng cm(-2), respectively), providing evidence for exposure potential. Very poor hygiene conditions were observed at all tree planting work sites. Hand washing facilities were not available at work sites and only 5.6% of subjects

  3. Statistical Analysis of Regularity of Pesticide Residues in Vegetables Produced in Inner Mongoli

    Fujin ZHANG; Dekun HOU; Jiang HE; Tianyun GAO; Hong LUO; Songyan LANG; Xinxin ZHANG; Yiping YAO

    2013-01-01

    [Objective] The paper was to study regularity of pesticide residues in veg-etables produced in Inner Mongolia. [Method] Mathematical statistic analysis was carried out on 6 800 samples of veggies, fruits, leguminous vegetables, nuts and seeds produced in Inner Mongolia. [Result] The dominated vegetables in Inner Mon-golia were green leafy vegetables, solanaceous vegetables and melon vegetables, and their yields accounted for 70% of the total vegetables production. Since 2003, with the rapid increase of detected vegetable numbers, the status of vegetable qual-ity safety had entered into a new stage of sustainable steady after a rapid decline or periodic fluctuation, and the differences in safety levels were obvious, of which the range of exceeding standard rate of pesticide residues in solanaceous vegeta-bles, melon vegetables and leguminous vegetables (about 55% of the total vegeta-bles) was under 2%, with average values of 1.1%, 1.6% and 3.1%, respectively. They belonged to stable type. The exceeding standard rate of pesticide residues in green leafy vegetables and Chinese cabbage group (about 30% of total vegetables) presented a decreasing trend year by year, wondering in the range of 7%-10%. They belonged to main risk type. The time period of exceeding standard of pesticide residues in root vegetables and cole vegetables was under predictable, and its ex-ceeding standard rate in some years was over 5% (amplitude variation is over 15 percentage points). They belonged to random risk type. The kinds of pesticides, which exceeding standard rate in vegetables were relatively intensive, presented vari-ance in different vegetable species. 70% of the pesticides belonged to intermittent over-limits and the probability was below 5%. About 20% tradition pesticides often exceeded standard and their probabilities were over 30%. The exceeding standard of organophosphorus and carbamates pesticides in vegetables presented a decreasing tend, while the risk of some new pesticides

  4. Bacterial Degradation of Pesticides

    Knudsen, Berith Elkær

    This PhD project was carried out as part of the Microbial Remediation of Contaminated Soil and Water Resources (MIRESOWA) project, funded by the Danish Council for Strategic Research (grant number 2104-08-0012). The environment is contaminated with various xenobiotic compounds e.g. pesticides......D student, to construct fungal-bacterial consortia in order to potentially stimulate pesticide degradation thereby increasing the chance of successful bioaugmentation. The results of the project are reported in three article manuscripts, included in this thesis. In manuscript I, the mineralization of 2...

  5. Control of pesticides 2003

    Krongaard, T.; Petersen, K. K.; Christoffersen, C.

    Four different groups of products covered by the pesticide regulation were included in the 2003 analytical chemical authority control: 1) Herbicides containing clodinafop- propargyl, clomazone, fluroxypyr and glyphosate. 2) Fungicides containing bitertanol, fuberidazole, fenhexamid and pencycuron...... containing methoprene complied with the accepted tolerance limits with respect to the content of the active ingredient as specified in Danish Statutory Order on pesticides. None of the 44 examined samples contained OPEO, but 5 of the samples contained NPEO. Three of these five samples were produced before...

  6. Temperature-dependent acute toxicity of methomyl pesticide on larvae of 3 Asian amphibian species.

    Lau, Edward Tak Chuen; Karraker, Nancy Elizabeth; Leung, Kenneth Mei Yee

    2015-10-01

    Relative to other animal taxa, ecotoxicological studies on amphibians are scarce, even though amphibians are experiencing global declines and pollution has been identified as an important threat. Agricultural lands provide important habitats for many amphibians, but often these lands are contaminated with pesticides. The authors determined the acute toxicity, in terms of 96-h median lethal concentrations, of the carbamate pesticide methomyl on larvae of 3 Asian amphibian species, the Asian common toad (Duttaphrynus melanostictus), the brown tree frog (Polypedates megacephalus), and the marbled pygmy frog (Microhyla pulchra), at 5 different temperatures (15 °C, 20 °C, 25 °C, 30 °C, and 35 °C) to examine the relationships between temperature and toxicity. Significant interspecific variation in methomyl sensitivity and 2 distinct patterns of temperature-dependent toxicity were found. Because high proportions of malformation among the surviving tadpoles were observed, a further test was carried out on the tree frog to determine effect concentrations using malformation as the endpoint. Concentrations as low as 1.4% of the corresponding 96-h median lethal concentrations at 25 °C were sufficient to cause malformation in 50% of the test population. As the toxicity of pesticides may be significantly amplified at higher temperatures, temperature effects should not be overlooked in ecotoxicological studies and derivation of safety limits in environmental risk assessment and management.

  7. Environmental impact of pesticides after sewage treatment plants removal in four Spanish Mediterranean rivers

    Campo, Julian; Masiá, Ana; Blasco, Cristina; Picó, Yolanda; Andreu, Vicente

    2013-04-01

    The re-use of sewage treatment plant (STP) effluents is currently one of the most employed strategies in several countries to deal with the water shortage problem. Some pesticides are bio-accumulative and due to their toxicity they can affect non-target organisms, especially in the aquatic ecosystems, threating their ecological status. Despite these facts, and to our knowledge, there are few peer-reviewed articles that report concentrations of pesticides in Spanish STPs. This work presents the results of an extensive survey that was carried out in October of 2010 in 15 of the STPs of Ebro, Guadalquivir, Jucar and Llobregat rivers in Spain. Forty-three currently used pesticides, belonging to anilide, neonicotinoid, thiocarbamate, acaricide, juvenile hormone mimic, insect growth regulator, urea, azole, carbamate, chloroacetanilide, triazine and organophosphorus, have been monitored. Integrated samples of influent and effluent, and dehydrated, lyophilized sludge from 15 STPs located along the rivers were analyzed for pesticide residues. With these data, removal efficiencies are also calculated. Extraction of water samples was performed through Solid Phase Extraction (SPE) and sludge samples were extracted using the QuEchERS method. Pesticide determination was carried out using Liquid Chromatograph - tandem Mass Spectrometry (LC-MS/MS). Recoveries ranged from 48% to 70%, in water samples, and from 40 to 105 %, in sludge samples. The limits of quantification were 0.01-5 ng L-1 for the former, and 0.1-5.0 ng g-1 for the latter. In terms of frequency of detection, 31 analytes were detected in influent, 29 in effluent and 11 in sludge samples. Organophosphorus pesticides were the most frequently detected in all wastewater samples, but azole, urea, triazine, neonicotinoid and the insect growth regulator were also commonly found. Imazalil revealed the maximum concentration in wastewater samples from all rivers except the Guadalquivir, in which diuron presented the maximum

  8. Knowledge, Attitudes, Practices and Biomonitoring of Farmers and Residents Exposed to Pesticides in Brazil

    Eloisa Dutra Caldas

    2012-08-01

    Full Text Available In this study, the knowledge, attitudes and practices regarding pesticide use and the levels of exposure of farmers and residents to organophosphorous and/or carbamates pesticides were evaluated in two rural settings in Brazil. A questionnaire was completed by 112 farm workers aged ≥18 years. Almost all farmers acknowledged that pesticides were potentially harmful to their health (87.5%; however, over half rarely (48.2% or never (7.2% used personal protective devices (PPDs. An association was found (p = 0.001 between the work regimen and the use of PPDs, with more frequent equipment use among hired laborers than those involved in family agriculture. A significant correlation (p = 0.027 was found between the reporting of adverse symptoms and the use of backpack sprayers. Mean AChE activities of farmers (n = 64 and residents (n = 18 during the exposure and non-exposure periods were significantly lower than their control groups. Mean BChE activities of farmers and residents were significantly lower than their controls during the exposure period. Among the 60 farmers that had blood samples collected in both the exposure and non-exposure (baseline periods, 10 (16.7% had AChE depletion of over 30% during the exposure period compared with the baseline level. Six residents living on the same farms also presented this depletion. AChE was over 30% higher than the baseline level for 19 farmers (31.7%, indicating a reboot effect. Special education programs are needed in these regions to promote the safe use of pesticides in the field to decrease the risks from exposure to pesticides for farmers, and from secondary exposure to these compounds for their families.

  9. Formation of Carbamate Anions by the Gas-phase Reaction of Anilide Ions with CO2.

    Liu, Chongming; Nishshanka, Upul; Attygalle, Athula B

    2016-05-01

    The anilide anion (m/z 92) generated directly from aniline, or indirectly as a fragmentation product of deprotonated acetanilide, captures CO2 readily to form the carbamate anion (m/z 136) in the collision cell, when CO2 is used as the collision gas in a tandem-quadrupole mass spectrometer. The gas-phase affinity of the anilide ion to CO2 is significantly higher than that of the phenoxide anion (m/z 93), which adds to CO2 only very sluggishly. Our results suggest that the efficacy of CO2 capture depends on the natural charge density on the nitrogen atom, and relative nucleophilicity of the anilide anion. Generally, conjugate bases generated from aniline derivatives with proton affinities (PA) less than 350 kcal/mol do not tend to add CO2 to form gaseous carbamate ions. For example, the anion generated from p-methoxyaniline (PA = 367 kcal/mol) reacts significantly faster than that obtained from p-nitroaniline (PA = 343 kcal/mol). Although deprotonated p-aminobenzoic acid adds very poorly because the negative charge is now located primarily on the carboxylate group, it reacts more efficiently with CO2 if the carboxyl group is esterified. Moreover, mixture of CO2 and He as the collision gas was found to afford more efficient adduct formation than CO2 alone, or as mixtures made with nitrogen or argon, because helium acts as an effective "cooling" gas and reduces the internal energy of reactant ions.

  10. Carbamate-linked cationic lipids with different hydrocarbon chains for gene delivery.

    Shi, Jia; Yu, Shijun; Zhu, Jie; Zhi, Defu; Zhao, Yinan; Cui, Shaohui; Zhang, Shubiao

    2016-05-01

    A series of carbamate-linked cationic lipids containing saturated or unsaturated hydrocarbon chains and quaternary ammonium head were designed and synthesized. After recrystallization, carbamate-linked cationic lipids with high purity (over 95%) were obtained. The structures of these lipids were proved by IR spectrum, HR-ESI-MS, HPLC, (1)H NMR and (13)C NMR. The liposomes were prepared by using these cationic lipids and neutral lipid DOPE. Particle size and zeta-potential were studied to show that they were suitable for gene transfection. The DNA-bonding ability of C12:0, C14:0 and C18:1 cationic liposomes was much better than others. The results of transfection showed that hydrophobic chains of these lipids have great effects on their transfection activity. The lipids bearing C12:0, C14:0 saturated chains or C18:1 unsaturated chain showed relatively higher transfection efficiency and lower cytotoxicity. So these cationic lipids could be used as non-viral gene carriers for further studies.

  11. Treatment of Toxocara canis infections in mice with liposome-incorporated benzimidazole carbamates and immunomodulator glucan.

    Hrckova, G; Velebný, S

    2001-06-01

    Benzimidazole carbamates (mebendazole, albendazole and fenbendazole) are the most commonly used anthelmintic drugs for the treatment of larval toxocariasis (Toxocara canis) in paratenic hosts. However, the bioavailability of these drugs for tissues is very low due to their extremely low solubility, resulting in the administration of relatively high doses over a long period. To overcome this problem, neutral, negatively or positively charged and stabilized liposome drug carriers were examined in the chronic phase of T. canis infections in mice each orally inoculated with 1000 eggs. Moreover, liposomized albendazole and fenbendazole were co-administered with liposomized immunomodulator glucan. The highest efficacy of both drugs, evaluated 4 weeks after treatment, was recorded after their subcutaneous administration (ten doses of 25 mg kg(-1)) in stabilized liposomes and intramuscular co-administration of liposomized glucan (two doses of 5 mg kg(-1)). Fenbendazole was more effective in muscles (91.5%) whereas albendazole was more effective in the brain (92.2%). Liposomes with incorporated benzimidazole carbamate anthelmintics provide sustained drug-release reservoirs and can considerably enhance drug efficacy. Moreover, despite suppression by T. canis antigens, stimulation of the immune system by the immunomodulator glucan potentiates the effects of these antiparasitic drugs.

  12. Blackberry subjected to in vitro gastrointestinal digestion affords protection against Ethyl Carbamate-induced cytotoxicity.

    Chen, Wei; Xu, Yang; Zhang, Lingxia; Su, Hongming; Zheng, Xiaodong

    2016-12-01

    Ethyl Carbamate (EC) was detected in many fermented foods. Previous studies indicated that frequent exposure to ethyl carbamate may increase the risk to suffer from cancers. Blackberry is rich in polyphenols and possesses potent antioxidant activity. This study aims to investigate the protective effect of blackberry homogenates produced before (BH) and after in vitro simulated gastrointestinal digestion (BD) on EC-induced toxicity in Caco-2 cells. Our results showed that blackberry homogenates after digestion (BD) was more effective than that before digestion (BH) in ameliorating EC-induced toxicity in Caco-2 cells. Further investigation revealed that BD remarkably attenuated EC-induced toxicity through restoring mitochondrial function, inhibiting glutathione depletion and decreasing overproduction of intracellular reactive oxygen species. Additionally, LC-MS result implied that the better protective capacity of BD may be related to the increased content of two anthocyanins (cyanidin-3-glucoside and cyanidin-3-dioxalyglucoside). Overall, the present study may give implication to prevent EC-induced health problem.

  13. Carbamate and Pyrethroid Resistance in the Akron Strain of Anopheles gambiae

    Mutunga, James M.; Anderson, Troy D.; Craft, Derek T.; Gross, Aaron D.; Swale, Daniel R.; Tong, Fan; Wong, Dawn M.; Carlier, Paul R.; Bloomquist, Jeffrey R.

    2015-01-01

    Insecticide resistance in the malaria vector, Anopheles gambiae is a serious problem, epitomized by the multi-resistant Akron strain, originally isolated in the country of Benin. Here we report resistance in this strain to pyrethroids and DDT (13-fold to 35-fold compared to the susceptible G3 strain), but surprisingly little resistance to etofenprox, a compound sometimes described as a “pseudo-pyrethroid.” There was also strong resistance to topically-applied commercial carbamates (45-fold to 81-fold), except for the oximes aldicarb and methomyl. Biochemical assays showed enhanced cytochrome P450 monooxygenase and carboxylesterase activity, but not that of glutathione-S-transferase. A series of substituted α,α,α,-trifluoroacetophenone oxime methylcarbamates were evaluated for enzyme inhibition potency and toxicity against G3 and Akron mosquitoes. The compound bearing an unsubstituted phenyl ring showed the greatest toxicity to mosquitoes of both strains. Low cross resistance in Akron was retained by all analogs in the series. Kinetic analysis of acetylcholinesterase activity and its inhibition by insecticides in the G3 strain showed inactivation rate constants greater than that of propoxur, and against Akron enzyme inactivation rate constants similar to that of aldicarb. However, inactivation rate constants against recombinant human AChE were essentially identical to that of the G3 strain. Thus, the acetophenone oxime carbamates described here, though potent insecticides that control resistant Akron mosquitoes, require further structural modification to attain acceptable selectivity and human safety. PMID:26047119

  14. Synthesis and fungicidal activity of aryl carbamic acid-5-aryl-2-furanmethyl ester.

    Li, Ying; Li, Bao-Ju; Ling, Yun; Miao, Hong-Jian; Shi, Yan-Xia; Yang, Xin-Ling

    2010-03-10

    Chitin, a major structural component of insect cuticle and fungus cell wall but absent in plants and vertebrates, is regarded as a safe and selective target for pest control agents. Chitin synthesis inhibitors (CSIs) have been well-known as insect growth regulators (IGRs) but rarely found as fungicides in agriculture. To find novel CSIs with good activity, benzoylphenylurea, a typical kind of CSIs, was chosen as the lead compound and 26 novel aryl carbamic acid-5-aryl-2-furanmethyl esters were designed by converting the urea linkages of benzoylphenylureas to carbamic acid esters and changing the aniline parts into furanmethyl groups. The title compounds were synthesized and their structures confirmed by IR, (1)H NMR, and elemental analysis. Preliminary insecticidal and fungicidal bioassays were carried out. The results indicated that the title compounds had no insecticidal effect on Culex pipiens pallens and Plutella xylostella Linnaeus , but most compounds exhibited good fungicidal activities against Corynespora cassiicola , Thanatephorus cucumeris , Botrytis cinerea , and Fusarium oxysporum . In particular, compounds V-4, V-6, V-7, and V-8 showed better activities against the four strains than those of the commercialized fungicides. The morphologic result suggested that compound V-21 had disturbed the cell wall formation of C. cassiicola. The results indicated that modification on the urea linkage of benzoylphenylurea was an effective way to discover new candidates for fungicides.

  15. Synthesis and Evaluation as Prodrugs of Hydrophilic Carbamate Ester Analogues of Resveratrol.

    Azzolini, Michele; Mattarei, Andrea; La Spina, Martina; Marotta, Ester; Zoratti, Mario; Paradisi, Cristina; Biasutto, Lucia

    2015-09-08

    Resveratrol (3,5,4'-trihydroxy-trans-stilbene) is an unfulfilled promise for health care: its exploitation is hindered by rapid conjugative metabolism in enterocytes and hepatocytes; low water solubility is a serious practical problem. To advantageously modify the physicochemical properties of the compound we have developed prodrugs in which all or part of the hydroxyl groups are linked via an N-monosubstituted carbamate ester bond to promoieties derived from glycerol or galactose, conferring higher water solubility. Kinetic studies of hydrolysis in aqueous solutions and in blood indicated that regeneration of resveratrol takes place in an appropriate time frame for delivery via oral administration. Despite their hydrophilicity some of the synthesized compounds were absorbed in the gastrointestinal tract of rats. In these cases the species found in blood after administration of a bolus consisted mainly of partially deprotected resveratrol derivatives and of the products of their glucuronidation, thus providing proof-of-principle evidence of behavior as prodrugs. The soluble compounds largely reached the lower intestinal tract. Upon administration of resveratrol, the major species found in this region was dihydroresveratrol, produced by enzymes of the intestinal flora. In experiments with a fully protected (trisubstituted) deoxygalactose containing prodrug, the major species were the prodrug itself and partially deprotected derivatives, along with small amounts of dihydroresveratrol. We conclude that the N-monosubstituted carbamate moiety is suitable for use in prodrugs of polyphenols.

  16. Pesticides water decontamination in oxygen-limited conditions.

    Suciu, Nicoleta Alina; Ferrari, Federico; Vasileiadis, Sotirios; Merli, Annalisa; Capri, Ettore; Trevisan, Marco

    2013-01-01

    This study was undertaken to develop a laboratory bioreactor, with a functioning principle similar with that of biobed systems but working in oxygen-limited conditions, suitable for decontaminating wastewater mixtures with pesticides. The system is composed by two cylindrical plastic containers. The first one, where the pesticides solution is collected, is open, whereas the second one, where the biomass is disposed, is closed. The pesticides solution was pumped at the biomass surface and subsequently recollected and disposed in the first container. Four pesticides with different physical-chemical characteristics were tested. The results obtained showed a relatively good capacity of the developed prototype to decontaminate waste water containing the mixture of pesticides. The time of the experiment, the number of cycles that the solution made in the system and the environmental temperature have a significantly influence for the decontamination of acetochlor and chlorpyrifos whereas for the decontamination of terbuthylazine and metalaxyl no significant influence was observed. Even if the present prototype could represent a valid solution to manage the water pesticides residues in a farm and to increase the confidence of bystanders and residents, the practical difficulties when replacing the biomass could represent a limit of the system.

  17. Synthesis and biological activity of beta-glucuronyl carbamate-based prodrugs of paclitaxel as potential candidates for ADEPT

    deBont, DBA; Leenders, RGG; Haisma, HJ; vanderMeulenMuileman, [No Value; Scheeren, HW

    1997-01-01

    The syntheses of prodrugs of paclitaxel, which can be used in ADEPT in order to target paclitaxel towards tumor cells, are described. The prodrugs 1 and 2a,b consist of a spacer molecule connected via a carbamate linkage to a beta-glucuronic acid. The spacer molecule is also connected via an ester l

  18. Lithium choreography: intramolecular arylations of carbamate-stabilised carbanions and their mechanisms probed by in situ IR spectroscopy and DFT calculations.

    Fournier, Anne M; Nichols, Christopher J; Vincent, Mark A; Hillier, Ian H; Clayden, Jonathan

    2012-12-14

    Deprotonation of O-allyl, O-propargyl or O-benzyl carbamates in the presence of a lithium counterion leads to carbamate-stabilised organolithium compounds that may be quenched with electrophiles. We now report that when the allylic, propargylic or benzylic carbamate bears an N-aryl substituent, an aryl migration takes place, leading to stereochemical inversion and C-arylation of the carbamate α to oxygen. The aryl migration is an intramolecular S(N) Ar reaction, despite the lack of anion-stabilising aryl substituents. Our in situ IR studies reveal a number of intermediates along the rearrangement pathway, including a "pre-lithiation complex," the deprotonated carbamate, the rearranged anion, and the final arylated carbamate. No evidence was obtained for a dearomatised intermediate during the aryl migration. DFT calculations predict that during the reaction the solvated Li cation moves from the carbanion centre, thus freeing its lone pair for nucleophilic attack on the remote phenyl ring. This charge separation leads to several alternative conformations. The one having Li(+) bound to the carbamate oxygen gives rise to the lowest-energy transition structure, and also leads to inversion of the configuration. In agreement with the IR studies, the DFT calculations fail to locate a dearomatised intermediate.

  19. Genotoxicity of Pesticide Waste Contaminated Soil and Its Leachate

    S. D. SIVANESAN; K. KRISHNAMURTHI; S. D. WACHASUNDER; T. CHAKRABARTI

    2004-01-01

    Improper land disposal of hazardous waste can result in leaching of hazardous constituents which may contaminate ground and surface water leading to adverse impact on human health and environment consequences. The present study utilized mammalian cell culture for the genotoxicity assessment of waste and its leachate. Methods Genotoxic potential and chemical analysis of pesticide derived tarry waste contaminated soil extract and its leachate was assessed using in vitro human lymphocyte cultures and GC-MS. Results The investigation revealed that the soil extract could cause significant to highly significant genotoxicity in the form of DNA strand break at 25 μL (P<0.01), 50 μL, 100 μL and 200 μL (P<0.001) and chromosomal aberration at 25 μL (P<0.01) and 50 μL and 100 μL (P<0.001). The leachate could cause significant DNA strand break and chromosomal aberration only at 100 μL and 200 μL (P<0.01) dose levels. Conclusion The genotoxicity observed is attributed to carbaril and tetra methyl naphthyl carbamate, the major ingredients of the extracts, as revealed by GC-MS.

  20. Radiation induced microbial pesticide

    Kim, Ki Yup; Lee, Young Keun; Kim, Jae Sung; Kim, Jin Kyu; Lee, Sang Jae

    2000-01-01

    To control plant pathogenic fungi, 4 strains of bacteria (K1, K3, K4, YS1) were isolated from mushroom compost and hot spring. K4, K1, K3, YS1 strain showed wide antifungal spectrum and high antifungal activities against 13 kinds of fungi. Mutants of K1 and YS1 strains were induced by gamma-ray radiation and showed promising antifungal activities. These wild type and mutants showed resistant against more than 27 kinds of commercial pesticides among 30 kinds of commercial pesticides test particularly, YS1-1006 mutant strain showed resistant against hydrogen oxide. And mutants had increased antifungal activity against Botryoshaeria dothidea. These results suggested that radiation could be an useful method for the induction of functional mutants. (author)

  1. 2011 EPA Pesticide General Permit (PGP)

    U.S. Environmental Protection Agency — The 2011 EPA Pesticide General Permit (PGP) covers discharges of biological pesticides, and chemical pesticides that leave a residue, in areas where EPA is the NPDES...

  2. Modelling pesticides residues

    2004-01-01

    This work is a contribution to the development of a specific method to assess the presence of residues in agricultural commodities. The following objectives are formulated: to identify and describe main processes in environment — plant exchanges, to build of a model to assess the residue concentration at harvest in agricultural commodities, to understand the functioning of the modelled system, to characterise pesticides used in field crops and identify optimisation potentials in phytosanitary...

  3. Bioeconomic Analysis of Pesticide Demand

    Moffitt, L. Joe; Farnsworth, Richard L.

    1981-01-01

    The ability of insects to develop resistance to specific pesticides affects pesticide demand. However, the affect of resistance on demand cannot be observed or measured. This analysis substitutes an expression for the unobserved resistance variable in a pesticide demand model and then illustrates the model's potential by estimating demand for DDT. To arrive at the expression characterizing the unobserved resistance variable a biological resistance model is constructed then incorporated into t...

  4. Pesticides residues in water treatment plant sludge: validation of analytical methodology using liquid chromatography coupled to Tandem mass spectrometry (LC-MS/MS); Residuos de agrotoxicos em lodo de estacao de tratamento de agua: validacao de metodologia analitica utilizando cromatografia liquida acoplada a espectrometria de massas em Tandem (LC-MS/MS)

    Moracci, Luiz Fernando Soares

    2008-07-01

    The evolving scenario of Brazilian agriculture brings benefits to the population and demands technological advances to this field. Constantly, new pesticides are introduced encouraging scientific studies with the aim of determine and evaluate impacts on the population and on environment. In this work, the evaluated sample was the sludge resulted from water treatment plant located in the Vale do Ribeira, Sao Paulo, Brazil. The technique used was the reversed phase liquid chromatography coupled to electrospray ionization tandem mass spectrometry. Compounds were previously liquid extracted from the matrix. The development of the methodology demanded data processing in order to be transformed into reliable information. The processes involved concepts of validation of chemical analysis. The evaluated parameters were selectivity, linearity, range, sensitivity, accuracy, precision, limit of detection, limit of quantification and robustness. The obtained qualitative and quantitative results were statistically treated and presented. The developed and validated methodology is simple. As results, even exploring the sensitivity of the analytical technique, the work compounds were not detected in the sludge of the WTP. One can explain that these compounds can be present in a very low concentration, can be degraded under the conditions of the water treatment process or are not completely retained by the WTP. (author)

  5. Development and validation of method for the determination of organochlorine pesticides and trihalomethanes in the water by HRGC-ECD = Desenvolvimento e validação de método para a determinação de pesticidas organoclorados e trihalometanos em água usando HRGC-ECD

    Maria Isabel Ribeiro Alves

    2010-10-01

    Full Text Available The development and validation of a simultaneous liquid-liquid extraction method for organochlorine pesticides and trihalomethanes in surface and drinking water by HRGC-ECD is described. The method presents acceptable recovery, with detection ranging from 2.7 to 49.0 ng L-1 for organochlorine pesticides and from 18.0 to 860.0 ng L-1for trihalomethanes. The extraction method also presents excellent linearity for all the analytes, with excellent repeatability. Extraction is simple, fast, and low cost, uses small amounts of solvent and aqueous sample, and is suitable for routine analyses.O presente trabalho trata do desenvolvimento e validação de um método de extração para a determinação simultânea de trihalometanos e pesticidas organoclorados em água superficial e água potável por HRGC-ECD. O método apresenta recuperação aceitável, com limites dedetecção que variam de 2,7 a 49,0 ng L-1 para pesticidas organoclorados e de 18,0 a 860,0 ng L-1 para trihalometanos. O método de extração apresenta também excelente linearidade para todos os analitos e boa repetibilidade. A extração é simples, rápida, de baixo custo, além de utilizar pequenas quantidades de solvente e de amostra aquosa, sendo, portanto, de alta aplicabilidade em análises de rotina.

  6. A general method for tritium labelling of benzimidazole carbamates by catalytic exchange in dioxane solutions

    Lacey, E. (Commonwealth Scientific and Industrial Research Organization, Glebe, NSW (Australia). Div. of Animal Health, McMaster Lab.); Dawson, M. (Sydney Univ. (Australia). Dept. of Pharmacy); Long, M.A.; Than, C. (New South Wales Univ., Kensington (Australia). School of Chemistry)

    1989-12-01

    Benzimidazole carbamates (BZCs) act as inhibitors of the tubulin-microtubule equilibria in eukaryotic organisms. Recently drug resistance to this class of compounds in helminth parasites has been shown to be due to a reduced ability of resistant tubulin to bind BZCs. In order to quantitate the nature of the tubulin-BZC interaction a general method for the specific tritium labelling of BZCs has been developed. The BZCs: mebendazole, oxfendazole, parbendazole, oxibendazole, albendazole and fenbendazole were labelled by catalytic exchange using palladium on calcium carbonate in pure dioxane at 60{sup 0}C under tritium gas. The position of label incorporation for tritiated albendazole was determined by tritium-NMR as the 4-position of benzimadazole nucleus. The yields for individual BZCs varied from 8 to 68% for a range of specific activity of 0.44 to 13.4 Ci/mmole. (author).

  7. Carbamate derivatives and sesquiterpenoids from the South China Sea gorgonian Melitodes squamata

    Li-Si Huang

    2012-01-01

    Full Text Available Five carbamate derivatives, obtucarbamates C and D (1, 2, dimethyl ((carbonylbis(azanediylbis(2-methyl-5,1-phenylenedicarbamate (3, obtucarbamates A and B (4, 5, and four aromadendrane-type sesquiterpenoids, (+-4β-N-methenetauryl-10β-methoxy-1β,5α,6β,7β-aromadendrane (6, (−-4β-N-methenetauryl-10β-methoxy-1β,5β,6α,7α-aromadendrane (7, (−-4α,10β-aromadendranediol (8, (+-4β,10β-aromadendranediol (9 were obtained from the South China Sea gorgonian coral Melitodes squamata Nutting. Compounds 1, 2, 6, and 7 were new, and their structures were established by spectroscopic analyses. Compounds 6 and 7 contained a taurine group that was rarely found in marine natural compounds, and 7 showed moderate antibacterial activity. The possible biosynthesis routes of 1–5 were conjectured.

  8. [Plasma cholesterol determination in birds--a diagnostic tool for detection of organophosphate and carbamate intoxication].

    Kiesau, B; Kummerfeld, N

    1998-07-01

    An investigation was done on the clinical usefulness of the dry chemistry analyzer Vitros DT 60 II for determination of avian plasma cholinesterase. The analytical reliability of the method, evaluated by precision and accuracy, proved to be high for plasma of numerous pet and wild birds. Values of normal plasma-cholinesterase activity were established for different psittacine and European wild birds. Significant differences in physiologic plasma-cholinesterase activity were noted between closely related species as well as between juvenile and adult birds. These findings emphasize the necessity to use control values of the same species and age group for comparison. Dry chemistry plasma-cholinesterase determination can be used as a diagnostic tool for detection of organophosphate and carbamate poisonings in the majority of investigated birds.

  9. Children poisoning by carbamate: a descriptive study - doi:10.5020/18061230.2004.p193

    Luiza Jane Eyre de Souza Vieira

    2012-01-01

    Full Text Available The study had as its aim to characterize the children under 5 years old, attended with exogenous poisoning by carbamate (popularly called “chumbinho” – “small shot” at an emergency hospital in Fortaleza and to relate the signs and symptoms detected in this type of poisoning. It concerned a descriptive study, with a sample of 65 children attended during the period of 1998 to 2000, in Fortaleza, Ceará. It was noticed that the most affected age group was of those with 1 to 3 years old, not being verified any significant difference between sexes. The most evident signs and symptoms were myosis, vomits, profuse perspiration and sialorrhea and the predominant treatment was the use of active coal. It is concluded, therefore, that there is a need of putting into effect the health education, calling the society’s attention to the risks of the inadequate “chumbinho” use in the domiciliar environment.

  10. Solubility improvement of an anthelmintic benzimidazole carbamate by association with dendrimers

    Fernandez, L.; Sigal, E.; Santo, M., E-mail: msanto@exa.unrc.edu.ar [Departamento de Fisica, Facultad de Ciencias Exactas Fisicoquimicas y Naturales, Universidad Nacional de Rio Cuarto (Argentina); Otero, L.; Silber, J. J. [Departamento de Quimica. Facultad de Ciencias Exactas Fisicoquimicas y Naturales, Universidad Nacional de Rio Cuarto, Rio Cuarto (Argentina)

    2011-10-15

    The improvement of aqueous solubility of methyl (5-[propylthio]-1H-benzimidazole-2-yl) carbamate, albendazole (ABZ) using polyamidoamine (PAMAM) dendrimers as solubility enhancers was investigated. Full generation PAMAM dendrimers with amine terminal groups, (G3), with hydroxyl terminal groups (G3OH) and half generation PAMAM dendrimers with carboxylate terminal groups (G2.5 and G3.5), were chosen for this study. The nature of dendrimer-ABZ association was investigated by UV absorption, fluorescence emission measurements and by {sup 1}H-NMR spectroscopy. The results obtained show that these polymeric structures have the capacity to enhance the solubility of ABZ, both lipophilic and specific hydrogen bond interactions contributing to the guest-host association. Although all studied dendrimers have hydrophobic internal nanoenvironments with similar dimensions, their surfaces differ significantly and the nature and the localization of the interactions involved in ABZ-dendrimer association depend on the type of terminal groups. (author)

  11. Anticonvulsant properties of histamine H3 receptor ligands belonging to N-substituted carbamates of imidazopropanol.

    Sadek, Bassem; Shehab, Safa; Więcek, Małgorzata; Subramanian, Dhanasekaran; Shafiullah, Mohamed; Kieć-Kononowicz, Katarzyna; Adem, Abdu

    2013-09-01

    Ligands targeting central histamine H3 receptors (H3Rs) for epilepsy might be a promising therapeutic approach. Therefore, the previously described and structurally strongly related imidazole-based derivatives belonging to carbamate class with high H3R in vitro affinity, in-vivo antagonist potency, and H3R selectivity profile were investigated on their anticonvulsant activity in maximal electroshock (MES)-induced and pentylenetetrazole (PTZ)-kindled seizure models in Wistar rats. The effects of systemic injection of H3R ligands 1-13 on MES-induced and PTZ-kindled seizures were screened and evaluated against the reference antiepileptic drug (AED) Phenytoin (PHT) and the standard histamine H3R inverse agonist/antagonist Thioperamide (THP) to determine their potential as new antiepileptic drugs. Following administration of the H3R ligands 1-13 (5, 10 and 15 mg/kg, ip) there was a significant dose dependent reduction in MES-induced seizure duration. The protective action observed for the pentenyl carbamate derivative 4, the most protective H3R ligand among 1-13, was significantly higher (P histamine (RAMH) (10mg/kg), or with the CNS penetrant H1R antagonist Pyrilamine (PYR) (10mg/kg). In addition, subeffective dose of H3R ligand 4 (5mg/kg, ip) significantly potentiated the protective action in rats pretreated with PHT (5mg/kg, ip), a dose without appreciable protective effect when given alone. In contrast, pretreatment with H3R ligand 4 (10mg/kg ip) failed to modify PTZ-kindled convulsion, whereas the reference drug PHT was found to fully protect PTZ-induced seizure. These results indicate that some of the investigated imidazole-based H3R ligands 1-13 may be of future therapeutic value in epilepsy.

  12. Novel Cholinesterase Inhibitors Based on O-Aromatic N,N-Disubstituted Carbamates and Thiocarbamates

    Martin Krátký

    2016-02-01

    Full Text Available Based on the presence of carbamoyl moiety, twenty salicylanilide N,N-disubstituted (thiocarbamates were investigated using Ellman’s method for their ability to inhibit acetylcholinesterase (AChE and butyrylcholinesterase (BChE. O-Aromatic (thiocarbamates exhibited weak to moderate inhibition of both cholinesterases with IC50 values within the range of 1.60 to 311.0 µM. IC50 values for BChE were mostly lower than those obtained for AChE; four derivatives showed distinct selectivity for BChE. All of the (thiocarbamates produced a stronger inhibition of AChE than rivastigmine, and five of them inhibited BChE more effectively than both established drugs rivastigmine and galantamine. In general, 5-chloro-2-hydroxy-N-[4-(trifluoromethyl-phenyl]benzamide, 2-hydroxy-N-phenylbenzamide as well as N-methyl-N-phenyl carbamate derivatives led to the more potent inhibition. O-{4-Chloro-2-[(4-chlorophenylcarbamoyl]phenyl} dimethylcarbamothioate was identified as the most effective AChE inhibitor (IC50 = 38.98 µM, while 2-(phenylcarbamoylphenyl diphenylcarbamate produced the lowest IC50 value for BChE (1.60 µM. Results from molecular docking studies suggest that carbamate compounds, especially N,N-diphenyl substituted representatives with considerable portion of aromatic moieties may work as non-covalent inhibitors displaying many interactions at peripheral anionic sites of both enzymes. Mild cytotoxicity for HepG2 cells and consequent satisfactory calculated selectivity indexes qualify several derivatives for further optimization.

  13. Kinetic characterization of arginine deiminase and carbamate kinase from Streptococcus pyogenes M49.

    Hering, Silvio; Sieg, Antje; Kreikemeyer, Bernd; Fiedler, Tomas

    2013-09-01

    Streptococcus pyogenes (group A Streptococcus, GAS) is an important human pathogen causing mild superficial infections of skin and mucous membranes, but also life-threatening systemic diseases. S. pyogenes and other prokaryotic organisms use the arginine deiminase system (ADS) for survival in acidic environments. In this study, the arginine deiminase (AD), and carbamate kinase (CK) from S. pyogenes M49 strain 591 were heterologously expressed in Escherichia coli DH5α, purified, and kinetically characterized. AD and CK from S. pyogenes M49 share high amino acid sequence similarity with the respective enzymes from Lactococcus lactis subsp. lactis IL1403 (45.6% and 53.5% identical amino acids) and Enterococcus faecalis V583 (66.8% and 66.8% identical amino acids). We found that the arginine deiminase of S. pyogenes is not allosterically regulated by the intermediates and products of the arginine degradation (e.g., ATP, citrulline, carbamoyl phosphate). The Km and Vmax values for arginine were 1.13±0.12mM (mean±SD) and 1.51±0.07μmol/min/mg protein. The carbamate kinase is inhibited by ATP but unaffected by arginine and citrulline. The Km and Vmax values for ADP were 0.72±0.08mM and 1.10±0.10μmol/min/mg protein and the Km for carbamoyl phosphate was 0.65±0.07mM. The optimum pH and temperature for both enzymes were 6.5 and 37°C, respectively.

  14. Structural Basis for Inactivation of Giardia lamblia Carbamate Kinase by Disulfiram*

    Galkin, Andrey; Kulakova, Liudmila; Lim, Kap; Chen, Catherine Z.; Zheng, Wei; Turko, Illarion V.; Herzberg, Osnat

    2014-01-01

    Carbamate kinase from Giardia lamblia is an essential enzyme for the survival of the organism. The enzyme catalyzes the final step in the arginine dihydrolase pathway converting ADP and carbamoyl phosphate to ATP and carbamate. We previously reported that disulfiram, a drug used to treat chronic alcoholism, inhibits G. lamblia CK and kills G. lamblia trophozoites in vitro at submicromolar IC50 values. Here, we examine the structural basis for G. lamblia CK inhibition of disulfiram and its analog, thiram, their activities against both metronidazole-susceptible and metronidazole-resistant G. lamblia isolates, and their efficacy in a mouse model of giardiasis. The crystal structure of G. lamblia CK soaked with disulfiram revealed that the compound thiocarbamoylated Cys-242, a residue located at the edge of the active site. The modified Cys-242 prevents a conformational transition of a loop adjacent to the ADP/ATP binding site, which is required for the stacking of Tyr-245 side chain against the adenine moiety, an interaction seen in the structure of G. lamblia CK in complex with AMP-PNP. Mass spectrometry coupled with trypsin digestion confirmed the selective covalent thiocarbamoylation of Cys-242 in solution. The Giardia viability studies in the metronidazole-resistant strain and the G. lamblia CK irreversible inactivation mechanism show that the thiuram compounds can circumvent the resistance mechanism that renders metronidazole ineffectiveness in drug resistance cases of giardiasis. Together, the studies suggest that G. lamblia CK is an attractive drug target for development of novel antigiardial therapies and that disulfiram, an FDA-approved drug, is a promising candidate for drug repurposing. PMID:24558036

  15. Structural basis for inactivation of Giardia lamblia carbamate kinase by disulfiram.

    Galkin, Andrey; Kulakova, Liudmila; Lim, Kap; Chen, Catherine Z; Zheng, Wei; Turko, Illarion V; Herzberg, Osnat

    2014-04-11

    Carbamate kinase from Giardia lamblia is an essential enzyme for the survival of the organism. The enzyme catalyzes the final step in the arginine dihydrolase pathway converting ADP and carbamoyl phosphate to ATP and carbamate. We previously reported that disulfiram, a drug used to treat chronic alcoholism, inhibits G. lamblia CK and kills G. lamblia trophozoites in vitro at submicromolar IC50 values. Here, we examine the structural basis for G. lamblia CK inhibition of disulfiram and its analog, thiram, their activities against both metronidazole-susceptible and metronidazole-resistant G. lamblia isolates, and their efficacy in a mouse model of giardiasis. The crystal structure of G. lamblia CK soaked with disulfiram revealed that the compound thiocarbamoylated Cys-242, a residue located at the edge of the active site. The modified Cys-242 prevents a conformational transition of a loop adjacent to the ADP/ATP binding site, which is required for the stacking of Tyr-245 side chain against the adenine moiety, an interaction seen in the structure of G. lamblia CK in complex with AMP-PNP. Mass spectrometry coupled with trypsin digestion confirmed the selective covalent thiocarbamoylation of Cys-242 in solution. The Giardia viability studies in the metronidazole-resistant strain and the G. lamblia CK irreversible inactivation mechanism show that the thiuram compounds can circumvent the resistance mechanism that renders metronidazole ineffectiveness in drug resistance cases of giardiasis. Together, the studies suggest that G. lamblia CK is an attractive drug target for development of novel antigiardial therapies and that disulfiram, an FDA-approved drug, is a promising candidate for drug repurposing.

  16. Intoxicación por plaguicidas Pesticide poisoning

    A. Ferrer

    2003-01-01

    or by their chemical family (organochlorates, organophosphates, carbamates, pyrethroids, Bipyridilium compounds, inorganic salts…. All of them are biocides, which normally implies a high toxicity for humans, which has been a cause for concern since the mid-XX century due to the widespread and indiscriminate use of these products. Exposure to pesticides can have effects that are acute, chronic and long-term. Some organochlorate compounds (such as DDT were the first to be used in massive fumigations to fight malaria and have had to be banned because of their capacity for bioaccumulation and environmental persistence. The danger represented by the widespread presence of these agents has been demonstrated in numerous episodes of human toxic epidemics, producers of a high morbidity/mortality, described for nearly all chemical families: organochlorate insecticides and fungicides, organophosphate and carbamate insecticides, organomercurial fungicides and inorganic salts. These episodes have above all been caused through the ingestion of foodstuffs and in the occupational field. Other causes of health concern are their carcinogenic capacity and occasional reproductive alterations. The principal characteristics of some of the most relevant families are presented.

  17. Prediction of Multi-Target Networks of Neuroprotective Compounds with Entropy Indices and Synthesis, Assay, and Theoretical Study of New Asymmetric 1,2-Rasagiline Carbamates

    Francisco J. Romero Durán

    2014-09-01

    Full Text Available In a multi-target complex network, the links (Lij represent the interactions between the drug (di and the target (tj, characterized by different experimental measures (Ki, Km, IC50, etc. obtained in pharmacological assays under diverse boundary conditions (cj. In this work, we handle Shannon entropy measures for developing a model encompassing a multi-target network of neuroprotective/neurotoxic compounds reported in the CHEMBL database. The model predicts correctly >8300 experimental outcomes with Accuracy, Specificity, and Sensitivity above 80%–90% on training and external validation series. Indeed, the model can calculate different outcomes for >30 experimental measures in >400 different experimental protocolsin relation with >150 molecular and cellular targets on 11 different organisms (including human. Hereafter, we reported by the first time the synthesis, characterization, and experimental assays of a new series of chiral 1,2-rasagiline carbamate derivatives not reported in previous works. The experimental tests included: (1 assay in absence of neurotoxic agents; (2 in the presence of glutamate; and (3 in the presence of H2O2. Lastly, we used the new Assessing Links with Moving Averages (ALMA-entropy model to predict possible outcomes for the new compounds in a high number of pharmacological tests not carried out experimentally.

  18. PPA-SiO2 Catalyzed Multi-component Synthesis of N-[α-(β-Hydroxy-α-naphthyl)(benzyl)]O-Alkyl Carbamate Derivatives

    SHATERIAN,Hamid Reza; HOSSEINIAN,Asghar; GHASHANG,Majid

    2009-01-01

    Silica-supported polyphosphoric acid (PPA-SiO2) was found to be an efficient catalyst for the multi-component condensation reaction of benzaldehydes,2-naphthol,and methyl/benzyl carbamate to afford the corresponding N-[α-(β-hydroxy-α-naphthyl)(benzyl)]O-alkyl carbamate derivatives in good to excellent yields.This new approach consistently has the advantage of short reaction time,high conversions,clean reaction profiles,and simple experimental and work-up procedures.

  19. Organofosforados e carbamatos no leite produzido em quatro regiões leiteiras no Brasil: ocorrência e ação sobre Listeria monocytogenes e Salmonella spp. Organophosphates and carbamates in milk produced in four milk producing regions from Brazil: occurrence and activity against Listeria monocytogenes and Salmonella spp.

    Luís Augusto Nero

    2007-03-01

    Full Text Available Organofosforados e carbamatos são compostos utilizados no controle de parasitas em animais e podem gerar resíduos nos produtos alimentícios derivados, representando um risco para o consumidor. O presente estudo objetivou pesquisar a presença de resíduos de organofosforados e carbamatos em leite cru produzido em quatro regiões leiteiras no Brasil e verificar se a presença desses compostos teria alguma relação com a ausência de Listeria monocytogenes e Salmonella spp., anteriormente observada nessas amostras. Entre 209 amostras analisadas, a presença de ao menos um desses compostos foi detectada em 196 (93,8%. Para a avaliação da sua interferência na detecção de L. monocytogenes e Salmonella spp., 28 amostras de leite positivas e negativas para esses compostos foram submetidas à fervura por 10 minutos e adicionadas desses patógenos, monitorando-se sua multiplicação durante armazenamento a 4 °C e a 25 °C. Não houve diferença significativa (p Chemical residues may be present in foods due to contamination in early stages of production, posing a potential risk to consumers. Organophosphates and carbamates are used in the control of parasites in animals and may generate residues in foods derived from these animals, like milk. This study aimed to survey the presence of these two pesticides in raw milk samples collected in four important milk-producing regions in Brazil and observe any possible relationship between presence of these compounds and the previously reported absence of Listeria monocytogenes e Salmonella spp. in the same milk samples. Organophosphates and/or carbamates were detected in 196 (93.8% out of 209 samples. For evaluation of the interference of these products on detection of L. monocytogenes and Salmonella spp., 28 milk samples containing these pesticides were boiled for 10 minutes, added of the pathogens, and their multiplication was monitored during storage at 4 °C and 25 °C. No significant differences (p

  20. Effets perturbateurs endocriniens des pesticides organochlores.

    Charlier, C; Plomteux, G

    2002-01-01

    Xenoestrogens such organochlorine pesticides are known to induce changes in reproductive development, function or behaviour in wildlife. Because these compounds are able to modify the estrogens metabolism, or to compete with estradiol for binding to the estrogen receptor, it may be possible that these products affect the risk of developing impaired fertility, precocious puberty or some kinds of cancer in man. Le plus ancien récit de lutte contre la pollution remonte à une légende indienne racontant que la divinité Sing-bonga était incommodée par les émanations des fours dans lesquels les Asuras fondaient leurs métaux (1). Evidemment depuis, la problématique n-a cessé de s-accroître et la contamination de la Terre par de nombreux polluants est devenue aujourd-hui un problème majeur de notre Société. La protection de notre environnement est une question capitale qui doit être respectée malgré la pression économique actuelle et qui ne cessera de croître au cours des prochaines années même si l-identification objective et indiscutable de ce qui est essentiel - donc devant être prioritairement garanti sur la planète - est difficile à cerner (2). « Un oiseau en mauvais état ne pond pas de bons oeufs » disait un proverbe grec. Mais ce n-est qu-à partir de la seconde moitié du XXème siècle que les toxicologues ont commencé à identifier les effets qu-avaient entraînés à l-échelle mondiale les pollutions émises aux XIXème siècle sur la faune sauvage et sur le cheptel (3). L-histoire contemporaine des pesticides industriels commence vers 1874 (synthèse des organochlorés) et se poursuit tout au long de ces 2 siècles en passant par la synthèse des organophosphorés (1950), des carbamates (1970) et des pyréthroïdes (1975) (4). Le dichlorodiphényltrichloroéthane (DDT) a été synthétisé pour la première fois par un étudiant en cours de préparation de sa thèse de doctorat : Othmer Zeidler. La production, reprise par les

  1. Pesticide residues in Portuguese strawberries grown in 2009-2010 using integrated pest management and organic farming.

    Fernandes, Virgínia C; Domingues, Valentina F; Mateus, Nuno; Delerue-Matos, Cristina

    2012-11-01

    Pesticides are among the most widely used chemicals in the world. Because of the widespread use of agricultural chemicals in food production, people are exposed to low levels of pesticide residues through their diets. Scientists do not yet have a total understanding of the health effects of these pesticide residues. This work aims to determine differences in terms of pesticide residue content in Portuguese strawberries grown using different agriculture practices. The Quick, Easy, Cheap, Effective, Rugged, and Safe sample preparation method was conducted and shown to have good performance for multiclass pesticides extraction in strawberries. The screening of 25 pesticides residue was performed by gas chromatography-tandem mass spectrometry. In quantitative validation, acceptable performances were achieved with recoveries of 70-120 and integrated pest management (IPM) practices harvested in 2009-2010. The results showed the presence of fludioxonil, bifenthrin, mepanipyrim, tolylfluanid, cyprodinil, tetraconazole, and malathion when using IPM below the maximum residue levels.

  2. Novel Preparation of Methoxy Carbamates of 1-Protected Indole- 3-methylamines as Precursor of Indole-3-methylamine

    SONG,Hao; XIN,Jun-Guo; WANG,Yin; CHEN,Wei; YANG,Jun; QIN,Yong

    2004-01-01

    @@ Indole-3-methylamine (1) has been well demonstrated to be a very useful intermediate as a pharmaceutical building block and starting material for syntheses of phytoalexins.[1] The instability of indole-3-methylamine (1) has undoubtedly restricted its application in synthetic chemistry. Hofmann rearrangement that directly converts carboxamides to alky carbamates in the presence of alcohol required unexceptionally a strong base,[2] which devaluated the possible usefulness of Hofmann rearrangement in preparation of base sensitive amines, especially for the preparation of unstable indole-3-methylamine (1). Herein we would like to report a convenient method for the preparation of alkyl carbamates of 1-protected indole-3-methylamines (4) via the diacetoxyiodobenzene (DIB) promoted Hofmann rearrangement under neutral condition.

  3. Efficient hydrogenation of organic carbonates, carbamates and formates indicates alternative routes to methanol based on CO2 and CO.

    Balaraman, Ekambaram; Gunanathan, Chidambaram; Zhang, Jing; Shimon, Linda J W; Milstein, David

    2011-07-22

    Catalytic hydrogenation of organic carbonates, carbamates and formates is of significant interest both conceptually and practically, because these compounds can be produced from CO2 and CO, and their mild hydrogenation can provide alternative, mild approaches to the indirect hydrogenation of CO2 and CO to methanol, an important fuel and synthetic building block. Here, we report for the first time catalytic hydrogenation of organic carbonates to alcohols, and carbamates to alcohols and amines. Unprecedented homogeneously catalysed hydrogenation of organic formates to methanol has also been accomplished. The reactions are efficiently catalysed by dearomatized PNN Ru(II) pincer complexes derived from pyridine- and bipyridine-based tridentate ligands. These atom-economical reactions proceed under neutral, homogeneous conditions, at mild temperatures and under mild hydrogen pressures, and can operate in the absence of solvent with no generation of waste, representing the ultimate 'green' reactions. A possible mechanism involves metal-ligand cooperation by aromatization-dearomatization of the heteroaromatic pincer core.

  4. [A case of carbamate poisoning in which GCMS was useful to identify causal substance and to decide the appropriate treatment].

    Kinoshita, H; Hirose, Y; Tanaka, T; Hori, Y; Nakajima, M; Fujisawa, M; Oseki, M

    2001-10-01

    We often have cases of insecticide poisoning where the patient is unconscious and the causal substances are unknown. We report an 83-year-old unconscious man who had apparently ingested several agricultural chemicals, possibly organophosphate or carbamate. According to his family, there were three kinds of containers of agricultural chemicals with their caps opened around him. When he was transferred to our hospital, he presented hypertension, hypersalivation, and muscle fasciculation. His pupils were markedly miotic. In order to identify the substances ingested we used a gas chromatographymass spectrometer (GCMS) using his gastric content. Within 30 minutes we were able to identify the causal substance as methomyl, one of the popular carbamates, thereby eliminating the need to use pralidoxime (PAM). GCMS makes it possible to identify unknown substances quickly and accurately and is therefore extremely useful in deciding the appropriate treatment.

  5. Solid-phase extraction of flavonoids in honey samples using carbamate-embedded triacontyl-modified silica sorbent.

    Liu, Houmei; Zhang, Mingliang; Guo, Yong; Qiu, Hongdeng

    2016-08-01

    In this study, carbamate-embedded triacontyl-modified silica (Sil-CBM-C30) is successfully prepared and used as an efficient sorbent for solid-phase extraction. The extraction performance of the resultant sorbent is evaluated with five flavonoids including myricetin, quercetin, luteolin, kaempferol and isorhamnetin. Main parameters, which affect extraction efficiencies, are carefully investigated and optimized. Comparative experiments between Sil-CBM-C30 and commercial C18 sorbents indicate that the extraction efficiencies of the former one surpass the latter one. The modification of carbamate-embedded triacontyl group on surface of silica causes analytes extracted by hydrophobic, hydrogen bonding and π-π interactions. Under optimal conditions, good linearities and satisfied LODs and LOQs are achieved. The SPE-HPLC-DAD method is successfully developed and applied for the honey sample analysis.

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

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

    2016-01-11

    A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed for determination of 229 pesticides compounds (113 pesticides and 116 pesticide degradates) in filtered water samples from stream and groundwater sites. The pesticides represent a broad range of chemical classes and were selected based on criteria such as current-use intensity, probability of occurrence in streams and groundwater, and toxicity to humans or aquatic organisms. More than half of the analytes are pesticide degradates. The method involves direct injection of a 100-microliter (μL) sample onto the LC-MS/MS without any sample preparation other than filtration. Samples are analyzed with two injections, one in electrospray ionization (ESI) positive mode and one in ESI negative mode, using dynamic multiple reaction monitoring (MRM) conditions, with two MRM transitions for each analyte. The LC-MS/MS instrument parameters were optimized for highest sensitivity for the most analytes. This report describes the analytical method and presents characteristics of the method validation including bias and variability, detection levels, and holding-time studies.

  7. Fact Sheets on Pesticides in Schools.

    National Coalition against the Misuse of Pesticides, Washington, DC.

    This document consists of a collection of fact sheets about the use of pesticides in schools and how to reduce it. The sheets are: (1) "Alternatives to Using Pesticides in Schools: What Is Integrated Pest Management?"; (2) "Health Effects of 48 Commonly Used Pesticides in Schools"; (3) "The Schooling of State Pesticide Laws--2002 Update: A Review…

  8. PESTICIDE APPLICATION TECHNICS IMPROVEMENT

    Đuro Banaj

    2011-06-01

    Full Text Available The academic textbook Pesticide application tehnics improvement is the result of several-year recording theoretical models, numerous practical tests, and data collection relating to technical systems in plant protection and its environment in the narrowest sense. In this first edition, the authors cover the area they have dealt with for many years. The authors aimed to present complete and clear methods how to solve specific problems in the agricultural practice management, plant protection, and direct practice application – ‘‘Know- How'', with as many as possible useful data. References used, along with local ones, are mostly American and from Western Europe. This textbook is intended for those who already use the agricultural technique in plant protection and those who are just acquiring the basics of technical systems proper application in daily practice, regardless the size of the agricultural farm. The authors covered in details and explained some bases of physics logic, analysis, and synthesis of specific laws while using pesticides due to extremely importance in understanding the problem area.

  9. Cholinesterase activities and sensitivity to pesticides in different tissues of silver European eel, Anguilla anguilla.

    Valbonesi, P; Brunelli, F; Mattioli, M; Rossi, T; Fabbri, E

    2011-11-01

    Cholinesterase (ChE) activities were characterized in silver European eel, Anguilla anguilla, grown in the brackish lagoon of Comacchio (Italy). All specimens were harvested at the "lavoriero", a traditional eel trapping weir that captures eels while leaving internal waters at the onset of reproductive migration. To our knowledge, no investigation on ChE was reported in silver eels. Therefore a first characterization of enzyme activity in muscle, brain, liver and plasma of silver eel was carried out, in the presence of different substrates, selective inhibitors, and four pesticides representative of the carbamate and organophosphate classes. Brain and white skeletal muscle showed similar ChE activities, 5- and 10-fold higher than those detected in liver and plasma, respectively. Km values of 0.31 and 0.30 mM, and Vmax values of 40.28 and 35.47 nmol min(-1) mg protein(-1) were obtained in brain and muscle ChE, respectively. Acetycholinesterase was the predominant ChE form in all tissues, as concluded by comparing the effects of BW 284c51, iso-OMPA and eserine. ChE activities in brain and muscle were significantly inhibited by in vitro treatment with pesticides, with the following order of potency: carbofuran>carbaryl>chlorpyrifos≥diazinon.

  10. A bi-enzymatic whole cell conductometric biosensor for heavy metal ions and pesticides detection in water samples.

    Chouteau, Celine; Dzyadevych, Sergei; Durrieu, Claude; Chovelon, Jean-Marc

    2005-08-15

    A conductometric biosensor using immobilised Chlorella vulgaris microalgae as bioreceptors was used as a bi-enzymatic biosensor. Algae were immobilised inside bovine serum albumin membranes reticulated with glutaraldehyde vapours deposited on interdigitated conductometric electrodes. Local conductivity variations caused by algae alkaline phosphatase and acetylcholinesterase activities could be detected. These two enzymes are known to be inhibited by distinct families of toxic compounds: heavy metals for alkaline phosphatase, carbamates and organophosphorous (OP) pesticides for acetylcholinesterase. The bi-enzymatic biosensors were tested to study the influence of heavy metal ions and pesticides on the corresponding enzyme. It has finally appeared that these biosensors are quite sensitive to Cd2+ and Zn2+ (limits of detection (LOD) = 10 ppb for a 30 min long exposure) while Pb2+ gives no significant inhibition as this ion seems to adsorb on albumin preferably. For pesticides, first experiments showed that paraoxon-methyl inhibits C. vulgaris AChE contrary to parathion-methyl and carbofuran. Biosensors were then exposed to different mixtures (Cd2+/Zn2+, Cd2+/paraoxon-methyl) but no synergetic or antagonist effect could be observed. A good repeatability could be achieve with biosensors since the relative standard deviation did not exceed 8% while response time was 5-7 min. A comparison between inhibition levels obtained with biosensors (after a 30 min long exposure) and bioassays (after a 240 min long exposure) has finally shown a similar LOD for both Cd and Zn (LOD = 10 ppb).

  11. Novel chiral stationary phases based on peptoid combining a quinine/quinidine moiety through a C9-position carbamate group.

    Wu, Haibo; Wang, Dongqiang; Song, Guangjun; Ke, Yanxiong; Liang, Xinmiao

    2014-04-01

    By connecting a quinine or quinidine moiety to the peptoid chain through the C9-position carbamate group, we synthesized two new chiral selectors. After immobilizing them onto 3-mercaptopropyl-modified silica gel, two novel chiral stationary phases were prepared. With neutral, acid, and basic chiral compounds as analytes, we evaluated these two stationary phases and compared their chromatographic performance with chiral columns based on quinine tert-butyl carbamate and the previous peptoid. From the resolution of neutral and basic analytes under normal-phase mode, it was found that the new stationary phases exhibited much better enantioselectivity than the quinine tert-butyl carbamate column; the peptoid moiety played an important role in enantiorecognition, which controlled the elution orders of enantiomers; the assisting role of the cinchona alkaloid moieties was observed in some separations. Under acid polar organic phase mode, it was proved that cinchona alkaloid moieties introduced excellent enantiorecognitions for chiral acid compounds; in some separations, the peptoid moiety affected enantioseparations as well. Overall, chiral moieties with specific enantioselectivity were demonstrated to improve the performance of peptoid chiral stationary phase efficiently.

  12. Trabalho rural e fatores de risco associados ao regime de uso de agrotóxicos em Minas Gerais, Brasil Rural work and risk factors associated with pesticide use in Minas Gerais, Brazil

    Wagner Soares

    2003-08-01

    Full Text Available O objetivo deste artigo foi caracterizar o processo do trabalho rural em nove municípios de Minas Gerais, considerando indicadores sócio-demográficos, a estrutura agrária dos estabelecimentos rurais, práticas de trabalho relacionadas ao uso de agrotóxicos e, a intoxicação associada a seu uso. Os dados foram obtidos de uma pesquisa realizada pela Fundação Jorge Duprat Figueiredo, de Segurança e Medicina do Trabalho, que aplicou um questionário a 1.064 trabalhadores rurais, entre os anos de 1991 a 2000. Por meio de uma regressão logística, foram obtidos os fatores de risco associados à intoxicação por agrotóxicos dos grupos organofosforados e carbamatos. Cerca de 50% dos entrevistados se encontravam ao menos moderadamente intoxicados. Os fatores de risco encontrados foram: ter o último contato a menos de duas semanas com agrotóxicos; não usar proteção; ser orientado pelo vendedor; citar organofosforado ou carbamato como agrotóxico principal e trabalhar nos municípios de Teófoli Otoni, Guidoval ou Piraúba. Os resultados apontam para o alto grau de risco de agravos à saúde a que estão sujeitos trabalhadores rurais em contato com agrotóxicos.This paper aimed to characterize the rural work process in nine counties in Minas Gerais State, considering socio-demographic indicators, the land tenure structure of farm operations, and work practices related to pesticide use and poisoning Data were obtained through the Jorge Duprat Figueiredo Foundation for Workers' Safety and Occupational Medicine, which applied a questionnaire to 1,064 rural workers from 1991 to 2000. Through a logistic regression, risk factors associated with pesticide poisoning were obtained for the carbamate and organophosphate groups. Some 50% of interviewees displayed at least moderate pesticide toxicity. Risk factors for pesticide poisoning were: last contact with pesticides less than two weeks before the blood cholinesterase test; no use of personal

  13. Health and environmental hazards of pesticides.

    Iyaniwura, T T

    1991-01-01

    The increase in world population and in demand for food and economic crops has put a pesticide burden on man and the environment. Pesticide residues from vector control and agricultural uses contaminate the terrestrial and aquatic surroundings and contribute to the pollution problem of the environment. Various human toxicoses have resulted from pesticide use. The major pathogenic pesticides are chlorinated hydrocarbons and organophosphates. With careful and enlightened use, pesticide toxicity, to both man and the environment, could be significantly reduced.

  14. Trace analysis of pesticides in paddy field water by direct injection using liquid chromatography-quadrupole-linear ion trap-mass spectrometry.

    Pareja, Lucía; Martínez-Bueno, M J; Cesio, Verónica; Heinzen, Horacio; Fernández-Alba, A R

    2011-07-29

    A multiresidue method was developed for the quantification and confirmation of 70 pesticides in paddy field water. After its filtration, water was injected directly in a liquid chromatograph coupled to a hybrid triple quadrupole-linear ion trap-mass spectrometer (QqLIT). The list of target analytes included organophosphates, phenylureas, sulfonylureas, carbamates, conazoles, imidazolinones and others compounds widely used in different countries where rice is cropped. Detection and quantification limits achieved were in the range from 0.4 to 80 ng L(-1) and from 2 to 150 ng L(-1), respectively. Correlation coefficients for the calibration curves in the range 0.1-50 μg L(-1) were higher than 0.99 except for diazinon (0.1-25 μg L(-1)). Only 9 pesticides presented more than 20% of signal suppression/enhancement, no matrix effect was observed in the studied conditions for the rest of the target pesticides. The method developed was used to investigate the occurrence of pesticides in 59 water samples collected in paddy fields located in Spain and Uruguay. The study shows the presence of bensulfuron methyl, tricyclazole, carbendazim, imidacloprid, tebuconazole and quinclorac in a concentration range from 0.08 to 7.20 μg L(-1).

  15. Non-Hodgkin Lymphoma and Occupational Exposure to Agricultural Pesticide Chemical Groups and Active Ingredients: A Systematic Review and Meta-Analysis

    Leah Schinasi

    2014-04-01

    Full Text Available This paper describes results from a systematic review and a series of meta-analyses of nearly three decades worth of epidemiologic research on the relationship between non-Hodgkin lymphoma (NHL and occupational exposure to agricultural pesticide active ingredients and chemical groups. Estimates of associations of NHL with 21 pesticide chemical groups and 80 active ingredients were extracted from 44 papers, all of which reported results from analyses of studies conducted in high-income countries. Random effects meta-analyses showed that phenoxy herbicides, carbamate insecticides, organophosphorus insecticides and the active ingredient lindane, an organochlorine insecticide, were positively associated with NHL. In a handful of papers, associations between pesticides and NHL subtypes were reported; B cell lymphoma was positively associated with phenoxy herbicides and the organophosphorus herbicide glyphosate. Diffuse large B-cell lymphoma was positively associated with phenoxy herbicide exposure. Despite compelling evidence that NHL is associated with certain chemicals, this review indicates the need for investigations of a larger variety of pesticides in more geographic areas, especially in low- and middle-income countries, which, despite producing a large portion of the world’s agriculture, were missing in the literature that were reviewed.

  16. Analytical methods for detecting pesticide switches with evolution of pesticide resistance

    Liang, Juhua; Tang, Sanyi; Juan J. Nieto; Cheke, Robert A.

    2013-01-01

    After a pest develops resistance to a pesticide, switching between different unrelated pesticides is a common management option, but this raises the following questions: (1) What is the optimal frequency of pesticide use? (2) How do the frequencies of pesticide applications affect the evolution of pesticide resistance? (3) How can the time when the pest population reaches the economic injury level (EIL) be estimated and (4) how can the most efficient frequency of pesticide applications be dete...

  17. Radiation induced pesticidal microbes

    Kim, Ki Yup; Lee, Y. K.; Kim, J. S.; Kim, J. K.; Lee, S. J.; Lim, D. S

    2001-01-01

    To isolate pesticidal microbes against plant pathogenic fungi, 4 strains of bacteria(K1. K3, K4, YS1) were isolated from mushroom compost and hot spring. K4, K1, K3, YS1 strain showed wide antifungal spectrum and high antifungal activities against 12 kinds of fungi. Specific proteins and the specific transcribed genes were found from the YS1 and its radiation-induced mutants. And knock-out mutants of antifungal activity were derived by transposon mutagenesis. From these knock-out mutants, the antifungal activity related genes and its modification by gamma-ray radiation are going to be studied. These results suggested that radiation could be an useful tool for the induction of functional mutants.

  18. Estrogenic and esterase-inhibiting potency in rainwater in relation to pesticide concentrations, sampling season and location

    Hamers, T.; Brink, P.J. van den; Mos, L.; Linden, S.C. van der; Legler, J.; Koeman, J.H.; Murk, A.J

    2003-05-01

    Estrogenic potency of rainwater correlated well with organochlorine concentrations, but could not be attributed to specific pesticides. - In a year-round monitoring program (1998), pesticide composition and toxic potency of the mix of pollutants present in rainwater were measured. The goal of the study was to relate atmospheric deposition of toxic potency and pesticide composition to each other and to sampling period and local agricultural activity. Rainwater was collected in 26 consecutive periods of 14 days in a background location (BACK) and in two locations representative for different agricultural practices, i.e. intensive greenhouse horticulture (HORT) and flower bulb culture (BULB). Samples were chemically analyzed for carbamate (CARB), organophosphate (OP) and organochlorine (OC) pesticides and metabolites. Esterase inhibiting potency of rainwater extracts was measured in a specially developed bio-assay with honeybee esterases and was expressed as an equivalent concentration of the model inhibitor dichlorvos. Estrogenic potency of the extracts was measured in the ER-CALUX reporter gene assay and was expressed as an equivalent concentration of estradiol. Multivariate principal component analysis (PCA) techniques proved to be valuable tools to analyze the numerous pesticide concentrations in relation to toxic potency, sampling location, and sampling season. Pesticide composition in rainwater depended much more on sampling season than on sampling location, but differences between SPRING and SUMMER were mainly attributed to local differences in agricultural practice. On average, the esterase inhibiting potency exceeded the maximum permissible concentration set for dichlorvos in The Netherlands, and was significantly higher in HORT than in BACK and BULB. Esterase inhibition correlated significantly with OP and CARB concentrations, as expected given the working mechanism of these insecticides. The estrogenic potency incidentally exceeded NOEC levels reported for

  19. A pesticide monitoring survey in rivers and lakes of northern Greece and its human and ecotoxicological risk assessment.

    Papadakis, Emmaluel N; Vryzas, Zisis; Kotopoulou, Athena; Kintzikoglou, Katerina; Makris, Konstantinos C; Papadopoulou-Mourkidou, Euphemia

    2015-06-01

    A pesticide monitoring study covering the main rivers and lakes of Northern Greece (Macedonia, Thrace and Thessaly) was undertaken. A total of 416 samples were collected over a 1.5-year sampling period (September 1999- February 2001) from six rivers and ten lakes. The water samples were analyzed with an off-line solid phase extraction technique coupled with a gas chromatography ion trap mass spectrometer using an analytical method for 147 pesticides and their metabolites, including organochlorines, organophosphates, triazines, chloroacetanilides, pyrethroids, carbamates, phthalimides and other pesticides (herbicides, insecticides and fungicides). Based on the pesticide survey results, a human health carcinogenic and non-carcinogenic risk assessment was conducted for adults and children. Ecotoxicological risk assessment was also conducted using default endpoint values and the risk quotient method. Results showed that the herbicides metolachlor, prometryn, alachlor and molinate, were the most frequently detected pesticides (29%, 12.5%, 12.5% and 10%, respectively). They also exhibited the highest concentration values, often exceeding 1 μg/L. Chlorpyrifos ethyl was the most frequently detected insecticide (7%). Seasonal variations in measured pesticide concentrations were observed in all rivers and lakes. The highest concentrations were recorded during May-June period, right after pesticide application. Concentrations of six pesticides were above the maximum allowable limit of 0.1 μg/L set for drinking water. Alachlor, atrazine and a-HCH showed unacceptable carcinogenic risk estimates (4.5E-06, 4.6E-06 and 1.3E-04, respectively). Annual average concentrations of chlorpyriphos ethyl (0.031 μg L), dicofol (0.01 μg/L), dieldrin (0.02 μg/L) and endosulfan a (0.065 μg/L) exceeded the EU environmental quality standards. The risk quotient estimates for the insecticides chorpyrifos ethyl, diazinon and parathion methyl and herbicide prometryn were above acceptable risk

  20. [Degradation of urea and ethyl carbamate in Chinese Rice wine by recombinant acid urease].

    Zhou, Jianli; Kang, Zhen; Liu, Qingtao; Du, Guocheng; Chen, Jian

    2016-01-01

    Ethyl carbamate (EC) as a potential carcinogen commonly exists in traditional fermented foods. It is important eliminate urea that is the precursors of EC in many fermented foods, including Chinese Rice wine. On the basis of achieving high-level overexpression of food-grade ethanol-resistant acid urease, we studied the hydrolysis of urea and EC with the recombinant acid urease. Recombinant acid urease showed degraded urea in both the simulated system with ethanol and Chinese Rice wine (60 mg/L of urea was completely degraded within 25 h), indicating that the recombinant enzyme is suitable for the elimination of urea in Chinese Rice wine. Although recombinant acid urease also has degradation catalytic activity on EC, no obvious degradation of EC was observed. Further investigation results showed that the Km value for urea and EC of the recombinant acid urease was 0.7147 mmol/L and 41.32 mmol/L, respectively. The results provided theoretical foundation for realizing simultaneous degradation of urea and EC.

  1. Unidirectional cross-tolerance between the carbamate insecticide propoxur and the organophosphate disulfoton in mice.

    Costa, L G; Murphy, S D

    1983-01-01

    Previous studies have shown that subchronic treatment of mice with the organophosphate insecticide, disulfoton, or the carbamate insecticide, propoxur, leads to the development of tolerance to their toxicity. Tolerance to disulfoton was due to a decrease in the number of muscarinic cholinergic receptors, while tolerance to propoxur appeared to be due to an induction of hepatic microsomal enzymes. In the present study we investigated if cross-tolerance between disulfoton and propoxur would occur. Cross-tolerance was evaluated by measuring acute toxicities, cholinesterase and carboxylesterase inhibition and hypothermic and antinociceptive effects. Mice tolerant to propoxur were cross-tolerant to the hypothermic and anticholinesterase effects of disulfoton. Similarly, when mice were pretreated with the microsomal enzyme inducer, phenobarbital, the toxicity of disulfoton was decreased. Mice made tolerant to disulfoton were cross-tolerant to the organophosphate chlorpyrifos, but were more sensitive than controls to the toxicity of propoxur. The acute toxicity of the organophosphate malathion was also increased in disulfoton-tolerant mice. Propoxur is metabolized by mixed function oxidases and possibly by a carboxylesterase. While hepatic microsomal enzymes appeared to be unchanged in disulfoton-tolerant mice, brain and liver carboxylesterase activities were significantly inhibited. Pretreatment of mice with the specific carboxylesterase inhibitor triorthotolylphosphate is known to greatly potentiate the toxicity of malathion and also potentiated, to a lesser extent, the toxicity of propoxur.(ABSTRACT TRUNCATED AT 250 WORDS)

  2. Determination of Ethyl Carbamate in Alcoholic Beverages and Fermented Foods Sold in Korea

    Ryu, Dayeon; Choi, Bogyoung; Kim, Eunjoo; Park, Seri; Paeng, Hwijin; Kim, Cho-il; Lee, Jee-yeon; Yoon, Hae Jung

    2015-01-01

    Ethyl carbamate (EC) classified as a probable human carcinogen (Group 2A) is naturally formed in alcoholic beverages and fermented foods during fermentation process and/or during storage. The objective of this study was to analyze EC in 34 food items including 14 alcoholic beverages and 20 fermented foods sold in Korea. Each food was collected from 18 supermarkets in 9 metropolitan cities in Korea, and then made into composite. According to food composition and alcohol content, samples were divided into four matrices such as apple juice, milk, Soju (liquor containing about 20% alcohol), and rice porridge. The maximum EC value of 151.06 µg/kg was found in Maesilju (liquor made from Maesil and Soju). Whisky and Bokbunjaju (Korean black raspberry wine) contained 9.90 µg/kg and 6.30 µg/kg, respectively. EC was not detected in other alcoholic beverages. Of 20 fermented foods, Japanese-style soy sauce had highest level of 15.59 µg/kg and traditional one contained 4.18 µg/kg. Soybean paste had 1.18 µg/kg, however, EC was not found in other fermented foods. PMID:26483888

  3. Reduced production of ethyl carbamate for wine fermentation by deleting CAR1 in Saccharomyces cerevisiae.

    Guo, Xue-Wu; Li, Yuan-Zi; Guo, Jian; Wang, Qing; Huang, Shi-Yong; Chen, Ye-Fu; Du, Li-Ping; Xiao, Dong-Guang

    2016-05-01

    Ethyl carbamate (EC), a pluripotent carcinogen, is mainly formed by a spontaneous chemical reaction of ethanol with urea in wine. The arginine, one of the major amino acids in grape musts, is metabolized by arginase (encoded by CAR1) to ornithine and urea. To reduce the production of urea and EC, an arginase-deficient recombinant strain YZ22 (Δcarl/Δcarl) was constructed from a diploid wine yeast, WY1, by successive deletion of two CAR1 alleles to block the pathway of urea production. The RT-qPCR results indicated that the YZ22 almost did not express CAR1 gene and the specific arginase activity of strain YZ22 was 12.64 times lower than that of parent strain WY1. The fermentation results showed that the content of urea and EC in wine decreased by 77.89 and 73.78 %, respectively. Furthermore, EC was forming in a much lower speed with the lower urea during wine storage. Moreover, the two CAR1 allele deletion strain YZ22 was substantially equivalent to parental strain in terms of growth and fermentation characteristics. Our research also suggested that EC in wine originates mainly from urea that is produced by the arginine.

  4. In Case of Pesticide Emergency

    ... Call the Poison Control Center at 1-800-222-1222 for help with first aid information. The ... Health Land, Waste, and Cleanup Lead Mold Pesticides Radon Science Water A-Z Index Laws & Regulations By ...

  5. Consumer Products Treated with Pesticides

    Many products (e.g., cutting boards, kitchen sponges, cat litter, toothbrushes and juvenile toys) are being treated with antimicrobial pesticides. Learn about requirements that apply to such products.

  6. Pesticides' influence on wine fermentation.

    Caboni, Pierluigi; Cabras, Paolo

    2010-01-01

    Wine quality strongly depends on the grape quality. To obtain high-quality wines, it is necessary to process healthy grapes at the correct ripeness stage and for this reason the farmer has to be especially careful in the prevention of parasite attacks on the grapevine. The most common fungal diseases affecting grape quality are downy and powdery mildew (Plasmopara viticola and Uncinula necator), and gray mold (Botrytis cinerea). On the other hand, the most dangerous insects are the grape moth (Lobesia botrana), vine mealybug (Planococcus ficus), and the citrus mealybug (Planococcus citri). Farmers fight grape diseases and insects applying pesticides that can be found at harvest time on grapes. The persistence of pesticides depends on the chemical characteristic of the active ingredients as well as on photodegradation, thermodegradation, codistillation, and enzymatic degradation. The pesticide residues on grapes can be transferred to the must and this can influence the selection and development of yeast strains. Moreover, yeasts can also influence the levels of the pesticides in the wine by reducing or adsorbing them on lees. During the fermentative process, yeasts can cause the disappearance of pesticide residues by degradation or absorption at the end of the fermentation when yeasts are deposited as lees. In this chapter, we reviewed the effect of commonly used herbicides, insecticides, and fungicides on yeasts. We also studied the effect of alcoholic and malolactic fermentation on pesticide residues.

  7. Progress in pesticide and POPs hair analysis for the assessment of exposure.

    Tsatsakis, Aristidis; Tutudaki, Maria

    2004-10-29

    The present paper reviews the work that has been done in the field of pesticide and persistent organic pollutants (POPs) hair analysis during the last 15 years. It summarizes the compounds of interest, the methods of analyte extraction from the hair matrix, the analytical techniques employed and the results obtained. The most widely studied POPs are the polychlorinated dibenzodioxins (PCDDs), the dibenzofurans (PCDFs) the co-planar biphenyls (co-PCBs) and total biphenyls (PCBs). The most widely studied pesticides are the organochlorine ones, like the hexachlorocyclohexanes and the DDTs, which nowadays are only found as environmental pollutants, some organophosphates, selected pyrethroids and the carbamate methomyl. The most widely applied technique was gas chromatography (GC) coupled to mass spectrometry (MS). Other detectors like the ECD in the case of organochlorine analysis and the NPD in the case of organophosphate analysis were also used. The presented data concern human and animal studies. The levels of DDTs detected in hair were between 19 and 400 ng/g, of co-PCBs 0.27 and 0.45 ng/g, of total PCBs 5-13 ng/g of PCDDs and PCDFs 0.1-10 pg/g of lindane 20-400 ng/g of HCHs 14-40 ng/g of diazinon 110-520 ng/g and of methomyl 900-1800 ng/g. These results strongly support the possibility of using hair as a suitable indicator for the assessment of long-term exposure to POPs and pesticides.

  8. Molecular recognition by cholesterol esterase of active site ligands: structure-reactivity effects for inhibition by aryl carbamates and subsequent carbamylenzyme turnover.

    Feaster, S R; Lee, K; Baker, N; Hui, D Y; Quinn, D M

    1996-12-24

    Interactions of mammalian pancreatic cholesterol esterases from pig and rat with a family of aryl carbamates CnH2n+1NHCOOAr [n = 4-9; Ar = phenyl, p-X-phenyl (X = acetamido, bromo, fluoro, nitro, trifluoromethyl), 2-naphthyl, 2-tetrahydronaphthyl, estronyl] have been investigated, with an aim of delineating the ligand structural features which lead to effective molecular recognition by the active site of the enzyme. These carbamates inhibit the catalytic activity of CEase by rapid carbamylation of the active site, a process that shows saturation kinetics. Subsequent slow decarbamylation usually leads to full restoration of activity, and therefore aryl carbamates are transient inhibitors, or pseudo-substrates, of CEase. Structural variation of carbamate inhibitors allowed molecular recognition in the fatty acid binding and steroid binding loci of the extended active site to be probed, and the electronic nature of the carbamylation transition state to be characterized. Optimal inhibitory activity is observed when the length of the carbamyl function is n = 6 and n = 7 for porcine and rat cholesterol esterases, respectively, equivalent to eight- and nine-carbon fatty acyl chains. In contrast, inhibitory activity increases progressively as the partial molecular volume of the aromatic fragment increases. Hammett plots for p-substituted phenyl-N-hexyl carbamates indicate that the rate-determining step for carbamate inhibition is phenolate anion expulsion. Effects of the bile salt activator taurocholate on the kinetically resolved phases of the pseudo-substrate turnover of aryl carbamates were also studied. Taurocholate increases the affinity of the carbamate for the active site of cholesterol esterase in the reversible, noncovalent complex that precedes carbamylation and increases the rate constants of the serial carbamylation and decarbamylation steps. Structural variation of the N-alkyl chain and of the aryl fused-ring system provides an accounting of bile salt

  9. Hair as a marker for pesticides exposure.

    Smith-Baker, Charlotte; Saleh, Mahmoud A

    2011-01-01

    Rats were orally treated with mixtures of chlorinated pesticides. Hair was collected and analyzed for pesticide residues over a period of up to four weeks. Quantitative and qualitative analysis of the recovered pesticides in hair were determined using gas chromatography with electron capture detector. Results suggest that hair can be used as a biomarker for the monitoring of organochlorinated pesticide residues at low parts per billion levels. Chlorinated pesticides were also detected in human hair of environmentally exposed and occupationally exposed individuals, which indicates that hair can be used for monitoring pesticides exposure.

  10. 40 CFR 158.2010 - Biochemical pesticides data requirements.

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Biochemical pesticides data...) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Biochemical Pesticides § 158.2010 Biochemical pesticides... required to support registration of biochemical pesticides. Sections 158.2080 through 158.2084 identify...

  11. 40 CFR 158.2110 - Microbial pesticides data requirements.

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Microbial pesticides data requirements...) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Microbial Pesticides § 158.2110 Microbial pesticides data requirements. (a) For all microbial pesticides. (1) The following § 158.2120 through §...

  12. Application of pesticide transport model for simulating diazinon runoff in California’s central valley

    Joyce, Brian A.; Wallender, Wesley W.; Mailapalli, Damodhara R.

    2010-12-01

    Dormant spray application of pesticides to almond and other stone fruit orchards is the main source of diazinon during the winter in California's central valley. Understanding the pesticide transport and the tradeoffs associated with the various management practices is greatly facilitated by the use of physically-based contaminant transport models. In this study, performance of Joyce's et al. (2008) pesticide transport model was evaluated using experimental data collected from two ground treatments such as resident vegetation and bare soil. The model simulation results obtained in calibration and validation process were analyzed for pesticide concentration and total load. The pesticide transport model accurately predicted the pesticide concentrations and total load in the runoff from bare field and was capable of simulating chemical responses to rainfall-runoff events. In case of resident vegetation, the model results exhibited a larger range of variation than was observed in the bare soil simulations due to increased model parameterization with the addition of foliage and thatch compartments. Furthermore, the model was applied to study the effect of runoff lag time, extent of crop cover, organic content of soil and post-application irrigation on the pesticide peak concentration and total load. Based on the model results, recommendations were suggested to growers prior to implementing certain management decisions to mitigate diazinon transport in the orchard's spray runoff.

  13. Applicability of ELISA-based Determination of Pesticides for Groundwater Quality Monitoring

    Tsuchihara, Takeo; Yoshimoto, Shuhei; Ishida, Satoshi; Imaizumi, Masayuki

    The principals and procedures of ELISA (Enzyme-linked Immunosorbent Assay)-based determination of pesticides (Fenitrothion) in environmental samples were reviewed, and the applicability of the ELISA method for groundwater quality monitoring were validated through the experimental tracer tests in soil columns and the field test in Okinoerabu Island. The test results showed that the ELISA method could be useful not only for screening but also for quantitative analysis of pesticides. In the experimental tracer tests in soil columns, the retardation of pesticides leaching compared with conservative tracers were observed. In the field test, the contamination of the pesticide was detected in groundwater samples in Okinoerabu Island, even though the targeted pesticide was considered to be applied to the upland field 4 months ago. In order to investigate the transport and fate of pesticides in groundwater taking into account retardation from the field to groundwater table and the residue in groundwater, continuous observations of pesticides in groundwater are in a strong need, and the ELISA method is applicable to the long-term quality groundwater monitoring.

  14. Long-term relationships among pesticide applications, mobility, and soil erosion in a vineyard watershed

    Sabatier, Pierre; Poulenard, Jérôme; Fanget, Bernard; Reyss, Jean-Louis; Develle, Anne-Lise; Wilhelm, Bruno; Ployon, Estelle; Pignol, Cécile; Naffrechoux, Emmanuel; Dorioz, Jean-Marcel; Montuelle, Bernard; Arnaud, Fabien

    2014-11-01

    Agricultural pesticide use has increased worldwide during the last several decades, but the long-term fate, storage, and transfer dynamics of pesticides in a changing environment are poorly understood. Many pesticides have been progressively banned, but in numerous cases, these molecules are stable and may persist in soils, sediments, and ice. Many studies have addressed the question of their possible remobilization as a result of global change. In this article, we present a retro-observation approach based on lake sediment records to monitor micropollutants and to evaluate the long-term succession and diffuse transfer of herbicides, fungicides, and insecticide treatments in a vineyard catchment in France. The sediment allows for a reliable reconstruction of past pesticide use through time, validated by the historical introduction, use, and banning of these organic and inorganic pesticides in local vineyards. Our results also revealed how changes in these practices affect storage conditions and, consequently, the pesticides' transfer dynamics. For example, the use of postemergence herbicides (glyphosate), which induce an increase in soil erosion, led to a release of a banned remnant pesticide (dichlorodiphenyltrichloroethane, DDT), which had been previously stored in vineyard soil, back into the environment. Management strategies of ecotoxicological risk would be well served by recognition of the diversity of compounds stored in various environmental sinks, such as agriculture soil, and their capability to become sources when environmental conditions change.

  15. Long-term relationships among pesticide applications, mobility, and soil erosion in a vineyard watershed.

    Sabatier, Pierre; Poulenard, Jérôme; Fanget, Bernard; Reyss, Jean-Louis; Develle, Anne-Lise; Wilhelm, Bruno; Ployon, Estelle; Pignol, Cécile; Naffrechoux, Emmanuel; Dorioz, Jean-Marcel; Montuelle, Bernard; Arnaud, Fabien

    2014-11-04

    Agricultural pesticide use has increased worldwide during the last several decades, but the long-term fate, storage, and transfer dynamics of pesticides in a changing environment are poorly understood. Many pesticides have been progressively banned, but in numerous cases, these molecules are stable and may persist in soils, sediments, and ice. Many studies have addressed the question of their possible remobilization as a result of global change. In this article, we present a retro-observation approach based on lake sediment records to monitor micropollutants and to evaluate the long-term succession and diffuse transfer of herbicides, fungicides, and insecticide treatments in a vineyard catchment in France. The sediment allows for a reliable reconstruction of past pesticide use through time, validated by the historical introduction, use, and banning of these organic and inorganic pesticides in local vineyards. Our results also revealed how changes in these practices affect storage conditions and, consequently, the pesticides' transfer dynamics. For example, the use of postemergence herbicides (glyphosate), which induce an increase in soil erosion, led to a release of a banned remnant pesticide (dichlorodiphenyltrichloroethane, DDT), which had been previously stored in vineyard soil, back into the environment. Management strategies of ecotoxicological risk would be well served by recognition of the diversity of compounds stored in various environmental sinks, such as agriculture soil, and their capability to become sources when environmental conditions change.

  16. Immunotoxicity of organophosphorous pesticides.

    Galloway, Tamara; Handy, Richard

    2003-01-01

    This study reviews the toxic effects of organophosphate (OP) pesticides on the immune systems and immune functions of invertebrates, fish, and higher vertebrate wildlife. The fundamental features and mechanisms of OP-induced immunotoxicity are illustrated with reference to parathion, chlorpyrifos, malathion, and diazinon. Immunotoxicity may be direct via inhibition of serine hydrolases or esterases in components of the immune system, through oxidative damage to immune organs, or by modulation of signal transduction pathways controlling immune functions. Indirect effects include modulation by the nervous system, or chronic effects of altered metabolism/nutrition on immune organs. Immunotoxicities are varied and include pathology of immune organs, and decreased humoral and/or cell mediated immunity. Altered non-specific immunity, decreased host resistance, hypersensitivity and autoimmunity are also features of immunotoxicity; although not all of these have been conclusively demonstrated in terms of pollutant exposure and immunotoxic effects in wildlife within individual experiments. Immunotoxicological biomarkers and biological monitoring tools are urgently needed to assess the extent of immunotoxicity in wildlife. Selection of universal biomarkers is hampered by the physiological diversity of immune systems in animals. However, by drawing on evidence from human epidemiology and tiered approaches in mammalian immunotoxicity evaluation, a selection of generic biomarkers of immunotoxicity in animals is suggested. Priorities for future research are also identified.

  17. Effects of organophosphate,carbamate and pyrethroid insecticides and their mixtures on neuromuscular junction transmission

    HeFS; XiaoC

    2002-01-01

    To investigate the effects of organophosphorus (OP),carbamate (Carb),pyrehroid (Pyr) insecticides and their mixtures on neuromuscular junction transmission (NMJT),dimethoate(D) and phoxim(P),methomyl(M),and fenvalerate(F) were selected.Rats were intraperitoneally intoxicated by D,P,M,F,D+M,D+F,P+M,or P+F with the dosage of each LD50 respectively.The function of the NMJT was assessed with the mean consecutive differences (MCD) of the latencies of single fiber action potentials detected by stimulation single fiber electromyography(SSFEMG) at the stimulus frequency of 20 Hz.The SSFEMG was also applied to detect the function of NMJT in 40 patients with OPs and their mixtures poisoning in this study.The results showed that (1)the myasthenia occurred only in rats with OPs and their mixtures poisoning,but not in F,M intoxicated rats.The increase of MCD shown by SSFEMG and induced by OP and their mixtures indicating a post-synaptic block was well correlated with the occurrence of myasthenia both in rats and patients(P<0.001);(2)the increase of MCD in rats of OP poisoning was significant in comparison with the control and F,M intoxicated rats;but was not significantly different from those in rats intoxicated by OP mixtures;(3)the MCDs were significantly increased in IMS patients of both acute OP poisoning and OP mixtures poisoning,but showing no significant difference between the two groups of patients.It is concluded that OP is the only responsible agent for the dysfunction of neuromuscular transmission induced by single OP and OP mixture insecticides which could be sensitively detected by SSFEMG.

  18. Detection of Methomyl, a Carbamate Insecticide, in Food Matrices Using Terahertz Time-Domain Spectroscopy

    Baek, Seung Hyun; Kang, Ju Hee; Hwang, Yeun Hee; Ok, Kang Min; Kwak, Kyungwon; Chun, Hyang Sook

    2016-05-01

    The aim of this study was to investigate the feasibility of detecting methomyl, a carbamate insecticide, in food matrices (wheat and rice flours) using terahertz time-domain spectroscopy (THz-TDS). In the frequency range 0.1-3 THz, the characteristic THz absorption peaks of methomyl at room temperature were detected at 1 (33.4 cm-1), 1.64 (54.7 cm-1), and 1.89 (63.0 cm-1) THz. For detailed spectral analysis, the vibrational frequency and intensity of methomyl were calculated using solid-state density functional theory to mimic molecular interactions in the solid state. Qualitatively, the simulated spectrum was in good agreement with the experimental spectrum. Analysis of the individual absorption modes revealed that all of the features in the THz spectrum of methomyl were mainly generated from intermolecular vibrations. The peak appearing at 1 THz (33.4 cm-1) was then selected and tested for its suitability as a fingerprint for detecting methomyl in food matrices. Its absorbance was dose-dependently distinguishable from that of wheat and rice flours. The calibration curve of methomyl had a regression coefficient of >0.974 and a detection limit of <3.74 %. Accuracy and precision expressed as recovery and relative standard deviation in interday repeatability were in the ranges 78.0-96.5 and 2.83-4.98 %, respectively. Our results suggest that THz-TDS can be used for the rapid detection of methomyl in foods, but its sensitivity needs to be improved.

  19. 77 FR 23713 - Pesticides; Final Guidance on Material Safety Data Sheets as Pesticide Labeling; Request for...

    2012-04-20

    ... relationship between EPA-approved labels for pesticides registered under the Federal Insecticide, Fungicide... AGENCY Pesticides; Final Guidance on Material Safety Data Sheets as Pesticide Labeling; Request for.... SUMMARY: The Agency is announcing the availability of a Pesticide Registration Notice (PR Notice)...

  20. Ethyl-bridged hybrid column as an efficient alternative for HPLC analysis of plasma amino acids by pre-column derivatization with 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate.

    Castellanos, Mar; Van Eendenburg, Cecile Van; Gubern, Carme; Sanchez, Juan M

    2016-09-01

    Conventional C18 silica columns have proven to be useful for the analysis of amino acids (AA) from protein hydrolysates but undesirable peak overlapping is usually found when analyzing body fluids given that a large number of AAs are present in the samples. As an alternative to silica packings, an ethyl-bridged packing for reversed-phase liquid chromatography of derivatized AAs with 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) has been evaluated. The new packing material improves the separation efficiency allowing better separations when analyzing biological fluids. Moreover, this packing has advantages for routine AA analysis, such as a decrease in the total running time and an increase in the life-time of the columns. The pH of the mobile phase has a significant effect on the elution behavior of the AQC hydrolysis product (AMQ) and on the AA derivatives. It is not possible to elute AMQ before detecting the first AA derivative, which requires an accurate adjustment of the pH in the range of 5.30-5.35 to obtain good separation and resolution for the most polar compounds. Under the conditions proposed, it is possible to separate all AAs except the Gly-Gln pair, which is not a problem when hydrolyzed samples are analyzed. The AMQ-Ser pair requires either the use of a different mobile phase pH for its baseline separation or the use of fluorescence detection. Two different procedures for protein removal from plasma samples have been evaluated, solvent precipitation and ultrafiltration (UF) and it has been found that UF gives better results as no significant losses of AAs were observed. The validation of the proposed method with UV detection gives method detection limits in the range of 8-12μM, with repeatability values<8% (n=6) and inter-day precision in plasma samples ranging from 4 to 13% (n=4).

  1. ERK-dependent phosphorylation of HSF1 mediates chemotherapeutic resistance to benzimidazole carbamates in colorectal cancer cells.

    Wales, Christina T K; Taylor, Frederick R; Higa, Allan T; McAllister, Harvey A; Jacobs, Aaron T

    2015-07-01

    Drugs containing the benzimidazole carbamate scaffold include anthelmintic and antifungal agents, and they are now also recognized as having potential applications in the treatment of colorectal and other cancers. These agents act by binding to β-tubulin, and in doing so they disrupt microtubules, arrest cell division, and promote apoptotic cell death in malignant cells. We have evaluated several commercially available benzimidazole carbamates for cytotoxic activity in colorectal cancer cells. In addition to cytotoxicity, we also observe activation of the transcription factor, heat shock factor-1 (HSF1). HSF1 is well known to mediate a cytoprotective response that promotes tumor cell survival and drug resistance. Here, we show that biochemical inhibition with the HSF1 inhibitor KRIBB11 or siRNA-based silencing of HSF1 results in a significant enhancement of drug potency, causing an approximately two-fold decrease in IC50 values of parbendazole and nocodazole. We also define a mechanism for drug-induced HSF1 activation, which results from a phosphorylation event at Ser326 that is dependent on the activation of the extracellular regulated protein kinase-1/2 (ERK-1/2) mitogen-activated protein kinase pathway. Inhibition of the upstream kinase MEK-1/2 with U0126 attenuates the phosphorylation of both ERK-1/2 and HSF1, and significantly enhances drug cytotoxicity. From these data we propose a unique model whereby the ERK-1/2-dependent activation of HSF1 promotes chemotherapeutic resistance to benzimidazole carbamates. Therefore, targeting the ERK-1/2 signaling cascade is a potential strategy for HSF1 inhibition and a means of enhancing the cytotoxicity of these agents.

  2. Estrogenic and esterase-inhibiting potency in rainwater in relation to pesticide concentrations, sampling season and location.

    Hamers, Timo; van den Brink, Paul J; Mos, Lizzy; van der Linden, Sander C; Legler, Juliette; Koeman, Jan H; Murk, Albertinka J

    2003-01-01

    In a year-round monitoring program (1998), pesticide composition and toxic potency of the mix of pollutants present in rainwater were measured. The goal of the study was to relate atmospheric deposition of toxic potency and pesticide composition to each other and to sampling period and local agricultural activity. Rainwater was collected in 26 consecutive periods of 14 days in a background location (BACK) and in two locations representative for different agricultural practices, i.e. intensive greenhouse horticulture (HORT) and flower bulb culture (BULB). Samples were chemically analyzed for carbamate (CARB), organophosphate (OP) and organochlorine (OC) pesticides and metabolites. Esterase inhibiting potency of rainwater extracts was measured in a specially developed bio-assay with honeybee esterases and was expressed as an equivalent concentration of the model inhibitor dichlorvos. Estrogenic potency of the extracts was measured in the ER-CALUX reporter gene assay and was expressed as an equivalent concentration of estradiol. Multivariate principal component analysis (PCA) techniques proved to be valuable tools to analyze the numerous pesticide concentrations in relation to toxic potency, sampling location, and sampling season. Pesticide composition in rainwater depended much more on sampling season than on sampling location, but differences between and were mainly attributed to local differences in agricultural practice. On average, the esterase inhibiting potency exceeded the maximum permissible concentration set for dichlorvos in The Netherlands, and was significantly higher in than in and . Esterase inhibition correlated significantly with OP and CARB concentrations, as expected given the working mechanism of these insecticides. The estrogenic potency incidentally exceeded NOEC levels reported for aquatic organisms and was highest in . Although estrogenic potency of rainwater correlated with OC concentrations, the ER-CALUX responses could not be attributed to

  3. Chiral Pesticides: Identification, Description and Environmental Implications

    Anthropogenic chemicals, including pesticides, are a major source of contamination and pollution in the environment. Pesticides have many positive uses: increased food production, decreased damage to crops and structures, reduced disease vector populations, and more. Nevertheless...

  4. Neurobehavioral and neurodevelopmental effects of pesticide exposures

    London, L.; Beseler, C.; Bouchard, M.F.; Bellinger, D.C.; Colosio, C.; Grandjean, P.; Harari, R.; Kootbodien, T.; Kromhout, H.; Little, F.; Meijster, T.; Moretto, A.; Rohlman, D.S.; Stallones L.

    2012-01-01

    The association between pesticide exposure and neurobehavioral and neurodevelopmental effects is an area of increasing concern. This symposium brought together participants to explore the neurotoxic effects of pesticides across the lifespan. Endpoints examined included neurobehavioral, affective and

  5. Pesticide risks around the home (image)

    Pesticides are substances which kill or deter unwanted pests, such as insects or rodents. These substances can ... avoid an accidental ingestion is to keep all pesticides out of the reach of children.

  6. Pesticide Exposures May Alter Mouth Bacteria

    ... fullstory_162249.html Pesticide Exposures May Alter Mouth Bacteria Study of Washington farm workers finds alterations persist ... News) -- Pesticide exposure may change the makeup of bacteria in the mouths of farm workers, a new ...

  7. Neurobehavioral and neurodevelopmental effects of pesticide exposures

    London, Leslie; Beseler, Cheryl; Bouchard, Maryse F

    2012-01-01

    The association between pesticide exposure and neurobehavioral and neurodevelopmental effects is an area of increasing concern. This symposium brought together participants to explore the neurotoxic effects of pesticides across the lifespan. Endpoints examined included neurobehavioral, affective ...

  8. Organochlorine Pesticides in the Environment

    Stickel, L.F.

    1968-01-01

    Each year for nearly 20 years, thousands of pounds of persistent organochlorine pesticides have been applied to outdoor areas in many countries. These compounds may last for a very long time in the environment, and be carried by wind, water, and animals to places far distant from where they are used. As a result, most living organisms now contain organochlorine residues. This paper constitutes a selective review of the literature concerning the occurrence, distribution, and effects of organochlorines in the environment. Highest concentrations generally occur in carnivorous species. Thus predatory and fish-eating birds ordinarily have higher residues than do herbivores; quantities are similar in birds of similar habits in different countries. Any segment of the ecosystem - marshland, pond, forest, or field - receives various amounts and kinds of pesticides at irregular intervals. The different animals absorb, detoxify, store, and excrete pesticides at different rates. Different degrees of magnification of pesticide residues by living organisms in an environment are the practical result of many interactions that are far more complex than implied by the statement of magnification up the food chain. These magnifications may be millions of times from water to mud or only a few times from food to first consumer. Direct mortality of wild animals as an aftermath of recommended pesticide treatments has been recorded in the literature of numerous countries. However, accidents and carelessness also accompany pesticide use on a percentage basis and are a part of the problem. More subtle effects on the size and species composition of populations are more difficult to perceive in time to effect remedies. The possibility of ecological effects being mediated through changes in physiology and behavior has received some attention and has resulted in some disquieting findings. These include discovery of the activity of organochlorines in stimulating the breakdown of hormones or in

  9. tert-Butyl N-[6-(N,N-dipropylcarbamoyl-1,3-benzothiazol-2-yl]carbamate

    Xin Fang

    2010-05-01

    Full Text Available The title compound C19H27N3O3S, crystallizes with two unique molecules in the asymmetric unit. The benzene ring of each benzothiazole unit carries a dipropylcarbamoyl substituent in the 6-position and a tert-butyl carbamate unit on each thiazole ring. In the crystal structure, intermolecular N—H...N and weak C—H...O hydrogen bonds form centrosymmetric dimers. Additional C—H...O contacts construct a three-dimensional network. A very weak C—H...π contact is also present.

  10. Synthesis and antimicrobial activities of new oxime carbamates of 3-aryl-2-thioquinazolin-4(3H)-one

    Suresh S Patil; Swati D Jadhav; M B Deshmukh

    2012-09-01

    S-alkylation of 3-aryl-2-thioquinazolin-4(3H)-one (1) with chloroacetone gave 2-(propanonyl thio)-3-arylquinazol-4(3H)ones (2). Further, the treatment of compound (2) with hydroxylamine hydrochloride gave the corresponding oximes (3) which on reaction with phenyl isocyanate in THF yielded corresponding oxime carbamates 4. The synthesized compounds have been confirmed using IR and 1H NMR, mass spectral data together with elemental analysis. All newly synthesized compounds have been tested for their antibacterial and antifungal activities.

  11. Resíduos de pesticidas em águas superficiais de área de nascente do Rio São Lourenço-MT: validação de método por extração em fase sólida e cromatografia líquida Pesticide residues in surface waters at the headwaters of São Lourenço River-MT, Brazil: validation of a method using solid-phase extraction and liquid chromatography

    Anna Carolina Araújo Ribeiro

    2013-01-01

    Full Text Available A multiresidue method using HPLC/DAD for the determination of fourteen pesticides in water based on SPE, using SDVB (styrene divynilbenzene copolymer as adsorbent was validated. Recoveries from 61 to 120%, relative standard deviation between 2 and 15% and detection limits from 0.07 to 0.75 µg L-1 were obtained. It was applied to 66 surface water samples collected in a degraded area at the headwaters of São Lourenço river, Mato Grosso, Brazil. Eight pesticides were detected in concentrations ranging from 0.15 to 35.25 µg L-1. Considering ecotoxicological data, carbendazim and carbofuran may represent a risk to aquatic organisms. These results draw attention to the contamination of this vulnerable degraded area.

  12. Identification and quantification of carbamate pesticides in dried lime tree flowers by means of excitation-emission molecular fluorescence and parallel factor analysis when quenching effect exists.

    Rubio, L; Ortiz, M C; Sarabia, L A

    2014-04-11

    A non-separative, fast and inexpensive spectrofluorimetric method based on the second order calibration of excitation-emission fluorescence matrices (EEMs) was proposed for the determination of carbaryl, carbendazim and 1-naphthol in dried lime tree flowers. The trilinearity property of three-way data was used to handle the intrinsic fluorescence of lime flowers and the difference in the fluorescence intensity of each analyte. It also made possible to identify unequivocally each analyte. Trilinearity of the data tensor guarantees the uniqueness of the solution obtained through parallel factor analysis (PARAFAC), so the factors of the decomposition match up with the analytes. In addition, an experimental procedure was proposed to identify, with three-way data, the quenching effect produced by the fluorophores of the lime flowers. This procedure also enabled the selection of the adequate dilution of the lime flowers extract to minimize the quenching effect so the three analytes can be quantified. Finally, the analytes were determined using the standard addition method for a calibration whose standards were chosen with a D-optimal design. The three analytes were unequivocally identified by the correlation between the pure spectra and the PARAFAC excitation and emission spectral loadings. The trueness was established by the accuracy line "calculated concentration versus added concentration" in all cases. Better decision limit values (CCα), in x0=0 with the probability of false positive fixed at 0.05, were obtained for the calibration performed in pure solvent: 2.97 μg L(-1) for 1-naphthol, 3.74 μg L(-1) for carbaryl and 23.25 μg L(-1) for carbendazim. The CCα values for the second calibration carried out in matrix were 1.61, 4.34 and 51.75 μg L(-1) respectively; while the values obtained considering only the pure samples as calibration set were: 2.65, 8.61 and 28.7 μg L(-1), respectively.

  13. Geostatistics as a basis to the CMLS pesticide simulation model with validation in soil columns Geoestatística como suporte ao modelo de simulação de agrotóxico CMLS com validação em colunas de solos

    Gilberto Nicolella

    2005-01-01

    Full Text Available The use of simulation models is probably the most efficient means for predicting the behavior of pesticides in the soil-plant-water system. The CMLS (Chemical Movement in Layered Soils simulation model for predicting the fate of pesticides was used for studying the behavior of tebuthiuron, a herbicide used in sugar cane crops, from a sampling grid with 111 sampling points 200 m apart from one another and encompassing three types of soil: Ustic Quartzipsamment, Rhodic Hapludox and Typic Hapludox, all with medium and clay textures. The 373 points assessed by the simulator, generated from samples coming from the original grid and through the geostatistical methods of variography and ordinary kriging, returned the depth values reached by the herbicide after six years of simulation (1989-1995. For the Ustic Quartzipsamment, tebuthiuron, in four simulated points, returned depth values above 43 m and a maximum 50 m, with a certain amount of the product still remaining in the soil that was close to 10% of the original 1.1 kg ha-1 applied. Results from the column assay used for validating the model showed that the model overestimated the depth reached by the herbicide in 6.6% as compared to the column value for the Ustic Quartzipsamment. The depth was underestimated in 4.5% and 20% for the Typic Hapludox and the Rhodic Hapludox, respectively. These data support the adequacy of the model for assessing the fate of tebuthiuron in both Ustic Quartzipsamment and Typic Hapludox.O uso de modelos de simulação é provavelmente a maneira mais eficiente para predizer o comportamento de agrotóxicos no sistema solo/água/planta. O modelo de simulação de destino de agrotóxicos CMLS (Chemical Movement in Layered Soils, foi usado para estudar o comportamento do herbicida tebuthiuron, utilizado na cultura de cana-de-açúcar, a partir de uma grade de amostragem composta de 111 pontos amostrais, equi-espaçados de 200 m e englobando três tipos de solo: Neossolo

  14. 茶树油清除豇豆农药残留的效果%Effects of tea tree oils on removing pesticide residue in cowpea

    林丽静; 程盛华; 李积华; 黄茂芳; 唐永富; 朱德明

    2013-01-01

    Pesticides are widely used as an insurance policy against devastating crop losses from pests and diseases. Excessive usage of pesticides may lead to contamination of the crop and the environment, eventually posing a risk of pesticide-related illnesses to humans. Previous literature has shown that water washing is only partially effective in removing pesticides, and in the case of liposoluble pesticides, a cosolvent must be used as an adjuvant. Recently, naturally occurring adjuvants are gaining prominence over synthetic chemical compounds. Tea tree oil (TTO, the oil of Melaleuca alternifolia), a natural, volatile essential oil, is mainly extracted by steam distillation from the fresh leaves and terminal branchlets of the plant. It has attracted significant interest due to its antifungal, antiviral, and antibacterial bioactivities. However, to the best of our knowledge, there are fewer experimental data evaluating its efficacy in the removal of pesticide residues. In this study, the effects of TTO on removing pesticide residue were carried out in the cowpea. Volume:volume (v:v) concentrations of 0.05%, 0.1%, 0.2%, 0.4% and 0.8% of TTO and water soluble tea tree oil (WTTO) in water were used to remove a standardized pesticide mixture (organophosphorus, pyrethroid, and carbamate compounds) from cowpeas. Sample pretreatment (pesticide application to cowpeas) was performed according to agricultural industry standards. The objective pesticide residues in cowpeas were assayed by gas chromatography (GC) and chromatography-mass spectrometry detection (GC-MS), and then the clearance rate was calculated. The results showed that TTO was able to remove the three kinds of pesticides from cowpeas. Moreover, the removal efficiency increased with increasing concentration of TTO. The effect of clearing organophosphate was much more obvious than that of either pyrethroid or carbamate. It was suggested that small liposoluble molecules of TTO rapidly infiltrate the cowpea surface to

  15. Equilibrium Dynamics of β-N-Methylamino-L-Alanine (BMAA) and Its Carbamate Adducts at Physiological Conditions

    Zimmerman, David; Goto, Joy J.; Krishnan, Viswanathan V

    2016-01-01

    Elevated incidences of Amyotrophic Lateral Sclerosis/Parkinsonism Dementia complex (ALS/PDC) is associated with β-methylamino-L-alanine (BMAA), a non-protein amino acid. In particular, the native Chamorro people living in the island of Guam were exposed to BMAA by consuming a diet based on the cycad seeds. Carbamylated forms of BMAA are glutamate analogues. The mechanism of neurotoxicity of the BMAA is not completely understood, and BMAA acting as a glutamate receptor agonist may lead to excitotoxicity that interferes with glutamate transport systems. Though the interaction of BMAA with bicarbonate is known to produce carbamate adducts, here we demonstrate that BMAA and its primary and secondary adducts coexist in solution and undergoes a chemical exchange among them. Furthermore, we determined the rates of formation/cleavage of the carbamate adducts under equilibrium conditions using two-dimensional proton exchange NMR spectroscopy (EXSY). The coexistence of the multiple forms of BMAA at physiological conditions adds to the complexity of the mechanisms by which BMAA functions as a neurotoxin. PMID:27513925

  16. Investigations on Blood Activities of Some Enzymes in Dogs After Acute Intoxication with the Carbamate Insecticide Carbofuran

    Rumen Binev

    2016-10-01

    Full Text Available Experiments for monitoring of changes in blood enzyme activities were carried out in dogs after acute intoxication with the carbamate insecticide carbofuran (Carbosan 35 СТ. The studies involved one control and 6 experimental groups of dogs (total n=42, treated once orally with increasing doses of the preparation via oesophageal probe: 0.525 mg/kg (experimental group I, 1.05 mg/kg (experimental group II, 2.1 mg/kg (experimental group III, 3.5 mg/kg (experimental group IV, 5.25 mg/kg (experimental group V and 10.5 mg/kg (LD50, (experimental group VI, corresponding to 1/20, 1/10, 1/5, 1/3, 1/2 and LD50, oral doses for albino rats. Blood samples were obtained from v. antebrachi cephalica or v. jugularis in the course of 3 consecutive days prior to the treatment (hours -48, -24 and 0 and on post treatment hours 1, 3, 5, 7, 24 and 48 from all groups for analysis of acetylcholinesterase (AChE, aspartate aminotransferase (ASAT, alanine aminotransferase (ALAT, amylase (AMY, gamma-glutamyltransferase (g-GT, alkaline phosphatase (ALP and lactate dehydrogenase (LDH. It was established that the tested carbamate insecticide provoked lower blood activity of AChE and increased the levels of ASAT, ALAT, AMY, g-GT, AP and LDH between post treatment hours 1 and 7; afterwards, the studied parameters regained the respective control values.

  17. Cholinesterase activity as a biomarker of pesticide exposure in Allolobophora chlorotica earthworms living in apple orchards under different management strategies.

    Denoyelle, Renaud; Rault, Magali; Mazzia, Christophe; Mascle, Odile; Capowiez, Yvan

    2007-12-01

    The present study used cholinesterase (ChE) activity in earthworms as a biomarker of pesticide exposure at 17 apple orchards using different pest protection strategies (organic, integrated pest management [IPM], conventional, and abandoned) located within a 300-km(2) subregion near Avignon in southeastern France). The most common earthworm species in the 17 orchards was Allolobophora chlorotica. We examined inherent variability in ChE activity that might be attributable to soil characteristics and found that differences in soil structure or type did not significantly influence ChE activity. Furthermore, there was no relation between ChE specific activity and earthworm weight, and thus activity does not require correction for weight. Ten earthworms were collected in two successive months (April and May 2003) from each of the 17 orchards. Compared to the activity in worms from the control abandoned orchards, ChE activity was significantly decreased in earthworms from half the IPM and conventional orchards in April and all these orchards in May. Notably, ChE activity was also lower in earthworms from three organic orchards during May. No relation was observed between ChE decrease and the number of treatments (total or only organophosphorous and carbamate pesticides). Cholinesterase activity in earthworms from abandoned orchards varied between the two collecting periods, illustrating the difficulty in obtaining reference values for the use of ChE as a biomarker in field studies.

  18. Pesticide residues in Nile tilapia (Oreochromis niloticus) and Nile perch (Lates niloticus) from Southern Lake Victoria, Tanzania

    Henry, L. [Chemistry Department, University of Dar es Salaam. PO Box 35061, Dar es Salaam (Tanzania); Kishimba, M.A. [Chemistry Department, University of Dar es Salaam. PO Box 35061, Dar es Salaam (Tanzania)]. E-mail: kishimba@chem.udsm.ac.tz

    2006-03-15

    Nile tilapia (Oreochromis niloticus) and Nile perch (Lates niloticus) samples were collected from fish landing stations in nine riparian districts on the Tanzanian side of Lake Victoria and screened for residues of 64 organochlorine, organophosphorus, carbamate, and pyrethroid pesticides. The residue levels in the fish fillet were up to 0.003, 0.03 and 0.2 mg/kg fresh weight (0.7, 3.8 and 42 mg/kg lipid weight) of fenitrothion, DDT and endosulfan, respectively. Mean levels within sites were up to 0.002, 0.02 and 0.1 mg/kg fresh weight (0.5, 0.5 and 16 mg/kg lipid weight), respectively. The detection of higher levels of p,p'-DDT than the degradation products (p,p'-DDD and p,p'-DDE), and higher levels of endosulfan isomers ({alpha} and {beta}) than the sulphate, in fish samples, implied recent exposure of fish to DDT and endosulfan, respectively. Generally, most of the fish samples had residue levels above the average method detection limits (MDLs), but were within the calculated ADI. - Fish from Lake Victoria had relatively low pesticide levels.

  19. Pesticide bioconcentration modelling for fruit trees.

    Paraíba, Lourival Costa

    2007-01-01

    The model presented allows simulating the pesticide concentration evolution in fruit trees and estimating the pesticide bioconcentration factor in fruits. Pesticides are non-ionic organic compounds that are degraded in soils cropped with woody species, fruit trees and other perennials. The model allows estimating the pesticide uptake by plants through the water transpiration stream and also the time in which maximum pesticide concentration occur in the fruits. The equation proposed presents the relationships between bioconcentration factor (BCF) and the following variables: plant water transpiration volume (Q), pesticide transpiration stream concentration factor (TSCF), pesticide stem-water partition coefficient (K(Wood,W)), stem dry biomass (M) and pesticide dissipation rate in the soil-plant system (k(EGS)). The modeling started and was developed from a previous model "Fruit Tree Model" (FTM), reported by Trapp and collaborators in 2003, to which was added the hypothesis that the pesticide degradation in the soil follows a first order kinetic equation. The FTM model for pesticides (FTM-p) was applied to a hypothetic mango plant cropping (Mangifera indica) treated with paclobutrazol (growth regulator) added to the soil. The model fitness was evaluated through the sensitivity analysis of the pesticide BCF values in fruits with respect to the model entry data variability.

  20. Simulating pesticide transport in urbanized catchments: a new spatially-distributed dynamic pesticide runoff model

    Tang, Ting; Seuntjens, Piet; van Griensven, Ann; Bronders, Jan

    2016-04-01

    Urban areas can significantly contribute to pesticide contamination in surface water. However, pesticide behaviours in urban areas, particularly on hard surfaces, are far less studied than those in agricultural areas. Pesticide application on hard surfaces (e.g. roadsides and walkways) is of particular concern due to the high imperviousness and therefore high pesticide runoff potential. Experimental studies have shown that pesticide behaviours on and interactions with hard surfaces are important factors controlling the pesticide runoff potential, and therefore the magnitude and timing of peak concentrations in surface water. We conceptualized pesticide behaviours on hard surfaces and incorporated the conceptualization into a new pesticide runoff model. The pesticide runoff model was implemented in a catchment hydrological model WetSpa-Python (Water and Energy Transfer between Soil, Plants and Atmosphere, Python version). The conceptualization for pesticide processes on hard surfaces accounts for the differences in pesticide behaviour on different hard surfaces. Four parameters are used to describe the partitioning and wash-off of each pesticide on hard surfaces. We tested the conceptualization using experimental dataset for five pesticides on two types of hard surfaces, namely concrete and asphalt. The conceptualization gave good performance in accounting for the wash-off pattern for the modelled pesticides and surfaces, according to quantitative evaluations using the Nash-Sutcliffe efficiency and percent bias. The resulting pesticide runoff model WetSpa-PST (WetSpa for PeSTicides) can simulate pesticides and their metabolites at the catchment scale. Overall, it includes four groups of pesticide processes, namely pesticide application, pesticide interception by plant foliage, pesticide processes on land surfaces (including partitioning, degradation and wash-off on hard surface; partitioning, dissipation, infiltration and runoff in soil) and pesticide processes in

  1. Pesticides in the propolis at São Saulo State, Brazil=Pesticidas na própolis do Estado de São Paulo, Brasil

    Silvia Maria Alves Gomes

    2012-10-01

    Full Text Available The increasing demand for propolis has caused a raise in its production. However, an increasingly pesticide-dependent agriculture is a great concern with regard to bees, their produce and environmental contamination. Current analysis evaluates the presence of pesticides (organochlorines, organophosphates, pyrethroids, carbamates, herbicides, fungicides and acaricides in samples of propolis from the state of São Paulo, Brazil. Beekeepers from several localities in the state provided samples of propolis (50, which were collected, stored in non-toxic plastic bags and maintained in a freezer for analyses. Possible pesticide residues were examined by gas chromatography method but no pesticide residues were detected in the examined propolis samples. Propolis analyzed in the state of São Paulo did not show any pesticide contamination.A crescente procura pela própolis tem ocasionado aumento em sua produção. Entretanto, uma agricultura cada vez mais dependente de pesticidas representa preocupação com relação à contaminação ambiental, além das abelhas e seus produtos. Neste sentido, a proposta do presente trabalho foi avaliar a presença de pesticidas (organoclorados, organofosforados, piretroides, carbamatos, herbicidas, fungicidas e acaricidas em amostras de própolis do Estado de São Paulo. Apicultores de diversas localidades do Estado forneceram amostras de própolis (50. Estas foram coletadas, armazenadas em sacos plásticos atóxicos e mantidas em freezer até as análises. Os possíveis resíduos de pesticidas foram analisados por cromatografia gasosa. Não foi observada a presença dos pesticidas analisados nas amostras. Neste caso, a própolis analisada no Estado de São Paulo não apresentou contaminação por pesticidas.

  2. Pesticides, People, and the Environment

    Miller, Roxanne Greitz

    2005-01-01

    If a teacher were to ask his/her students what they do when they find ants or other insects in their homes, their most common response would probably be, "Get the bug spray!" Because students are not only being exposed to pesticides but are also developing patterns of behavior likely to continue throughout their lives. Discussions about…

  3. Chiral Synthons in Pesticide Syntheses

    Feringa, Bernard

    1988-01-01

    The use of chiral synthons in the preparation of enantiomerically pure pesticides is described in this chapter. Several routes to chiral synthons based on asymmetric synthesis or on natural products are illustrated. Important sources of chiral building blocks are reviewed. Furthermore the implicatio

  4. Validação de método para determinação de resíduos de agrotóxicos em tomate: uma experiência laboratorial Method validation for determination of pesticide residues in tomatoes: a laboratorial experience

    Maria Helena Wohlers Morelli Cardoso

    2010-05-01

    Full Text Available Um modelo de procedimento para validação de método de ensaio para determinação de cinco agrotóxicos (γ - HCH, clorotalonil, fenitrotiona, clorpirifós e procimidona em matriz tomate é demonstrado através da análise cromatográfica. A amostra processada é extraída com 30 mL de acetona e em seguida com 60 mL de uma mistura diclometano: éter de petróleo (1:1. O volume total é centrifugado e a alíquota orgânica é filtrada sob Na2SO4. Um mililitro de extrato orgânico é concentrado e dissolvido em um mililitro de iso-octano. Um microlitro do extrato é analisado no cromatógrafo a gás com detector por captura de elétrons - CG/DCE. Foram avaliados seletividade, linearidade, repetitividade, recuperação e limites de detecção e de quantificação. As recuperações obtidas variaram de 70 a 110%, considerando-se os níveis de adição de agrotóxicos/amostra de 0,02 a 2,50 mg.kg-1. Os limites de detecção do método variaram de 0,004 a 0,006 mg.kg-1 e os de quantificação entre 0,014 e 0,020 mg.kg-1.A validation procedure model of a multiresidue method is presented for chromatographic analyses of five pesticides residues γ-HCH, chlorothalonil, fenitrothion, chlorpyrifos and procymidone applied on tomatoes. The tomatoes were processed and extracted by acetone plus a mixture of dichloromethane:petroleum benzine (1:1. The volume was centrifuged and was then filtered under Na2SO4. One milliliter of organic extract was concentrated then diluted in isooctane and one microliter was analyzed in the gas chromatograph with electron capture detector - GC/ECD. The parameters evaluated were selectivity, linearity, repeatability, recovery, and limits of detection and quantification. The recovery ranged from 70 to 110% in the concentration range of 0.02 to 2.50 mg.kg-1. The limits of detection ranged from 0.004 to 0.006 mg.kg-1 and the limits of quantification were between 0.014 to 0.02 mg.kg-1.

  5. Multiresidue Analysis of Pesticides in Soil by Liquid-Solid Extraction Procedure

    Rada Đurović

    2012-01-01

    Full Text Available A multiresidue method for simultaneous determination of four pesticides (diazinon,acetochlor, aldrine and carbofuran belonging to different pesticide groups, extractedfrom soil samples, is described. The method presented is based on liquid-solid extraction(LSE and determination of pesticides, i.e. the pesticides were extracted by methanol-acetone mixture, purified on florisil column and eluted by ethyl acetate-acetone mixture.Optimization of the main parameters affecting the LSE procedure, such as the choiceof purification sorbent, as well as the elution solvent and its volume, were investigated indetails and optimized. Also, validation of the proposed method was done.Gas chromatography-mass spectrometry (GC-MS was used for detection and quantificationof the pesticides studied. Relative standard deviation (RSD and recovery values formultiple analysis of soil samples fortified with 30 μg/kg of each pesticide were below 8%and higher than 89%, respectively. Limits of detection (LOD for all the compounds studiedwere less than 4 μg/kg.

  6. Pesticide exposure and risk of Alzheimer’s disease: a systematic review and meta-analysis

    Yan, Dandan; Zhang, Yunjian; Liu, Liegang; Yan, Hong

    2016-09-01

    Evidence suggests that lifelong cumulative exposure to pesticides may generate lasting toxic effects on the central nervous system and contribute to the development of Alzheimer’s disease (AD). A number of reports indicate a potential association between long-term/low-dose pesticide exposure and AD, but the results are inconsistent. Therefore, we conducted a meta-analysis to clarify this association. Relevant studies were identified according to inclusion criteria. Summary odds ratios (ORs) were calculated using fixed-effects models. A total of seven studies were included in our meta-analysis. A positive association was observed between pesticide exposure and AD (OR = 1.34 95% confidence interval [CI] = 1.08, 1.67; n = 7). The summary ORs with 95% CIs from the crude and adjusted effect size studies were 1.14 (95% CI = 0.94, 1.38; n = 7) and 1.37 (95% CI = 1.09, 1.71; n = 5), respectively. The sensitivity analyses of the present meta-analysis did not substantially modify the association between pesticide exposure and AD. Subgroup analyses revealed that high-quality studies tended to show significant relationships. The present meta-analysis suggested a positive association between pesticide exposure and AD, confirming the hypothesis that pesticide exposure is a risk factor for AD. Further high-quality cohort and case-control studies are required to validate a causal relationship.

  7. Use of job-exposure matrices to estimate occupational exposure to pesticides: A review.

    Carles, Camille; Bouvier, Ghislaine; Lebailly, Pierre; Baldi, Isabelle

    2017-03-01

    The health effects of pesticides have been extensively studied in epidemiology, mainly in agricultural populations. However, pesticide exposure assessment remains a key methodological issue for epidemiological studies. Besides self-reported information, expert assessment or metrology, job-exposure matrices still appear to be an interesting tool. We reviewed all existing matrices assessing occupational exposure to pesticides in epidemiological studies and described the exposure parameters they included. We identified two types of matrices, (i) generic ones that are generally used in case-control studies and document broad categories of pesticides in a large range of jobs, and (ii) specific matrices, developed for use in agricultural cohorts, that generally provide exposure metrics at the active ingredient level. The various applications of these matrices in epidemiological studies have proven that they are valuable tools to assess pesticide exposure. Specific matrices are particularly promising for use in agricultural cohorts. However, results obtained with matrices have rarely been compared with those obtained with other tools. In addition, the external validity of the given estimates has not been adequately discussed. Yet, matrices would help in reducing misclassification and in quantifying cumulated exposures, to improve knowledge about the chronic health effects of pesticides.

  8. Formation of a unique zinc carbamate by CO2 fixation: implications for the reactivity of tetra-azamacrocycle ligated Zn(II) complexes.

    Notni, Johannes; Schenk, Stephan; Görls, Helmar; Breitzke, Hergen; Anders, Ernst

    2008-02-18

    The macrocyclic ligand [13]aneN 4 ( L1, 1,4,7,10-tetra-azacyclotridecane) was reacted with Zn(II) perchlorate and CO 2 in an alkaline methanol solution. It was found that, by means of subtle changes in reaction conditions, two types of complexes can be obtained: (a) the mu 3 carbonate complex 1, {[Zn( L1)] 3(mu 3-CO 3)}(ClO 4) 4, rhombohedral crystals, space group R3 c, with pentacoordinate zinc in a trigonal bipyramidal enviroment, and (b) an unprecedenced dimeric Zn(II) carbamate structure, 2, [Zn( L2)] 2(ClO 4) 2, monoclinic crystals, space group P2 1/ n. The ligand L2 (4-carboxyl-1,4,7,10-tetra-azacyclotridecane) is a carbamate derivative of L1, obtained by transformation of a hydrogen atom of one of the NH moieties into carbamate by means of CO 2 uptake. In compound 2, the distorted tetrahedral Zn(II) coordinates to the carbamate moiety in a monodentate manner. Most notably, carbamate formation can occur upon reaction of CO 2 with the [Zn L1] (2+) complex, which implicates that a Zn-N linkage is cleaved upon attack of CO 2. Since complexes of tetra-azamacrocycles and Zn(II) are routinely applied for enzyme model studies, this finding implies that the Zn-azamacrocycle moiety generally should no longer be considered to play always only an innocent role in reactions. Rather, its reactivity has to be taken into account in respective investigations. In the presence of water, 2 is transformed readily into carbonate 1. Both compounds have been additionally characterized by solid-state NMR and infrared spectroscopy. A thorough comparison of 1 with related azamacrocycle ligated zinc(II) carbonates as well as a discussion of plausible reaction paths for the formation of 2 are given. Furthermore, the infrared absorptions of the carbamate moiety have been assigned by calculating the vibrational modes of the carbamate complex using DFT methods and the vibrational spectroscopy calculation program package SNF.

  9. Pesticides and their effects on wildlife

    Driver, C.J.

    1994-07-01

    About 560 active ingredients are currently used as pesticides. Applications of these pesticides are made to agricultural lands and other areas inhabited by wildlife. Unfortunately, many agricultural-use pesticides also entail some measure of risk to organisms other than the pest species. Because testing of pesticides prior to registration cannot evaluate all the potential environmental-pesticide-wildlife/fish interactions, current methods of risk assessment do not always provide sufficient safety to nontarget organisms. This is evidenced by die-offs of fish and wildlife from applications of pesticides at environmentally {open_quotes}safe{close_quotes} rates, the linking of population declines of some species with agrochemical use, and observations of survival-threatening behavioral changes in laboratory and field animals exposed to typical field levels of pesticides. It is important to note, however, that the majority of pesticides, when properly applied, have not caused significant injury to wildlife. A brief summary of pesticide effects on wildlife and fish are presented for the common classes of pesticides in use today.

  10. Evidence of carbamate resistance in urban populations of Anopheles gambiae s.s. mosquitoes resistant to DDT and deltamethrin insecticides in Lagos, South-Western Nigeria

    Oduola Adedayo O

    2012-06-01

    Full Text Available Abstract Background Resistance monitoring is essential in ensuring the success of insecticide based vector control programmes. This study was carried out to assess the susceptibility status of urban populations of Anopheles gambiae to carbamate insecticide being considered for vector control in mosquito populations previously reported to be resistant to DDT and permethrin. Methods Two – three day old adult female Anopheles mosquitoes reared from larval collections in 11 study sites from Local Government Areas of Lagos were exposed to test papers impregnated with DDT 4%, deltamethrin 0.05% and propoxur 0.1% insecticides. Additional tests were carried out to determine the susceptibility status of the Anopheles gambiae population to bendiocarb insecticide. Members of the A. gambiae complex, the molecular forms, were identified by PCR assays. The involvement of metabolic enzymes in carbamate resistance was assessed using Piperonyl butoxide (PBO synergist assays. The presence of kdr-w/e and ace-1R point mutations responsible for DDT-pyrethroid and carbamate resistance mechanisms was also investigated by PCR. Results Propoxur resistance was found in 10 out of the 11 study sites. Resistance to three classes of insecticides was observed in five urban localities. Mortality rates in mosquitoes exposed to deltamethrin and propoxur did not show any significant difference (P > 0.05 but was significantly higher (P A. gambiae s.s (M form. The kdr -w point mutation at allelic frequencies between 45%-77% was identified as one of the resistant mechanisms responsible for DDT and pyrethroid resistance. Ace-1R point mutation was absent in the carbamate resistant population. However, the possible involvement of metabolic resistance was confirmed by synergistic assays conducted. Conclusion Evidence of carbamate resistance in A. gambiae populations already harbouring resistance to DDT and permethrin is a clear indication that calls for the implementation of

  11. Synthesis and reactivity of cyclic-carbamate derivatives%环状氨基甲酸酯衍生物的合成及反应研究

    王静; 郭爽; 王家喜

    2011-01-01

    Cyclic carbamate has been prepared by the reaction of ethanolamine with dimethyl carbonate as raw material and zinc acetate as catalyst. The cyclic carbamate reacted with methyl acrylate producing methyl 3- (2-oxo-oxazolidin-3-yl) propanoate, which reacted with n-butylamine and 1,6-hexanediamine to give mono and bis cyclic carbamate derivatives. The attack of amine to carbonyl of heterocyclic ring of carbamate produced the hydroxylethyl substituted urea, while the attack to carbon-oxygen bond generated carbamic acid, which further underwent dehydration forming cyclic urea and/or de-carbon dioxide forming polyamine. The products were characterized by NMR and FT-IR. The reaction mechanism is finally proposed.%以乙醇胺和碳酸二甲酯为原料,在醋酸锌的催化下合成环状氨基甲酸酯,与丙烯酸甲酯反应制备3-(2-噁唑烷酮)丙酸甲酯,在K2CO3催化下进一步与正丁胺、1,6-己二胺发生酰胺化反应,得到了单、双环状氨基甲酸酯衍生物.有机胺与环状氨基甲酸酯的羰基反应形成羟乙基取代脲,与烷氧基反应形成开环的胺基甲酸,该化合物进一步脱水形成环状脲,脱二氧化碳形成多胺化合物.用NMR和红外谱图对开环产物进行表征,并初步探讨了其反应历程.

  12. 氨基甲酸酯淀粉浆料的制备及上浆性能%Manufacture and Sizing Performance of Carbamate Starch Size Mixture

    刘志军; 许冬生

    2011-01-01

    探讨氨基甲酸酯淀粉的取代度对氨基甲酸酯淀粉浆料上浆性能的影响.通过改变氧化铵对淀粉的投料比,制备了一系列具有不同变性程度的氨基甲酸酯淀粉,对不同取代度的氨基甲酸酯淀粉浆料的浆液性能及对棉纤维的黏附性能进行了测试.结果表明:当取代度不超过0.053时,随氨基甲酸酯淀粉取代度的提高,浆液黏度降低,热稳定性提高,对棉纤维的黏着力增大.指出:氨基甲酸酯变性有利于改善淀粉对纯棉经纱的上浆性能.%Effect of carbamate starch substitution degree on size mixture property was discussed. Through changing feed ratio of ammonium chloride to starch,a series of carbamate starch with different substitution degree were made. Sizing property of carbamate starch with different substitution degree and adhesion performance to cotton fiber were tested. The result shows when the substitution degree is less 0. 053 and substitution degree of carbamate starch is increasing,sizing viscosity is reduced, the thermal stability is increased, the adhesion to cotton fiber is increased. It is pointed out that sizing property of carbamate starch to pure cotton yarn can be improved.

  13. The use and disposal of household pesticides.

    Grey, Charlotte N B; Nieuwenhuijsen, Mark J; Golding, Jean

    2005-01-01

    Most pesticides are synthetic chemicals manufactured specifically for their toxic properties to the target species, and widely used globally. Several epidemiological studies in the United States have suggested health concerns arising from the chronic exposure of young children to pesticides in the domestic environment. In the UK very little is currently known about how nonoccupational pesticides are being used or disposed of. Any use of pesticides is a potential risk factor for children's exposure, and any potential exposure is likely to be reduced by the parents' adopting precautionary behaviour when using these pesticide products. This was investigated using a sample of 147 parents from the Avon Longitudinal Study of Parents and Children cohort in and around Bristol, through an in-depth interview between August and November 2001. The results of this study add to the understanding of the underlying behaviour of parents applying pesticide products in the home environment in the UK. Pesticides are readily available, and are normally purchased in do-it-yourself shops and supermarkets and mostly disposed of in domestic waste. Safety was stated by 45% of parents to be the most important factor to consider when buying a pesticide. When buying pesticide products, labels were stated to be the most important source of information about pesticides. However, a third of parents stated they would not follow the product label exactly when using a product, just under half felt labels were both inadequate and hard to understand, and about 10% of parents would not take notice of warnings on the pesticide label. Less than half of parents would use gloves when applying a pesticide, although the use of protective equipment such as gloves during the application of pesticides could greatly reduce the exposure. It is a public health concern that the instructions on the labels of products may not always be understood or followed, and further understanding of user behaviour is needed.

  14. Exposure to non-persistent pesticides and thyroid function: A systematic review of epidemiological evidence.

    Campos, Élida; Freire, Carmen

    2016-08-01

    Numerous pesticides are recognized for their endocrine-disrupting properties. Non-persistent pesticides such as organophosphates, dithiocarbamates and pyrethroids may interfere with thyroid function as suggested by animal studies. However, the influence of chronic exposure to these compounds on thyroidal functions in humans remains to be determined. The present study aimed to review epidemiological evidence for an association between exposure to non-persistent pesticides and circulating levels of thyroid hormones (thyroxin [T4] and triiodothyronine [T3]) and thyroid-stimulating hormone (TSH). A systematic review was conducted using MEDLINE, SCOPUS and Virtual Health Library (BVS) databases. Articles were limited to original studies and reports published in English, Portuguese or Spanish. Nineteen epidemiological studies were identified, 17 of which were cross-sectional, 14 were of occupationally exposed workers and 11 used exposure biomarkers. Fungicides and organophosphates (OP) insecticides were the most studied pesticides. Although methodological heterogeneity between studies was noted, particularly regarding study design, exposure assessment, and control of confounding, most of them showed associations with changes in T3 and T4, and/or TSH levels, while results from a few of these are consistent with experimental data supporting the findings that non-persistent pesticide exposure exerts hypothyroid-like effects. However, reporting quality was moderate to poor in 50% of the studies, particularly regarding method of selection of participants and discussion of external validity. Overall, current knowledge regarding the impact of non-persistent pesticides on human thyroid function is still limited. Given the widespread use of pesticides, future research should assess effects of exposure to currently-used pesticides in cohort studies combining comprehensive questionnaire-based assessment and biomarkers. Investigators need to pay particular attention to exposure

  15. [Use of bioindicators for assessing and monitoring pesticides contamination in streams and rivers].

    Arias, Ana Rosa Linde; Buss, Daniel Forsin; de Alburquerque, Carla; Inácio, Alan Ferreira; Freire, Marina Moreira; Egler, Mariana; Mugnai, Riccardo; Baptista, Darcilio Fernandes

    2007-01-01

    The objective of this article is to present an analysis of the main bioindicators that are currently used to assess the environmental impact of pollution in water resources. The simple quantification of chemicals in the environment is not enough to reveal the real effects of contamination on ecosystems, making necessary the assessment of the biological effects that pollution causes at different hierarchical levels. The bioindicators used in this article on two case studies comprehend different hierarchical levels: in case study 1, three organization levels were utilized: individual, cellular and molecular, to detect the early effects of exposition to environmental pollutants in three hydrographic basins. By observing the inhibition of AChE activity in fish it was possible to assess the effects of organophosphorate and carbamate pesticides, showing the effects of agricultural activities. In case study 2, we present an assessment at the macroinvertebrate community level using the Extended Biotic Index. We discuss the advantages and limitations in the production of reliable data that could be used in the implementation of adequate actions to protect and/or recover ecosystems.

  16. Effects of film mulch and soil pesticides on nematodes, weeds, and yields of vegetable crops.

    Johnson, A W; Jaworski, C A; Glaze, N C; Sumner, D R; Chalfant, R B

    1981-04-01

    Field plots in Tifton loamy sand were treated with various soil pesticides in 1973 and 1974 and either left exposed or covered with biodegradable flint mulch. Test crops were cantaloup, slicing and pickling cucumber, squash, and sweet corn. Overhead sprinkler irrigation was used in 1973, and trickle irrigation under the film mulch was used on sweet corn in 1974. Soil was assayed for nematodes, and roots of plants were evaluated for damage by root-knot nematodes. Nematode populations were reduced by soil treatment with an organic phosphate or carbamate nematicide-herbicide-fungicide combination (NHF), DD-MENCS, methyl bromide-chloropicrin (MBR-CP), ethoprop, carbofuran, and sodium azide + ethoprop or carbofuran. Sodium azide, sodium azide + ethoprop or carbofuran, ethoprop, and carbofuran were less effective than DD-MENCS, MBR-CP, attd the NHF combination. The NHF combination controlled grasses and broadteaf weeds as effectively as the herbicide alone. Growth and yield were greatest when nematodes and weeds were controlled. Yields of marketable vegetables were highest from plants in plots treated with DD-MENCS with a film mulch.

  17. Analysis on monitoring results of multi-pesticide residues in vegetables in Anshan City in 2011%2011年鞍山市蔬菜中多种农药残留监测结果分析

    李晨光; 魏欧

    2013-01-01

    目的 了解鞍山市蔬菜食品中有机磷、氨基甲酸酯及拟除虫菊酯农药残留的情况.方法 按GB/T 5009-2003《食品卫生检验方法理化部分》检测有机磷、氨基甲酸酯及拟除虫菊酯农药残留量.结果 100份蔬菜中检出甲胺磷农药残留4份,乙酰甲胺磷农药残留4份,毒死蜱农药残留10份,克百威农药残留6份,灭多威农药残留20份,氯氰菊酯农药残留14份,氯氟氰菊酯农药残留2份,均无超标样品.结论 鞍山市蔬菜中农药残留水平较低.%[Objective]To know the condition of residues of organophosphorous pesticide, carbamate and pyrethroid in vegetables in Anshan City. [ Methods]The contents of residues of organophosphorous pesticide, carbamate and pyrethroid were detected according to the Methods of food hygienic analysis-Physical and chemical section ( GB/T 5009-2003). [Results] Among 100 samples of vegetables, there were 4 samples of methamidophos residue, 4 samples of acephate residue, 10 samples of chlorpyrifos residue, 6 samples of carbofuran residue, 20 samples of methomyl residue, 14 samples of cypermethrin residue and 2 samples of cyhalothrin residue, while no over standard samples were found. [ Conclusion] The level of pesticide residues in vegetables is low in Anshan City.

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

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

    2016-02-26

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

  19. Fate of pesticides during beer brewing.

    Inoue, Tomonori; Nagatomi, Yasushi; Suga, Keiko; Uyama, Atsuo; Mochizuki, Naoki

    2011-04-27

    The fates of more than 300 pesticide residues were investigated in the course of beer brewing. Ground malt artificially contaminated with pesticides was brewed via steps such as mashing, boiling, and fermentation. Analytical samples were taken from wort, spent grain, and beer produced at certain key points in the brewing process. The samples were extracted and purified with the QuEChERS (Quick Easy Cheap Effective Rugged and Safe) method and were then analyzed by LC-MS/MS using a multiresidue method. In the results, a majority of pesticides showed a reduction in the unhopped wort and were adsorbed onto the spent grain after mashing. In addition, some pesticides diminished during the boiling and fermentation. This suggests that the reduction was caused mainly by adsorption, pyrolysis, and hydrolysis. After the entire process of brewing, the risks of contaminating beer with pesticides were reduced remarkably, and only a few pesticides remained without being removed or resolved.

  20. Antibiotic, Pesticide, and Microbial Contaminants of Honey: Human Health Hazards

    Noori Al-Waili

    2012-01-01

    Full Text Available Agricultural contamination with pesticides and antibiotics is a challenging problem that needs to be fully addressed. Bee products, such as honey, are widely consumed as food and medicine and their contamination may carry serious health hazards. Honey and other bee products are polluted by pesticides, heavy metals, bacteria and radioactive materials. Pesticide residues cause genetic mutations and cellular degradation and presence of antibiotics might increase resistant human or animal's pathogens. Many cases of infant botulisms have been attributed to contaminated honey. Honey may be very toxic when produced from certain plants. Ingestion of honey without knowing its source and safety might be problematic. Honey should be labeled to explore its origin, composition, and clear statement that it is free from contaminants. Honey that is not subjected for analysis and sterilization should not be used in infants, and should not be applied to wounds or used for medicinal purposes. This article reviews the extent and health impact of honey contamination and stresses on the introduction of a strict monitoring system and validation of acceptable minimal concentrations of pollutants or identifying maximum residue limits for bee products, in particular, honey.

  1. Anthelmintic profile of methyl 5(6)-(4-methylpiperidin-1-yl) carbonylbenzimidazole-2-carbamate in experimental helminthiases.

    Gupta, S; Khan, A M; Jain, M K; Katiyar, J C; Naim, S S; Singh, S K; Sharma, S

    1990-05-01

    Biological evaluation of methyl 5(6)-(4-methylpiperidin-1-yl) carbonylbenzimidazole-2-carbamate against Ancylostoma ceylanicum, Nippostrongylus brasiliensis, Syphacia obvelata, Hymenolepis nana, H. diminuta and Cysticercus fasciolaris in experimental animals is reported. The compound (mg/kg) causes 100% elimination of A. ceylanicum (25 x 1), N. brasiliensis (100 x 1), S. obvelata (50 x 1), H. nana (250 x 3) and C. fasciolaris (50 x 10). It was also effective against the developing larvae (L3, L4 and L5) of A. ceylanicum at a single oral dose of 100 mg/kg. Another study indicated that the compound elicits 100% response within 32 hr of drug administration. The drug is well tolerated and LD50 is greater than 4500 mg/kg.

  2. The arginine deiminase pathway of koji bacteria is involved in ethyl carbamate precursor production in soy sauce.

    Zhang, Jiran; Fang, Fang; Chen, Jian; Du, Guocheng

    2014-09-01

    Ethyl carbamate (EC) is a group 2A carcinogen generated from a few precursors in many fermented foods and alcoholic beverages. Citrulline, urea, carbamoyl phosphate, and ethanol are common precursors detected in fermented foods. In this study, citrulline was proved to be the main EC precursor in soy sauce, which was found to be accumulated in moromi mash period and correlated with the utilization of arginine by koji bacteria. Six koji isolates belonging to three genera were identified to be able to accumulate citrulline via the arginine deiminase (ADI) pathway. Among these strains, only Pediococcus acidilactici retained high activities in synthesis and accumulation of citrulline in the presence of high concentration of sodium chloride. These results suggested that P. acidilactici is responsible for the accumulation of citrulline, one of the EC precursors, in the process of soy sauce fermentation.

  3. Chelation-Assisted Substrate-Controlled Asymmetric Lithiation-Allylboration of Chiral Carbamate 1,2,4-Butanetriol Acetonide

    Adeem Mahmood

    2015-05-01

    Full Text Available The lithiation of 2-(2,2-dimethyl-1,3-dioxolan-4-ylethyl diisopropylcarbamate (1 is achieved freely by sec-butyllithium in diethylether with high lk-diastereoselectivity: the bicyclic chelate complexes 3a and 3b are reacted with electrophiles to form optically active precursors 4a and 4b with >95% diastereoselectivity. In addition, tertiary diamines can undergo an external complexation in contest with the internal oxygen ligand, leading to improved stereoselectivities. The further reactions of lithiated carbamates with trans alkenyl-9-BBN derivatives after 1,2 metallate rearrangements, gave the key intermediate α-substituted allylic boranes 7. Subsequent allylboration of aldehydes gave (Z-anti-homoallylic alcohols 8 in good yield and excellent d.r.

  4. Enantioseparation of Neutral Compounds on a Quinine Carbamate-Immobilized Zirconia in Reversed-Phase Capillary Electrochromatography

    Lee, Mun Rak; Gwon, Ju Rim; Park, Jung Hag [Yeungnam University, Gyeongsan (Korea, Republic of)

    2010-01-15

    Quinine (QN) is a weak anion-exchange type chiral selector and QN-based silica stationary phases have been widely used for enantioseparation of acidic chiral analytes in HPLC and recently in CEC. In this work we report enantioseparation of non-acidic chiral analytes on a quinine carbamate-immobilized zirconia (QNZ) in reversed-phase (RP) CEC. Influences of pH, composition of the buffer, acetonitrile content and the applied voltage on enantioseparation were examined. Enantiomers of the analytes investigated are well separated in acetonitrile/phosphate buffer mobile phases. Separation data on QNZ were compared to those on QN-bonded silica (QNS). Retention was longer but better enantioselectivity and resolution were obtained on QNZ than QNS.

  5. Ethyl Carbamate in Alcoholic Beverages from Mexico (Tequila, Mezcal, Bacanora, Sotol and Guatemala (Cuxa: Market Survey and Risk Assessment

    Jürgen Rehm

    2009-01-01

    Full Text Available Ethyl carbamate (EC is a recognized genotoxic carcinogen, with widespread occurrence in fermented foods and beverages. No data on its occurrence in alcoholic beverages from Mexico or Central America is available. Samples of agave spirits including tequila, mezcal, bacanora and sotol (n=110, and of the sugarcane spirit cuxa (n=16 were purchased in Mexico and Guatemala, respectively, and analyzed for EC. The incidence of EC contamination was higher in Mexico than in Guatemala, however, concentrations were below international guideline levels (<0.15 mg/L. Risk assessment found the Margin of Exposure (MOE in line with that of European spirits. It is therefore unlikely that EC plays a role in high rates of liver cirrhosis reported in Mexico.

  6. Ethyl carbamate in alcoholic beverages from Mexico (tequila, mezcal, bacanora, sotol) and Guatemala (cuxa): market survey and risk assessment.

    Lachenmeier, Dirk W; Kanteres, Fotis; Kuballa, Thomas; López, Mercedes G; Rehm, Jürgen

    2009-01-01

    Ethyl carbamate (EC) is a recognized genotoxic carcinogen, with widespread occurrence in fermented foods and beverages. No data on its occurrence in alcoholic beverages from Mexico or Central America is available. Samples of agave spirits including tequila, mezcal, bacanora and sotol (n=110), and of the sugarcane spirit cuxa (n=16) were purchased in Mexico and Guatemala, respectively, and analyzed for EC. The incidence of EC contamination was higher in Mexico than in Guatemala, however, concentrations were below international guideline levels (<0.15 mg/L). Risk assessment found the Margin of Exposure (MOE) in line with that of European spirits. It is therefore unlikely that EC plays a role in high rates of liver cirrhosis reported in Mexico.

  7. Influence of Solvent on Reaction Path to Synthesis of Methyl N-Phenyl Carbamate from Aniline, CO2 and Methanol

    安华良; 张丽丽; 苑保国; 赵新强; 王延吉

    2014-01-01

    Methyl N-phenyl carbamate (MPC), an important organic chemical, can be synthesized from aniline, CO2 and methanol. Catalyst Cu-Fe/ZrO2-SiO2 was first prepared and its catalytic performance for MPC synthesis was evaluated. Then the influence of solvent on the reaction path of MPC synthesis was investigated. It is found that the reaction intermediate is different with acetonitrile or methanol as a solvent. With acetonitrile as a solvent, the synthesis of MPC follows the reaction path with diphenyl urea as the intermediate, while with methanol as a solvent the reaction occurs via the reaction path with dimethyl carbonate as the intermediate. The catalytic mecha-nism of cooperative catalysis comprising metal sites, Lewis acid sites and Lewis base sites is proposed according to different reaction intermediates.

  8. A mobile App for military operational entomology pesticide applications

    Multiple field studies conducted for the Deployed War Fighter Protection (DWFP) research program have generated over 80 specific guidance points for innovative combinations of pesticide application equipment, pesticide formulations, and application techniques for aerosol and residual pesticide treat...

  9. AFFINITY OF THE ALLIGATOR ESTROGEN RECEPTOR FOR SERUM PESTICIDE CONTAMINANTS

    Top predators, like the American alligator (Alligator mississippiensis) bioaccumulate and biomagnify persistent pollutants, such as organochlorine pesticides. In a recently published study, several pesticides and pesticide metabolites not previously reported in alligator eggs wer...

  10. Effect of Endocrine Disruptor Pesticides: A Review

    Benoit Roig; Olivier Thomas; Aghleb Bartegi; Wissem Mnif; Aicha Bouaziz; Aziza Ibn Hadj Hassine

    2011-01-01

    International audience; Endocrine disrupting chemicals (EDC) are compounds that alter the normal functioning of the endocrine system of both wildlife and humans. A huge number of chemicals have been identified as endocrine disruptors, among them several pesticides. Pesticides are used to kill unwanted organisms in crops, public areas, homes and gardens, and parasites in medicine. Human are exposed to pesticides due to their occupations or through dietary and environmental exposure (water, soi...

  11. The enzymatic basis for pesticide bioremediation

    Scott, Colin; Pandey, Gunjan; Hartley, Carol J.; Jackson, Colin J.; Cheesman, Matthew J.; Taylor, Matthew C.; Pandey, Rinku; Khurana, Jeevan L.; Teese, Mark; Coppin, Chris W; Weir, Kahli M.; Jain, Rakesh K.; Lal, Rup; Russell, Robyn J.; Oakeshott, John G.

    2008-01-01

    Enzymes are central to the biology of many pesticides, influencing their modes of action, environmental fates and mechanisms of target species resistance. Since the introduction of synthetic xenobiotic pesticides, enzymes responsible for pesticide turnover have evolved rapidly, in both the target organisms and incidentally exposed biota. Such enzymes are a source of significant biotechnological potential and form the basis of several bioremediation strategies intended to reduce the environmen...

  12. Analytical methods for detecting pesticide switches with evolution of pesticide resistance.

    Liang, Juhua; Tang, Sanyi; Nieto, Juan J; Cheke, Robert A

    2013-10-01

    After a pest develops resistance to a pesticide, switching between different unrelated pesticides is a common management option, but this raises the following questions: (1) What is the optimal frequency of pesticide use? (2) How do the frequencies of pesticide applications affect the evolution of pesticide resistance? (3) How can the time when the pest population reaches the economic injury level (EIL) be estimated and (4) how can the most efficient frequency of pesticide applications be determined? To address these questions, we have developed a novel pest population growth model incorporating the evolution of pesticide resistance and pulse spraying of pesticides. Moreover, three pesticide switching methods, threshold condition-guided, density-guided and EIL-guided, are modelled, to determine the best choice under different conditions with the overall aim of eradicating the pest or maintaining its population density below the EIL. Furthermore, the pest control outcomes based on those three pesticide switching methods are discussed. Our results suggest that either the density-guided or EIL-guided method is the optimal pesticide switching strategy, depending on the frequency (or period) of pesticide applications.

  13. Pesticides: Benefaction or Pandora's Box? A synopsis of the environmental aspects of 243 pesticides

    Linders JBHJ; Jansma JW; Mensink BJWG; Otermann K; ACT

    1994-01-01

    The report provides an overview of physical, chemical and environmental data of 243 pesticides. The data mentioned are based on confidential information supplied by the manufacturers of the pesticides. For all pesticides mentioned a Final Environmental File, which is public, is derived. Tables with

  14. 75 FR 74673 - Pesticides; Regulation To Clarify Labeling of Pesticides for Export; Notification to the...

    2010-12-01

    ... AGENCY 40 CFR Part 168 RIN 2070-AJ53 Pesticides; Regulation To Clarify Labeling of Pesticides for Export...(a) of the Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA). As described in the Agency's... specificity to existing labeling regulations for the export of unregistered pesticide products and...

  15. 77 FR 64990 - Pesticide Program Dialogue Committee; Request for Nominations to the Pesticide Program Dialogue...

    2012-10-24

    ... AGENCY Pesticide Program Dialogue Committee; Request for Nominations to the Pesticide Program Dialogue... Pesticide Program Dialogue Committee (PPDC). EPA values and welcomes diversity. In an effort to obtain... American food supply, the education and protection from unreasonable risk of those who apply or are...

  16. 75 FR 13284 - Pesticide Program Dialogue Committee; Request for Nominations to the Pesticide Program Dialogue...

    2010-03-19

    ... AGENCY Pesticide Program Dialogue Committee; Request for Nominations to the Pesticide Program Dialogue... to be considered for appointment to the Pesticide Program Dialogue Committee (PPDC). EPA values and... American food supply, the education and protection from unreasonable risk of those who apply or are...

  17. 40 CFR 158.2174 - Experimental use permit microbial pesticides nontarget organisms and environmental fate data...

    2010-07-01

    ... pesticides nontarget organisms and environmental fate data requirements table. 158.2174 Section 158.2174 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Microbial Pesticides § 158.2174 Experimental use permit microbial pesticides...

  18. 40 CFR 158.2080 - Experimental use permit data requirements-biochemical pesticides.

    2010-07-01

    ... requirements-biochemical pesticides. 158.2080 Section 158.2080 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Biochemical Pesticides § 158.2080 Experimental use permit data requirements—biochemical pesticides. (a) Sections...

  19. Occupational Pesticide Exposures and Respiratory Health

    Ming Ye

    2013-11-01

    Full Text Available Pesticides have been widely used to control pest and pest-related diseases in agriculture, fishery, forestry and the food industry. In this review, we identify a number of respiratory symptoms and diseases that have been associated with occupational pesticide exposures. Impaired lung function has also been observed among people occupationally exposed to pesticides. There was strong evidence for an association between occupational pesticide exposure and asthma, especially in agricultural occupations. In addition, we found suggestive evidence for a link between occupational pesticide exposure and chronic bronchitis or COPD. There was inconclusive evidence for the association between occupational pesticide exposure and lung cancer. Better control of pesticide uses and enforcement of safety behaviors, such as using personal protection equipment (PPE in the workplace, are critical for reducing the risk of developing pesticide-related symptoms and diseases. Educational training programs focusing on basic safety precautions and proper uses of personal protection equipment (PPE are possible interventions that could be used to control the respiratory diseases associated with pesticide exposure in occupational setting.

  20. Occupational pesticide exposures and respiratory health.

    Ye, Ming; Beach, Jeremy; Martin, Jonathan W; Senthilselvan, Ambikaipakan

    2013-11-28

    Pesticides have been widely used to control pest and pest-related diseases in agriculture, fishery, forestry and the food industry. In this review, we identify a number of respiratory symptoms and diseases that have been associated with occupational pesticide exposures. Impaired lung function has also been observed among people occupationally exposed to pesticides. There was strong evidence for an association between occupational pesticide exposure and asthma, especially in agricultural occupations. In addition, we found suggestive evidence for a link between occupational pesticide exposure and chronic bronchitis or COPD. There was inconclusive evidence for the association between occupational pesticide exposure and lung cancer. Better control of pesticide uses and enforcement of safety behaviors, such as using personal protection equipment (PPE) in the workplace, are critical for reducing the risk of developing pesticide-related symptoms and diseases. Educational training programs focusing on basic safety precautions and proper uses of personal protection equipment (PPE) are possible interventions that could be used to control the respiratory diseases associated with pesticide exposure in occupational setting.

  1. 75 FR 26668 - Flutriafol; Pesticide Tolerances

    2010-05-12

    ... class of pesticides. Although conazoles act similarly in plants (fungi) by inhibiting ergosterol... are no currently established Codex, Canadian, or Mexican maximum residue limits for flutriafol...

  2. Effect of endocrine disruptor pesticides: a review.

    Mnif, Wissem; Hassine, Aziza Ibn Hadj; Bouaziz, Aicha; Bartegi, Aghleb; Thomas, Olivier; Roig, Benoit

    2011-06-01

    Endocrine disrupting chemicals (EDC) are compounds that alter the normal functioning of the endocrine system of both wildlife and humans. A huge number of chemicals have been identified as endocrine disruptors, among them several pesticides. Pesticides are used to kill unwanted organisms in crops, public areas, homes and gardens, and parasites in medicine. Human are exposed to pesticides due to their occupations or through dietary and environmental exposure (water, soil, air). For several years, there have been enquiries about the impact of environmental factors on the occurrence of human pathologies. This paper reviews the current knowledge of the potential impacts of endocrine disruptor pesticides on human health.

  3. Effect of Endocrine Disruptor Pesticides: A Review

    Benoit Roig

    2011-06-01

    Full Text Available Endocrine disrupting chemicals (EDC are compounds that alter the normal functioning of the endocrine system of both wildlife and humans. A huge number of chemicals have been identified as endocrine disruptors, among them several pesticides. Pesticides are used to kill unwanted organisms in crops, public areas, homes and gardens, and parasites in medicine. Human are exposed to pesticides due to their occupations or through dietary and environmental exposure (water, soil, air. For several years, there have been enquiries about the impact of environmental factors on the occurrence of human pathologies. This paper reviews the current knowledge of the potential impacts of endocrine disruptor pesticides on human health.

  4. Sorption of pesticides to aquifer minerals

    Clausen, Liselotte; Fabricius, Ida Lykke

    2000-01-01

    This paper summarizes results from a work were the sorption of five pesticides on seven minerals were studied in order to quantify the adsorption to different mineral surfaces. Investigated mineral phases are: quartz, calcite, kaolinite, a-alumina, and three iron oxides (2-line ferrihydrite......, goethite, lepidocrocite). Selected pesticides are: atrazine, isoproturon, mecoprop, 2,4-D, and bentazone. The results demonstrate that pesticides adsorb to pure mineral surfaces. However, the size of the adsorption depends on the type of pesticide and the type of mineral....

  5. Efficient synthesis of a fluorescent tripod detection system for pesticides by microwave-assisted click chemistry.

    Mallard-Favier, Isabelle; Blach, Philippe; Cazier, Francine; Delattre, François

    2009-01-26

    A new tripod molecule containing an aromatic core bearing three peracetylated cyclodextrins was synthesized via a microwave-assisted Huisgen 1,3-dipolar cycloaddition and was studied by fluorescence spectroscopy. The photoluminescent properties of complexation phenomena with different pesticides were evaluated in acetonitrile. Fluorescence titrations have been performed to calculate binding constants, sensitivity factors, and limit of detection of the resulting complexes. 2D NMR experiments confirmed the inclusion of pesticide in the hydrophobic cavity of the macrocycle and validated the supramolecular association responsible for the quenching of the fluorescence.

  6. Synthesis, screening for antiacetylcholinesterase activity and binding mode prediction of a new series of [3-(disubstituted-phosphate)-4,4,4-trifluoro-butyl]-carbamic acid ethyl esters

    Zanatta, Nilo; Marchi, Tiago M.; Bonacorso, Helio G.; Martins, Marcos A.P.; Flores, Alex F.C. [Universidade Federal de Santa Maria, RS (Brazil). Dept. de Quimica. Nucleo de Quimica de Heterociclos]. E-mail: zanatta@base.ufsm.br; Borchhardt, Deise M.; Andricopulo, Adriano D.; Salum, Livia B. [Universidade de Sao Paulo (USP), Sao Carlos, SP (Brazil). Centro de Biotecnologia Molecular Estrutural. Lab. de Quimica Medicinal e Computacional; Carpes, Adriana D.; Schetinger, Maria R.C. [Universidade Federal de Santa Maria, RS (Brazil). Dept. de Quimica. Lab. de Enzimologia Toxicologica

    2008-07-01

    A series of nine new [3-(disubstituted-phosphate)-4,4,4-trifluoro-butyl]-carbamic acid ethyl esters (phosphate-carbamate compounds) was obtained through the reaction of (4,4,4-trifluoro-3-hydroxybut-1-yl)-carbamic acid ethyl esters with phosphorus oxychloride followed by the addition of alcohols. The products were characterized by {sup 1}H, {sup 13}C, {sup 31}P, and {sup 19}F NMR spectroscopy, GC-MS, and elemental analysis. All the synthesized compounds were screened for acetylcholinesterase (AChE) inhibitory activity using the Ellman method. All compounds containing phosphate and carbamate pharmacophores in their structures showed enzyme inhibition, being the compound bearing the diethoxy phosphate group (2b) the most active compound. Molecular modeling studies were performed to investigate the detailed interactions between AChE active site and small-molecule inhibitor candidates, providing valuable structural insights into AChE inhibition. (author)

  7. Different hydrogen-bonded chains in the crystal structures of three alkyl N-[(E-1-(2-benzylidene-1-methylhydrazinyl-3-hydroxy-1-oxopropan-2-yl]carbamates

    Thais C. M. Noguiera

    2015-07-01

    Full Text Available The crystal structures of three methylated hydrazine carbamate derivatives prepared by multi-step syntheses from l-serine are presented, namely benzyl N-{(E-1-[2-(4-cyanobenzylidene-1-methylhydrazinyl]-3-hydroxy-1-oxopropan-2-yl}carbamate, C20H20N4O4, tert-butyl N-{(E-1-[2-(4-cyanobenzylidene-1-methylhydrazinyl]-3-hydroxy-1-oxopropan-2-yl}carbamate, C17H22N4O4, and tert-butyl N-[(E-1-(2-benzylidene-1-methylhydrazinyl-3-hydroxy-1-oxopropan-2-yl]carbamate, C16H23N3O4. One of them shows that an unexpected racemization has occurred during the mild-condition methylation reaction. In each crystal structure, the molecules are linked into chains by O—H...O hydrogen bonds, but with significant differences between them.

  8. Pesticide poisoning in the developing world--a minimum pesticides list

    Eddleston, Michael; Karalliedde, Lakshman; Buckley, Nick

    2002-01-01

    In parts of the developing world, pesticide poisoning causes more deaths than infectious diseases. Use of pesticides is poorly regulated and often dangerous; their easy availability also makes them a popular method of self-harm. In 1985, the UN Food and Agriculture Organisation (FAO) produced...... pesticides be restricted--where this has been done, suicide rates have fallen. Since an Essential Drugs List was established in 1977, use of a few essential drugs has rationalised drug use in many regions. An analogous Minimum Pesticides List would identify a restricted number of less dangerous pesticides...... a voluntary code of conduct for the pesticide industry in an attempt to limit the harmful effects of pesticides. Unfortunately, a lack of adequate government resources in the developing world makes this code ineffective, and thousands of deaths continue today. WHO has recommended that access to highly toxic...

  9. PestLCI - A new model for estimation of inventory data for pesticide applications

    Birkved, Morten; Hauschild, Michael Zwicky

    2003-01-01

    and time of application, crop species and development stage, and properties of the pesticide active ingredients. The required physical-chemical information on the 69 organic pesticides approved for field-use in Denmark is included in the model as a data base. So is the relative leaf area for 28 common...... European crops on 2-5 development stages together with meteorological data for 12 stations in Denmark. The use and capability of the model is illustrated through Danish case studies but the modular structure of the model will allow its adaptation to conditions valid for other regions.......PestLCI is a new, modular model for estimation of pesticide emissions from field application to the different environmental compartments. It calculates emission fractions to the air, water, soil and groundwater compartments of the environment based on generally available information about: Type...

  10. Assessmet of temporal distribution of pesticide residues in vineyard soils of La Rioja (Spain)

    Pose Juan, Eva; Herrero Hernandez, Eliseo; Soledad Andrades, Maria; Rodriguez Cruz, Maria Sonia; Sanchez Martin, Maria Jesus

    2013-04-01

    The use and application of pesticides in vineyard is a common practice, which is important to prevent pest and diseases and improve the crop health and production, but on the other hand it could involve a potential risk for humans and the environment. For this reason, it is important to develop and validate a simple and fast multiresidue method to determine the presence of these compounds in soils. La Rioja region (Spain) is one of the most important wine-growing regions in Spain, which also entails that could be an important area of pesticide pollution. The objective of this work is to assess the temporal distribution of the possible pesticide pollution in soils from different areas of La Rioja (Spain). The pesticides selected in this study included fungicides (metalaxyl, and its metabolite CGA62826, pyrimethanil, tebuconazole, myclobutanil, kresoxim-methyl, triadimenol and flutriafol); herbicides (fluometuron, terbuthylazine and its metabolites desethylterbuthylazine and hydroxyterbuthylazine, lenacil, ethofumesate and acetochlor) and insecticides (methoxyfenozide and pirimicarb). The pesticide residues were evaluated by two analytical techniques, gas chromatography and liquid chromatography (GC-MS and LC-MS). The extraction procedure of pesticides from soils was optimized using two soil samples (blank soils) with different texture and characteristics collected from areas without pesticide application. Recoveries were studied in soil samples fortified with all pesticides at two levels of concentrations (the agronomic dose, 0.1 mg kg-1, and ten times this dose, 1 mg kg-1). Different extraction solvents were tested. The best results were obtained with methanol:acetone (50:50) mixture or methanol:CaCl2 0.01 M (50:50) mixture for hydroxyterbuthylazine and CGA62826. The accuracy (average recovery) and precision (reproducibility and repeatability) of the method were assessed using six replicates and the limits of detection (LODs) and quantification (LOQs) were

  11. Genetic Alterations in Pesticide Exposed Bolivian Farmers

    Jørs, Erik; González, Ana Rosa; Ascarrunz, Maria Eugenia

    2007-01-01

    Background: Pesticides are of concern in Bolivia because of increasing use. Frequent intoxications have been demonstrated due to use of very toxic pesticides, insufficient control of distribution and sale and little knowledge among farmers of protective measures and hygienic procedures. Method: Q...

  12. The impact of pesticides on male fertility.

    Roeleveld, N.; Bretveld, R.

    2008-01-01

    PURPOSE OF REVIEW: Observations in several Western countries point toward a decline in semen quality which may be associated with exposure to environmental endocrine disruptors such as several frequently used pesticides. The scarce literature on the effects of pesticides on male fertility will be re

  13. 33 CFR 274.4 - Pesticide management.

    2010-07-01

    ... 33 Navigation and Navigable Waters 3 2010-07-01 2010-07-01 false Pesticide management. 274.4... DEFENSE PEST CONTROL PROGRAM FOR CIVIL WORKS PROJECTS Project Operation § 274.4 Pesticide management. (a... control management personnel prior to advertisement of the contract and procurement of services....

  14. Aquatic Macrophyte Risk Assessment for Pesticides

    Maltby, L.; Arnold, D.; Arts, G.H.P.; Davies, J.; Heimbach, F.; Pickl, C.; Poulsen, V.

    2009-01-01

    Given the essential role that primary producers play in aquatic ecosystems, it is imperative that the potential risk of pesticides to the structure and functioning of aquatic plants is adequately assessed. This book discusses the assessment of the risk of pesticides with herbicidal activity to aquat

  15. 75 FR 6656 - Pesticide Product; Registration Application

    2010-02-10

    ... AGENCY Pesticide Product; Registration Application AGENCY: Environmental Protection Agency (EPA). ACTION: Notice. SUMMARY: This notice announces receipt of an application to register a new use for a pesticide... the Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA), as amended. EPA is publishing...

  16. 78 FR 53682 - Tetrachlorvinphos; Pesticide Tolerances

    2013-08-30

    ... AGENCY 40 CFR Part 180 Tetrachlorvinphos; Pesticide Tolerances AGENCY: Environmental Protection Agency... by converting them to permanent tolerances for the combined residues of the insecticide...-OPP-2011-0360, is available at http://www.regulations.gov or at the Office of Pesticide...

  17. Occupational pesticide exposure among Kenyan agricultural workers.

    Ohayo-Mitoko, G.J.A.

    1997-01-01

    This study was part of the Kenyan component of a multi-centre epidemiologic survey, the East African Pesticides Project. The general objective was to assess the health hazards posed by pesticide handling, storage and use in agricultural estates and small farms in selected rural agricultural communit

  18. Pesticide biotransformation and fate in heterogeneous environments.

    Vink, J.P.M.

    1997-01-01

    The effects and relative impacts of environmental variables on the behaviour of pesticides, through the effect on pesticide-degrading microorganisms, was studied in a broad spectrum and covered the most relevant emission routes. It is shown that the effect of landscape geochemistry, which is a pre-s

  19. Multi-Residue Analysis of Pesticides in Pistachio Using Gas Chromatography-Mass Spectrometry (GC/MS

    Azadeh Emami

    2014-12-01

    Full Text Available Background: Analysis of pesticide residues in food and other environmental commodities have become an essential requirement for consumers, producers, food inspectors and authorities. This study is focused on validation of an accurate, rapid and reliable method for multi-residual analysis of pesticides in pistachio as a strategic crop for export and one of the main nuts in Iranian food basket. Methods: We developed a "Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS method based on spiking blank samples and used the data for drawing calibration curves instead of standard solutions. Sample preparations were developed for determination of 12 pesticide residues in pistachio by gas chromatography-mass spectrometry (GC/MS. Results: Recovery of pesticides at 5 concentration levels (n=3 was in the range of 81.40% - 93.08 %. The method proved to be repeatable in the majority of samples with relative standard deviation (RSD of lower than 20%. The limits of detection and quantification for all pesticides were 2 ppb and 10 ppb, respectively. Conclusion: The calibration curves of pesticides were linear in the range of 10-500 (ng/g and correlation coefficient of entire pesticides was higher than 0.994. The recovery of pesticides at 5 concentration levels (n=3 was in range of 81.41- 91.80 %. The method was proved to be repeatable with the majority of RSDs being lower than 20%. The limits of detection and quantification for all pesticides were 2 and 10 ppb, respectively. The recoveries and repeatabilities were in accordance with the criteria set by SANCO Guideline (Commission of the European Communities, 2006.

  20. A Novel Non-phosgene Process for the Synthesis of Methyl N-Phenyl Carbamate from Methanol and Phenylurea:Effect of Solvent and Catalyst

    WANG,Xin-Kui(王心葵); YAN,Shi-Run(闫世润); CAO,Yong(曹勇); FAN,Kang-Nian(范康年); HE,He-Yong(贺鹤勇); KANG,Mao-Qing(亢茂青); PENG,Shao-Yi(彭少逸)

    2004-01-01

    A novel environmentally benign process for the synthesis of methyl N-phenyl carbamate (MPC) from methanol and phenylurea was studied. Effect of solvent and catalyst on the reaction behavior was investigated. The IR spectra of methanol and phenylurea dissolved in different solvents were also recorded. Compared with use of methanol as both a reactant and a solvent, phenylurea conversion and selectivity to MPC increased by using toluene, benzene or anisole as a solvent, while phenylurea conversion decreased slightly by using n-octane as a solvent. The phenylurea conversion declined nearly 50% when dimethyl sulfoxide (DMSO) was used as a reaction media, and MPC selectivity decreased as well. The catalytic reaction tests showed that a basic catalyst enhanced the selectivity to MPC while an acidic catalyst promoted the formation of methyl carbamate and aniline. Moderate degree of basicity showed the best catalytic performance in the cases studied.

  1. Trends and Challenges in Pesticide Resistance Detection.

    2016-10-01

    Pesticide resistance is a crucial factor to be considered when developing strategies for the minimal use of pesticides while maintaining pesticide efficacy. This goal requires monitoring the emergence and development of resistance to pesticides in crop pests. To this end, various methods for resistance diagnosis have been developed for different groups of pests. This review provides an overview of biological, biochemical, and molecular methods that are currently used to detect and quantify pesticide resistance. The agronomic, technical, and economic advantages and drawbacks of each method are considered. Emerging technologies are also described, with their associated challenges and their potential for the detection of resistance mechanisms likely to be selected by current and future plant protection methods.

  2. [Evidence of pesticide exposure by hair analysis].

    Cirimele, V; Kintz, P; Ludes, B

    1999-01-01

    The current report summarizes the development of an analytical method for the identification and the quantification of pesticides in hair by gas chromatography/mass spectrometry and its application to 75 real samples. Hair strands [table: see text] were obtained from wine workers exposed to one or more pesticides. After decontamination, hair were cut into small pieces and incubated overnight at 45 degrees C in methanol. The solvent was evaporated to dryness, the dry extract was redissolved in methanol and injected in a gas chromatography/mass spectrometry system. The detector was operated in electronic impact and in negative chemical ionization mode of detection (reactant gas: methane). In the first series of 75 hair specimens, obtained before the period of pesticide use, none of the 15 target compounds was detected. In the second series of 75 specimens, obtained from the same subjects but after the use of pesticides, 14 tested positive for 9 different pesticides.

  3. Agricultural pesticides and precocious puberty.

    Ozen, Samim; Goksen, Damla; Darcan, Sukran

    2014-01-01

    The onset and course of puberty is under the control of the neuroendocrine system. Factors affecting the regulation of timing and order of this system's functions may alter the onset and course of puberty. Several environmental endocrine disruptors (EDs) with significant influences on the normal course of puberty have been identified. Despite the numerous animal and human studies on EDs that may extensively affect human health, there are still several issues that need to be clarified. This chapter discusses the effects of pesticides, which constitute a significant portion of disruptors and have been increasingly used in agriculture, on precocious puberty.

  4. Pesticide residues in passifloras crops in regions of high production in Colombia

    Dario A. Bastidas

    2013-08-01

    Full Text Available As one of the most bio-diverse countries in the world, Colombia boasts a wide diversity of highly palatable tropical fruits. Even though Colombian fruit production has primarily targeted the domestic market, several fruit species, such as passion fruit (PassifloraSpp, are steadily gaining ground in the broader international arena.  Production of these crops and respond to raising domestic and international demand, many Colombian small-scale farmers use pesticides for pest and disease control. Inadequate use of pesticides could possibly entail public health risks, environmental contamination and ultimately interfere with international trade. Surveys were carried out to passifloras producers of three spices of passiflora crops, yellow passion fruit, sweet passion fruit and purple passion fruit  from the largest producers municipalities in Colombia with the aim to know the integrate pest control and agricultural practices related with pesticides applied in the crops. Ramdomly sampling was realized and samples were analyzed by multiresidue analysis methodology validated in the laboratory and based on IAEA-QuEChERS method. With the results of survey and laboratory analysis it is showed the presence of pesticide residues that exceed maximum residue limits in some samples and the pesticides identified in the samples correspond to those used by farmers. It was found that the presence of residues is mainly due to the shortcomings in the proper use of agricultural practices related primarily to the implementation of agricultural products no registered for such crops.

  5. Regio-, Diastereo-, and Enantioselective Nitroso-Diels-Alder Reaction of 1,3-Diene-1-carbamates Catalyzed by Chiral Phosphoric Acids.

    Pous, Jonathan; Courant, Thibaut; Bernadat, Guillaume; Iorga, Bogdan I; Blanchard, Florent; Masson, Géraldine

    2015-09-23

    Chiral phosphoric acid-catalyzed asymmetric nitroso-Diels-Alder reaction of nitrosoarenes with carbamate-dienes afforded cis-3,6-disubstituted dihydro-1,2-oxazines in high yields with excellent regio-, diastereo-, and enantioselectivities. Interestingly, we observed that the catalyst is able not only to control the enantioselectivity but also to reverse the regioselectivity of the noncatalyzed nitroso-Diels-Alder reaction. The regiochemistry reversal and asynchronous concerted mechanism were confirmed by DFT calculations.

  6. Effects of humic acids, para-aminobenzoic acid and ascorbic acid on the N-nitrosation of the carbamate insecticide propoxur and on the mutagenicity of nitrosopropoxur.

    Gichner, T; Badaev, S A; Pospísil, F; Velemínský, J

    1990-03-01

    Nitrosation of the carbamate insecticide propoxur at pH 3 and 37 degrees C was determined colorimetrically and found to be time- and sodium nitrite concentration-dependent. Nitrosated propoxur was mutagenic when exposed to the seeds of the higher plant Arabidopsis thaliana but the formation of nitrosopropoxur, the presumed mutagen, was inhibited by humic acids, para-aminobenzoic acid and ascorbic acid. These agents also reduced the mutagenicity of preformed nitrosopropoxur.

  7. Supercritical fluid extraction for some carbamate insecticides in potatoes samples, with HPLC/fluorescence determination and HPLC/mass spectrometry confirmation

    Gilvanda Silva Nunes; Teresa Cristina R. Santos; Damiá Barceló; Alexandre Santos Pimenta; Maria Lúcia Ribeiro

    2002-01-01

    Six supercritical fluid extraction (SFE) methods were tested, by varying the following operational parameters: CO2 pressure, time and temperature of extraction, type and proportion of static modifier, and Hydromatrix®/sample rate into cell. Firstly, insecticide carbamates were extracted from spiked potatoes samples (fortification level of 0,5 mg.Kg-1) by using SPE procedures, and then final extracts were analyzed HPLC/fluorescence. Good performance was observed with SFE methods that operated ...

  8. Wild Raspberry Subjected to Simulated Gastrointestinal Digestion Improves the Protective Capacity against Ethyl Carbamate-Induced Oxidative Damage in Caco-2 Cells.

    Chen, Wei; Xu, Yang; Zhang, Lingxia; Li, Ya; Zheng, Xiaodong

    2016-01-01

    Ethyl carbamate (EC), a probable human carcinogen, occurs widely in many fermented foods. Previous studies indicated that EC-induced cytotoxicity was associated with oxidative stress. Wild raspberries are rich in polyphenolic compounds, which possess potent antioxidant activity. This study was conducted to investigate the protective effect of wild raspberry extracts produced before (RE) and after in vitro simulated gastrointestinal digestion (RD) on EC-induced oxidative damage in Caco-2 cells. Our primary data showed that ethyl carbamate could result in cytotoxicity and genotoxicity in Caco-2 cells and raspberry extract after digestion (RD) may be more effective than that before digestion (RE) in attenuating toxicity caused by ethyl carbamate. Further investigation by fluorescence microscope revealed that RD may significantly ameliorate EC-induced oxidative damage by scavenging the overproduction of intracellular reactive oxygen species (ROS), maintaining mitochondrial function and preventing glutathione (GSH) depletion. In addition, HPLC-ESI-MS results showed that the contents of identified polyphenolic compounds (esculin, kaempferol O-hexoside, and pelargonidin O-hexoside) were remarkably increased after digestion, which might be related to the better protective effect of RD. Overall, our results demonstrated that raspberry extract undergoing simulated gastrointestinal digestion may improve the protective effect against EC-induced oxidative damage in Caco-2 cells.

  9. COMPARISON OF EEG CHANGES PRODUCED BY CARBARYL (CARBAMATE), PERMETHRIN (TYPE I PYRETHROID), AND DELTAMETHRIN (TYPE II PYRETHROID)

    We have reported that treatment with carbaryl may alter Theta activity in the EEG (Lyke et al., Toxicologist, 108(S-1):441, 2009). In this study, we examined the ability to detect changes in EEG activity produced by pesticides with different modes of action. Long Evans rats were ...

  10. Microbial pesticides [data requirements for environmental risk assessment

    Mensink BJWG; Linders JBHJ; CSR

    1997-01-01

    The market for microbial pesticides is, though slowly, expanding. Therefore more research with these pesticides will be carried out in the near future, not only for agronomical and economical, but also for environmental reasons. As more chemical pesticides are going to be banned, microbial pesticid

  11. 40 CFR 170.130 - Pesticide safety training for workers.

    2010-07-01

    ... (iii) Have completed a pesticide safety train-the-trainer program approved by a State, Federal, or... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Pesticide safety training for workers...) PESTICIDE PROGRAMS WORKER PROTECTION STANDARD Standard for Workers § 170.130 Pesticide safety training...

  12. [A Simultaneous Determination Method with Acetonitrile-n-Hexane Partitioning and Solid-Phase Extraction for Pesticide Residues in Livestock and Marine Products by GC-MS].

    Yoshizaki, Mayuko; Kobayashi, Yukari; Shimizu, Masanori; Maruyama, Kouichi

    2015-01-01

    A simultaneous determination method was examined for 312 pesticides (including isomers) in muscle of livestock and marine products by GC-MS. The pesticide residues extracted from samples with acetone and n-hexane were purified by acetonitrile-n-hexane partitioning, and C18 and SAX/PSA solid-phase extraction without using GPC. Matrix components such as cholesterol were effectively removed. In recovery tests performed by this method using pork, beef, chicken and shrimp, 237-257 pesticides showed recoveries within the range of 70-120% in each sample. Validity was confirmed for 214 of the target pesticides by means of a validation test using pork. In comparison with the Japanese official method using GPC, the treatment time of samples and the quantity of solvent were reduced substantially.

  13. Brain cholinesterase reactivation as a marker of exposure to anticholinesterase pesticides: a case study in a population of yellow-legged gull Larus michahellis (Naumann, 1840) along the northern coast of Portugal.

    Santos, Cátia S A; Monteiro, Marta S; Soares, Amadeu M V M; Loureiro, Susana

    2016-01-01

    Between late 2010 to early 2011, an increased mortality in gulls was observed along the northern coast of Portugal, with individuals exhibiting neurologic disorders consistent with an eventual anticholinesterase pesticide poisoning event. To clarify if this mortality was related to organophosphate (OP) and/or carbamate (CB) poisoning, chemical and spontaneous cholinesterase (ChE) reactivation was tested in the brain of the yellow-legged gull (Larus michahellis). Initial brain ChE activity in L. michahellis was 40.92 ± 5.23 U/mg of protein (average ± SE). Following chemical and spontaneous reactivation, ChE activity increased in average 70.38 ± 48.59% and 131.95 ± 92.64%, respectively. ChE reactivation was found to decrease at increasing concentrations of the oxime pyridine-2-aldoxime methochloride and dilution factor, underscoring the importance of first optimizing the assay conditions prior to its use on bird species. These results suggest that birds analysed could have been exposed to OP and CB pesticide compounds and that in most cases CB exposure appeared to be the main cause of birds poisoning. These results are an important contribution to environmental monitoring as it demonstrates the suitability of L. michaellis as sentinel species of OP and CB pesticides within an urban environment.

  14. Rat dried blood spot analysis of (R,S)-(-)- and (S,R)-(+)- enantiomers of emtricitabin on immobilized tris-(3,5-dimethylphenyl carbamate) amylose silica as a chiral stationary phase.

    Rao, Ramisetti Nageswara; Santhakumar, Kondapalli; Naidu, Challa Gangu

    2015-10-01

    An enantioselective high performance liquid chromatography method has been developed and validated by evaluating the suitability of newly introduced immobilized polysaccharide chiral stationary phases, the effect of different organic modifiers and temperature including the entropy and enthalpy on resolution of the (R,S)-(-) & (S,R)-(+) emtricitabine enantiomers on rat dried blood spots. Both the enantiomers were extracted from dried blood spots using ethanol: methanol (80:20 v/v) mixture and separated on an immobilized amylose tris-(3,5-dimethyl phenyl carbamate) chiral stationary phase using n-hexane:ethanol (65:35 v/v) as a mobile phase at a flow rate of 0.8mL/min. The detection was carried out at 280nm using photo diode array detector connected to a polarimeter in series to determine their order of eluton. The method was validated with respect to limits of detection and quantification, linearity, accuracy and precision. The calibration curves were linear over the concentration range of 0.5-500μg/mL for both enantiomers and the correlation coefficient (r(2)) was >0.998. The overall recovery of (R,S)- & (S,R)-enantiomers of emtricitabin from DBS were 90.4 and 90.6%, respectively. The limits of detection and quantification of enantiomers were 0.26, 0.30 and 0.85, 0.92μg/mL for (R,S)- and (S,R)-emtricitabin enantiomers, respectively. The assay was specific and precise (RSD <10%). The stability of emtricitabin was also performed and the results were found to be well within the limits. The effect of hematocrit on extraction of emtricitabin enantiomers from dried blood spots was evaluated and no interference from endogenous substances was observed.

  15. 40 CFR 152.10 - Products that are not pesticides because they are not intended for a pesticidal purpose.

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Products that are not pesticides... ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS PESTICIDE REGISTRATION AND CLASSIFICATION PROCEDURES General Provisions § 152.10 Products that are not pesticides because they are not intended for...

  16. Characterizing pesticide dissipation in food crops

    Fantke, Peter; Juraske, R.; Jolliet, O.

    2013-01-01

    Ingestion of residues via consumption of food crops is the predominant exposure route of the general population toward pesticides. However, pesticide dissipation in crops constitutes a main source of uncertainty in estimating residues in harvested crop parts and subsequent human exposure. Neverth......Ingestion of residues via consumption of food crops is the predominant exposure route of the general population toward pesticides. However, pesticide dissipation in crops constitutes a main source of uncertainty in estimating residues in harvested crop parts and subsequent human exposure....... Nevertheless, dissipation is a key mechanism in models assessing pesticide distribution in the cropenvironment and the magnitude of residues in harvest. We provide a consistent framework for characterizing pesticide dissipation in food crops for use in modeling approaches applied in health risk and impact...... degradation is dominating. We are currently testing the regression to predict degradation half-lives in crops. By providing mean degradation half-lives at 20°C for more than 300 pesticides, we reduce uncertainty and improve assumptions in current practice of health risk and impact assessments....

  17. Pesticides in Brazilian freshwaters: a critical review.

    Albuquerque, A F; Ribeiro, J S; Kummrow, F; Nogueira, A J A; Montagner, C C; Umbuzeiro, G A

    2016-07-13

    The widespread use of pesticides in agriculture can lead to water contamination and cause adverse effects on non-target organisms. Brazil has been the world's top pesticide market consumer since 2008, with 381 approved pesticides for crop use. This study provides a comprehensive literature review on the occurrence of pesticide residues in Brazilian freshwaters. We searched for information in official agency records and peer-reviewed scientific literature. Risk quotients were calculated to assess the potential risk posed to aquatic life by the individual pesticides based on their levels of water contamination. Studies about the occurrence of pesticides in freshwaters in Brazil are scarce and concentrated in few sampling sites in 5 of the 27 states. Herbicides (21) accounted for the majority of the substances investigated, followed by fungicides (11), insecticides (10) and plant growth regulators (1). Insecticides are the class of major concern. Brazil would benefit from the implementation of a nationwide pesticide freshwater monitoring program to support preventive, remediation and enforcement actions.

  18. A GIS-based method for household recruitment in a prospective pesticide exposure study

    Phillips Michael J

    2008-04-01

    Full Text Available Abstract Background Recent advances in GIS technology and remote sensing have provided new opportunities to collect ecologic data on agricultural pesticide exposure. Many pesticide studies have used historical or records-based data on crops and their associated pesticide applications to estimate exposure by measuring residential proximity to agricultural fields. Very few of these studies collected environmental and biological samples from study participants. One of the reasons for this is the cost of identifying participants who reside near study fields and analyzing samples obtained from them. In this paper, we present a cost-effective, GIS-based method for crop field selection and household recruitment in a prospective pesticide exposure study in a remote location. For the most part, our multi-phased approach was carried out in a research facility, but involved two brief episodes of fieldwork for ground truthing purposes. This method was developed for a larger study designed to examine the validity of indirect pesticide exposure estimates by comparing measured exposures in household dust, water and urine with records-based estimates that use crop location, residential proximity and pesticide application data. The study focused on the pesticide atrazine, a broadleaf herbicide used in corn production and one of the most widely-used pesticides in the U.S. Results We successfully used a combination of remotely-sensed data, GIS-based methods and fieldwork to select study fields and recruit participants in Illinois, a state with high corn production and heavy atrazine use. Our several-step process consisted of the identification of potential study fields and residential areas using aerial photography; verification of crop patterns and land use via site visits; development of a GIS-based algorithm to define recruitment areas around crop fields; acquisition of geocoded household-level data within each recruitment area from a commercial vendor; and

  19. Design, synthesis, and biological evaluation of scutellarein carbamate derivatives as potential multifunctional agents for the treatment of Alzheimer's disease.

    Sang, Zhi-Pei; Qiang, Xiao-Ming; Li, Yan; Wu, Bei; Zhang, Hui; Zhao, Ming-Gao; Deng, Yong

    2015-11-01

    A series of scutellarein carbamate derivatives were designed and synthesized based on the multitarget-directed drug design strategy for treatment of Alzheimer's disease. Their acetylcholinesterase and butyrylcholinesterase inhibitory activities, antioxidant activities, metals chelation, and neuroprotective effects against hydrogen peroxide-induced PC12 cell injury were evaluated in vitro. The preliminary results indicated that compound 7b exhibited good inhibitory potency toward AChE and BuChE with IC50 values of 1.2 ± 0.03 μm and 22.1 ± 0.15 μm, respectively, possessed the strong antioxidant potency (10.3 trolox equivalents), as well as acted as a selective metal chelator and neuroprotective agent. Furthermore, 7b could improve memory impairment induced by scopolamine, ethanol, and sodium nitrite using the step-down passive avoidance task in vivo and could remarkably decrease the activity of acetylcholinesterase in mice brain. This study indicated that 7b could be considered as a potential multitarget agent against AD.

  20. Detecting resistance to organophosphates and carbamates in the cattle tick Boophilus microplus, with a propoxur-based biochemical test.

    Baxter, G D; Green, P; Stuttgen, M; Barker, S C

    1999-11-01

    Rapid and sensitive detection of resistance to insecticides in arthropods is needed. In the cattle tick. Boophilus microplus, resistance to a variety of acaricides is widespread. The most commonly used assay for resistance, the larval packet test, takes at least two, but generally six weeks for a one-host tick like B. microplus to complete and may take up to three months to complete for three-host ticks. Here we describe a test for resistance to organophosphate acaricides that can be used on larvae and adult ticks which takes less than 24 hours. The test measures the difference in acetylcholinesterase (AChE) activity in homogenates of ticks in the presence and absence of propoxur, a carbamate acaricide. We found clear discrimination of organophosphate-susceptible and organophosphate-resistant adults with 100 microM propoxur. AChE from susceptible ticks had almost no activity at this concentration of propoxur whereas AChE from resistant ticks had 67% of its potential activity. AChE from heterozygote ticks could also be distinguished from AChE from homozygous-susceptible and homozygous-resistant ticks. This is the first biochemical test for resistance to an acaricide. Rapid, sensitive tests like ours will allow resistance to organophosphates to be detected soon after it develops in the field, thus, the spread of resistance might be slowed and the useful life of acaricides extended.

  1. The use of carbamates, atropine, and 2-pyridine aldoxime methoiodide in the protection of Artemia salina against poisoning by carbophenothion.

    Sánchez-Fortún, S; Barahona, V

    2001-09-01

    The acute toxicity of carbophenothion to three age classes of Artemia salina was evaluated. An increase in toxicity of carbophenothion was found following longer development of A. salina. The effect of pretreatment with the nonselective muscarinic antagonist atropine, the two reversible acetylcholinesterase-inhibitors physostigmine and pyridostigmine, and the cholinesterase-reactivating oxime 2-pyridine aldoxime methochloride (2-PAM) on carbophenothion-induced lethality in 24-h-old A. salina was also investigated. The lethal action of carbophenothion was completely prevented by pretreatment of A. salina with 2-PAM. Atropine and pyridostigmine afforded a maximal protection of approximately 87% and 72%, respectively, compared to control values. In contrast, physostigmine was ineffective. The inhibitory effects of combinations of 10(-5) M atropine with physostigmine, pyridostigmine, or 2-PAM were greater than those elicited by either drug alone, with the maximum protection afforded being 92.58%, 100%, and 100%, respectively. In the presence of 10(-7) M atropine, neither pyridostigmine nor 2-PAM provided additional inhibition of the lethality compared to that with either drug alone, whereas the protection afforded by 10(-7) M atropine plus physostigmine increased as the concentration of carbamate increased (up to 10(-3) M). Pretreatment with pyridostigmine or physostigmine plus 2-PAM (10(-6) M) slightly enhanced the maximal inhibition of carbophenothion lethality compared to that with either drug alone. It is suggested that the most active combined pretreatment studied here was physostigmine plus atropine.

  2. QSTR modeling for qualitative and quantitative toxicity predictions of diverse chemical pesticides in honey bee for regulatory purposes.

    Singh, Kunwar P; Gupta, Shikha; Basant, Nikita; Mohan, Dinesh

    2014-09-15

    Pesticides are designed toxic chemicals for specific purposes and can harm nontarget species as well. The honey bee is considered a nontarget test species for toxicity evaluation of chemicals. Global QSTR (quantitative structure-toxicity relationship) models were established for qualitative and quantitative toxicity prediction of pesticides in honey bee (Apis mellifera) based on the experimental toxicity data of 237 structurally diverse pesticides. Structural diversity of the chemical pesticides and nonlinear dependence in the toxicity data were evaluated using the Tanimoto similarity index and Brock-Dechert-Scheinkman statistics. Probabilistic neural network (PNN) and generalized regression neural network (GRNN) QSTR models were constructed for classification (two and four categories) and function optimization problems using the toxicity end point in honey bees. The predictive power of the QSTR models was tested through rigorous validation performed using the internal and external procedures employing a wide series of statistical checks. In complete data, the PNN-QSTR model rendered a classification accuracy of 96.62% (two-category) and 95.57% (four-category), while the GRNN-QSTR model yielded a correlation (R(2)) of 0.841 between the measured and predicted toxicity values with a mean squared error (MSE) of 0.22. The results suggest the appropriateness of the developed QSTR models for reliably predicting qualitative and quantitative toxicities of pesticides in honey bee. Both the PNN and GRNN based QSTR models constructed here can be useful tools in predicting the qualitative and quantitative toxicities of the new chemical pesticides for regulatory purposes.

  3. Impacts of pesticide mixtures in European rivers as predicted by the Species Sensitivity Distribution (SSD) models and SPEAR bioindication

    Jesenska, Sona; Liess, Mathias; Schäfer, Ralf; Beketov, Mikhail; Blaha, Ludek

    2013-04-01

    Species sensitivity distribution (SSD) is statistical method broadly used in the ecotoxicological risk assessment of chemicals. Originally it has been used for prospective risk assessment of single substances but nowadays it is becoming more important also in the retrospective risk assessment of mixtures, including the catchment scale. In the present work, SSD predictions (impacts of mixtures consisting of 25 pesticides; data from several catchments in Germany, France and Finland) were compared with SPEAR-pesticides, which a bioindicator index based on biological traits responsive to the effects of pesticides and post-contamination recovery. The results showed statistically significant correlations (Pearson's R, p<0.01) between SSD (predicted msPAF values) and values of SPEAR-pesticides (based on field biomonitoring observations). Comparisons of the thresholds established for the SSD and SPEAR approaches (SPEAR-pesticides=45%, i.e. LOEC level, and msPAF = 0.05 for SSD, i.e. HC5) showed that use of chronic toxicity data significantly improved the agreement between the two methods but the SPEAR-pesticides index was still more sensitive. Taken together, the validation study shows good potential of SSD models in predicting the real impacts of micropollutant mixtures on natural communities of aquatic biota.

  4. Pesticides

    ... off the ground. Close outdoor trash bins and compost containers securely. Remove any standing water in the ... Read More Alcohol use and safe drinking Cancer Review Date 4/21/2015 Updated by: Jacob L. ...

  5. Pesticides

    ... Home Page Brochures & Fact Sheets Environmental Health Topics Science Education Kids Environment | Kids Health Research Home Page At NIEHS ... Agents Water Pollution Environmental Science Basics Population Research Science Education Kids Environment | Kids Health Research Home Research At NIEHS ...

  6. Analysis of pesticides in fruit, vegetables and cereals using methanolic extraction and detection by LC-MS/MS

    Granby, Kit; Andersen, Jens Hinge; Christensen, Hanne Bjerre

    2004-01-01

    in Miniprep filter HPLC vials and detected by LC–MS–MS. To compensate for variations in the MS response [13C6]-carbaryl was used as internal standard and matrix-matched pesticide solutions were used as external standards for the quantification. The method has been validated for the matrices apple, avocado...

  7. A modeled comparison of direct and food web-mediated impacts of common pesticides on Pacific salmon.

    Kate H Macneale

    Full Text Available In the western United States, pesticides used in agricultural and urban areas are often detected in streams and rivers that support threatened and endangered Pacific salmon. Although concentrations are rarely high enough to cause direct salmon mortality, they can reach levels sufficient to impair juvenile feeding behavior and limit macroinvertebrate prey abundance. This raises the possibility of direct adverse effects on juvenile salmon health in tandem with indirect effects on salmon growth as a consequence of reduced prey abundance. We modeled the growth of ocean-type Chinook salmon (Oncorhynchus tshawytscha at the individual and population scales, investigating insecticides that differ in how long they impair salmon feeding behavior and in how toxic they are to salmon compared to macroinvertebrates. The relative importance of these direct vs. indirect effects depends both on how quickly salmon can recover and on the relative toxicity of an insecticide to salmon and their prey. Model simulations indicate that when exposed to a long-acting organophosphate insecticide that is highly toxic to salmon and invertebrates (e.g., chlorpyrifos, the long-lasting effect on salmon feeding behavior drives the reduction in salmon population growth with reductions in prey abundance having little additional impact. When exposed to short-acting carbamate insecticides at concentrations that salmon recover from quickly but are lethal to invertebrates (e.g., carbaryl, the impacts on salmon populations are due primarily to reductions in their prey. For pesticides like carbaryl, prey sensitivity and how quickly the prey community can recover are particularly important in determining the magnitude of impact on their predators. In considering both indirect and direct effects, we develop a better understanding of potential impacts of a chemical stressor on an endangered species and identify data gaps (e.g., prey recovery rates that contribute uncertainty to these

  8. Toxicity of the pesticide alpha-cypermethrin to four soil nontarget invertebrates and implications for risk assessment.

    Hartnik, Thomas; Sverdrup, Line E; Jensen, John

    2008-06-01

    Alpha-cypermethrin, a synthetic pyrethroid, is used as an insecticide in agricultural settings and is increasingly replacing organophosphates and carbamates because of lower application rates and lower toxicity to mammals. Because very little is known about the acute and chronic toxicity of this compound for soil-living organisms, the present study investigated acute and sublethal toxicity of alpha-cypermethrin for four terrestrial invertebrate species in an agricultural soil from Norway. Bioassays with the earthworm Eisenia fetida, the potworm Enchytraeus crypticus, the springtail Folsomia candida, and the land snail Helix aspersa were performed according to slightly modified versions of Organization for Economic Cooperation and Development (Paris, France) or International Organization for Standardization (Geneva, Switzerland) guidelines and resulted in median lethal concentrations of greater than >1,000 to 31.4 mg/kg and sublethal no-observed-effect concentrations of 2.51 to 82 mg/kg. A high acute to chronic ratio was found, especially in the earthworms. Interspecies differences in sensitivity may be explained by differences in exposure and differences in metabolization rate. When based on measured pore-water concentrations, terrestrial species overall appear to be approximately one order of magnitude less sensitive than aquatic species. Effect assessments conducted according to European guideline for risk assessment of pesticides reveal that assessments based on acute toxicity tests are not always conservative enough to determine environmentally safe concentrations in soil. Mandatory incorporation of sublethal toxicity data will ensure that in regions with temperate climate, the effects of pesticides on populations of soil-living organisms are unlikely.

  9. 77 FR 49732 - Cyprodinil; Pesticide Tolerances

    2012-08-17

    ... cyprodinil, causing mild anemia following subchronic exposure to cyprodinil in rats. Chronic effects in dogs... pesticide exposure assessment can be found at http://www.epa.gov/oppefed1/models/water/index.htm . Based...

  10. 78 FR 60709 - Methoxyfenozide; Pesticide Tolerances

    2013-10-02

    ... affected by exposure to methoxyfenozide. Mild anemia (decreases in red blood cell count, hematocrit and...://www.epa.gov/oppefed1/models/water/index.htm . Based on the Pesticide Root Zone Model/Exposure...

  11. How Stereochemistry Considerations can Improve Pesticide Safety

    About 30% of pesticides are chiral molecules and therefore exist as two or more stereoisomers, which can differ significantly in their toxicity, biodegradation, and persistence. Such differences can impact their relative safety to humans and environmental species. Enantiomers, mi...

  12. 75 FR 4279 - Pendimethalin; Pesticide Tolerances

    2010-01-27

    ... filing of a pesticide petition (PP 8F7396) by BASF Corporation, 26 Davis Drive, Research Triangle Park... for seed and dormant Bermuda grass as requested by the petitioner. The commodity names were...

  13. 78 FR 55635 - Prometryn; Pesticide Tolerances

    2013-09-11

    ... pesticides were identified as a common mechanism group (CMG) by EPA in a 2002 paper entitled, ``The Grouping... chromatography/flame photometric detection/sulfur (GC/FPD/S)), Method AG-559, is available to enforce...

  14. 77 FR 18710 - Acetamiprid; Pesticide Tolerances

    2012-03-28

    ... member of the neonicotinoid class of pesticides which also includes thiamethoxam, clothianidin... preliminary evidence suggests that clothianidin operates by direct competitive inhibition, while thiamethoxam...., testicular tubular atrophy with thiamethoxam; mineralized particles in thyroid colloid with...

  15. Neonatal outcome following exposure to organophosphorous pesticides

    Đorđević M.

    2010-01-01

    Full Text Available The aim of our study was to determine the neonatal outcome in mothers and children exposed to organophosphorous pesticides (OP. We found that 22.4% pregnant women were exposed to organophosphorous pesticides. OP pesticide concentration was higher in breast milk, newborn sera than maternal sera. Newborn parameters such as birth weight, birth length, head circumference, Apgar score and presence of meconium, as well as gestational age of delivery, showed no significant difference between the two groups. However, postpartum weight loss, hospitalization duration, levels of newborn bilirubin and glycaemia differed significantly between the two groups. Morbidity and presence of CNS disorders were six times and more than twelve times higher, respectively, in the OP-exposed than in the OP pesticide non-exposed group.

  16. High risk pesticides in sugar beet protection

    Šovljanski Radmila A.

    2006-01-01

    Full Text Available According to traits of pesticides permitted to use in sugar beet (oral percutaneus and inhalation toxicity, toxicity to wildlife, bees and aquatic organisms, re-entry interval, maximum number of treatments, effects on reproduction do not present health risk in sugar production/technology. However, the danger exists for workers by chronic exposure during the application, especially from pesticide being potential endocrine disruptors (EDS (fentin acetate, benomyl, endosulfan, methomyl, methidathion. EDS can cause sterility or decreased fertility, impaired development, birth defects of the reproductive tract and metabolic disorders. Authors recommend limited application of EDS pesticides (to limit the number of treatments to only one during the vegetation, replacement with pesticides with low risk to humans game and fishes, as well as mandatory submission of re-entry data for registration.

  17. Interim Policy for Evaluation of Stereoisomeric Pesticides

    An interim approach for determining data requirements for non-racemic mixtures of stereoisomeric pesticides. These data are needed in order to assess the risk posed to ecosystems and drinking water sources by these mixtures.

  18. Jiangsu Pesticide Research Institute Company Ltd.

    2007-01-01

    @@ Jiangsu Pesticide Research Institute Company Ltd. was established on June 22, 2005, with the registered capital of RMB 40.4 million. Its business includes R&D, manufacture and market of agrochemicals.

  19. CONTAMINANTS AND REMEDIAL OPTIONS AT PESTICIDE SITES

    Many types of soils, sediments, and sludges are contaminated with a wide variety of pesticides. ite-specific characteristics such as volume to be treated, extent of contamination, and applicable cleanup goals differ greatly, and contaminant toxicity, migration pathways, persisten...

  20. Earthworm tolerance to residual agricultural pesticide contamination

    Givaudan, Nicolas; Binet, Françoise; Le Bot, Barbara

    2014-01-01

    This study investigates if acclimatization to residual pesticide contamination in agricultural soils is reflected in detoxification, antioxidant enzyme activities and energy budget of earthworms. Five fields within a joint agricultural area exhibited different chemical and farming histories from ...

  1. 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.

    2008-01-01

    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 dela

  2. Pesticides in Wyoming Groundwater, 2008-10

    Eddy-Miller, Cheryl A.; Bartos, Timothy T.; Taylor, Michelle L.

    2013-01-01

    Groundwater samples were collected from 296 wells during 1995-2006 as part of a baseline study of pesticides in Wyoming groundwater. In 2009, a previous report summarized the results of the baseline sampling and the statistical evaluation of the occurrence of pesticides in relation to selected natural and anthropogenic (human-related) characteristics. During 2008-10, the U.S. Geological Survey, in cooperation with the Wyoming Department of Agriculture, resampled a subset (52) of the 296 wells sampled during 1995-2006 baseline study in order to compare detected compounds and respective concentrations between the two sampling periods and to evaluate the detections of new compounds. The 52 wells were distributed similarly to sites used in the 1995-2006 baseline study with respect to geographic area and land use within the geographic area of interest. Because of the use of different types of reporting levels and variability in reporting-level values during both the 1995-2006 baseline study and the 2008-10 resampling study, analytical results received from the laboratory were recensored. Two levels of recensoring were used to compare pesticides—a compound-specific assessment level (CSAL) that differed by compound and a common assessment level (CAL) of 0.07 microgram per liter. The recensoring techniques and values used for both studies, with the exception of the pesticide 2,4-D methyl ester, were the same. Twenty-eight different pesticides were detected in samples from the 52 wells during the 2008-10 resampling study. Pesticide concentrations were compared with several U.S. Environmental Protection Agency drinking-water standards or health advisories for finished (treated) water established under the Safe Drinking Water Act. All detected pesticides were measured at concentrations smaller than U.S. Environmental Protection Agency drinking-water standards or health advisories where applicable (many pesticides did not have standards or advisories). One or more pesticides

  3. Bacillus thuringiensis and Its Pesticidal Crystal Proteins

    Schnepf, E.; Crickmore, N; Van Rie, J.; Lereclus, D.; Baum, J; Feitelson, J.; Zeigler, D. R.; Dean, D H

    1998-01-01

    During the past decade the pesticidal bacterium Bacillus thuringiensis has been the subject of intensive research. These efforts have yielded considerable data about the complex relationships between the structure, mechanism of action, and genetics of the organism’s pesticidal crystal proteins, and a coherent picture of these relationships is beginning to emerge. Other studies have focused on the ecological role of the B. thuringiensis crystal proteins, their performance in agricultural and o...

  4. Morbidity in newborns exposed to organophosphorus pesticides

    Đorđević Momčilo

    2010-01-01

    Full Text Available Introduction. Insecticides are toxines by which we destroy harmful insects. The most frequent insecticides which are used today are organophosphorus pesticides. This group of compounds make substances whose activity mechanism is based on the inhibition of acetylcho­linesterase in nerve synapsis, thus producing holynergic syndrome, resulting from the accumulation of acetylcholine which developed due to the absence of decomposition under the influence of cholinesterase. In the clinical picture of acute toxication by cholinesterase inhibitors there is a clear difference between muscarinic and nicotine effects. The basic aim of the study was to establish the effects of organophosphorus pesticides present in blood and breast milk of mothers on newborns morbidity. Material and methods. The study group consisted of 18 newborns whose mothers had isolated organophosphorus pesticides in their blood and breast­milk on the third day after delivery, and the control group consisted of 84 newborns whose mothers did not have isolated organophosphorus pesticides in their blood and breastmilk. Results. Morbidity is three times greater, often in combination with some disorders of the central nervous system, and the relative risk for its appearance is eight time greater in newborns exposed to organophosphorus pesticides. Disscusion. Disorders that appear in newborns exposed to pesticides are mutagenic, cancerogenic and neurotoxic and some agenses could disturb the immune system which is reflected in morbidity increase, primarly of the central nervous system. Conclusion. The presence of organophosphorus pesticides in blood and breast milk has negative effects on newborns. In addition to acetylcho­linesterase inhibition, organophosphorus pesticides react by means of other mechanisms as well.

  5. Endocrine disrupting pesticides: implications for risk assessment.

    McKinlay, R; Plant, J A; Bell, J N B; Voulvoulis, N

    2008-02-01

    Endocrine disrupting (ED) chemicals are compounds that alter the normal functioning of the endocrine system, potentially causing disease or deformity in organisms and their offspring. Pesticides are used widely to kill unwanted organisms in crops, public areas, homes and gardens and medicinally to kill parasites. Many are proven or suspected to be EDs. Ancient physiological similarities between different vertebrate groups suggest that disorders observed in wildlife may indicate risks to humans. This makes accurate risk assessment and effective legislation difficult. In this paper, the hazardous properties of pesticides which are known to have ED properties are reviewed in order to assess the implications for risk assessment. As well as data on sources of exposure in the United Kingdom (UK) an assessment of the evidence on the health effects of ED pesticides is also included. In total, 127 have been identified from the literature and their effects and modes of action are listed in this paper. Using the UK as a case study, the types and quantities of pesticides used, and their methods of application are assessed, along with their potential pathways to humans. In the UK reliable data are available only for agricultural use, so non-agricultural routes of pesticide exposure have been poorly quantified. The exposure of people resident in or visiting rural areas could also have been grossly under-estimated. Material links between ED pesticide use and specific illnesses or deformities are complicated by the multifactorial nature of disease, which can be affected by factors such as diet. Despite these difficulties, a large body of evidence has accumulated linking specific conditions to ED pesticides in wildlife and humans. A more precautionary approach to the use of ED pesticides, especially for non-essential purposes is proposed.

  6. An assessment methodology for determining pesticides adsorption on granulated activated carbon

    Barthélemy J.-P.; Gérard M.-C.

    2003-01-01

    In many countries, water suppliers add granular activated carbon reactor in the drinking water treatment notably in order to remove pesticides residues. In Europe, their concentrations must lie below the values imposed by the EU directives (98/83/EC). Acouple of years ago, some mini-column tests were developed to improve the use of the activated carbon reactor in relation with lab experiments. Modelling, which was elaborated to predict the lifetime of reactors, did not bring validated results...

  7. Occupational exposure to pesticides and respiratory health

    Ali Mamane

    2015-06-01

    Full Text Available This article aims to review the available literature regarding the link between occupational exposure to pesticides and respiratory symptoms or diseases. Identification of epidemiological studies was performed using PubMed. 41 articles were included, 36 regarding agricultural workers and five regarding industry workers. Among the 15 cross-sectional studies focusing on respiratory symptoms and agricultural pesticide exposure, 12 found significant associations with chronic cough, wheeze, dyspnoea, breathlessness or chest tightness. All four studies on asthma found a relationship with occupational exposure, as did all three studies on chronic bronchitis. The four studies that performed spirometry reported impaired respiratory function linked to pesticide exposure, suggestive of either obstructive or restrictive syndrome according to the chemical class of pesticide. 12 papers reported results from cohort studies. Three out of nine found a significant relationship with increased risk of wheeze, five out of nine with asthma and three out of three with chronic bronchitis. In workers employed in pesticide production, elevated risks of chronic obstructive pulmonary disease (two studies out of three and impaired respiratory function suggestive of an obstructive syndrome (two studies out of two were reported. In conclusion, this article suggests that occupational exposure to pesticides is associated with an increased risk of respiratory symptoms, asthma and chronic bronchitis, but the causal relationship is still under debate.

  8. Environmental exposure to pesticides and respiratory health

    Ali Mamane

    2015-09-01

    Full Text Available Respiratory effects of environmental exposure to pesticides are debated. Here we aimed to review epidemiological studies published up until 2013, using the PubMed database. 20 studies dealing with respiratory health and non-occupational pesticide exposure were identified, 14 carried out on children and six on adults. In four out of nine studies in children with biological measurements, mothers' dichlorodiphenyldichloroethylene (DDE blood levels during pregnancy were associated with asthma and wheezing in young children. An association was also found between permethrin in indoor air during pregnancy and wheezing in children. A significant association between asthma and DDE measured in children's blood (aged 7–10 years was observed in one study. However, in three studies, no association was found between asthma or respiratory infections in children and pesticide levels in breast milk and/or infant blood. Lastly, in three out of four studies where post-natal pesticide exposure of children was assessed by parental questionnaire an association with respiratory symptoms was found. Results of the fewer studies on pesticide environmental exposure and respiratory health of adults were much less conclusive: indeed, the associations observed were weak and often not significant. In conclusion, further studies are needed to confirm whether there is a respiratory risk associated with environmental exposure to pesticides.

  9. Occupational exposure to pesticides and respiratory health.

    Mamane, Ali; Baldi, Isabelle; Tessier, Jean-François; Raherison, Chantal; Bouvier, Ghislaine

    2015-06-01

    This article aims to review the available literature regarding the link between occupational exposure to pesticides and respiratory symptoms or diseases. Identification of epidemiological studies was performed using PubMed. 41 articles were included, 36 regarding agricultural workers and five regarding industry workers. Among the 15 cross-sectional studies focusing on respiratory symptoms and agricultural pesticide exposure, 12 found significant associations with chronic cough, wheeze, dyspnoea, breathlessness or chest tightness. All four studies on asthma found a relationship with occupational exposure, as did all three studies on chronic bronchitis. The four studies that performed spirometry reported impaired respiratory function linked to pesticide exposure, suggestive of either obstructive or restrictive syndrome according to the chemical class of pesticide. 12 papers reported results from cohort studies. Three out of nine found a significant relationship with increased risk of wheeze, five out of nine with asthma and three out of three with chronic bronchitis. In workers employed in pesticide production, elevated risks of chronic obstructive pulmonary disease (two studies out of three) and impaired respiratory function suggestive of an obstructive syndrome (two studies out of two) were reported. In conclusion, this article suggests that occupational exposure to pesticides is associated with an increased risk of respiratory symptoms, asthma and chronic bronchitis, but the causal relationship is still under debate.

  10. Codex alimentarius approach to pesticide residue standards.

    Maybury, R B

    1989-01-01

    To protect consumers' health, most countries have maximum legal limits for pesticide residues in foods. Trade difficulties can arise when limits differ between countries. The Codex Alimentarius Commission was established in 1962 to implement the Joint FAO/WHO Food Standards Programme, the purpose of which is to protect consumer health and ensure fair practices in international food trade. The Codex Committee on Pesticide Residues (CCPR), an intergovernmental body which advises the Commission on matters related to pesticide residues, is responsible for establishing maximum residue limits (MRLs) for pesticides in foods and feeds that move in international trade. Codex MRLs are based on residue data obtained mainly from supervised trials that reflect approved pesticide use in accordance with "good agricultural practice." MRLs must be toxicologically acceptable in terms of estimated pesticide intake by consumers. CCPR Working Groups examine problems related to establishing and implementing MRLs, including sampling and methods of analysis. Despite time and effort expended, acceptance and application of Codex MRLs face many problems in international trade.

  11. Chlorination of organophosphorus pesticides in natural waters.

    Acero, Juan L; Benítez, F Javier; Real, Francisco J; González, Manuel

    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 degrees 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. Accumulation of current-use and organochlorine pesticides in crab embryos from Northern California, USA

    Smalling, Kelly L.; Morgan, Steven; Kuivila, Kathryn K.

    2010-01-01

    Invertebrates have long been used as resident sentinels for assessing ecosystem health and productivity. The shore crabs, Hemigrapsus oregonensis and Pachygrapsus crassipes, are abundant in estuaries and beaches throughout northern California, USA and have been used as indicators of habitat conditions in several salt marshes. The overall objectives of the present study were to conduct a lab-based study to test the accumulation of current-use pesticides, validate the analytical method and to analyze field-collected crabs for a suite of 74 current-use and legacy pesticides. A simple laboratory uptake study was designed to determine if embryos could bioconcentrate the herbicide molinate over a 7-d period. At the end of the experiment, embryos were removed from the crabs and analyzed by gas chromatography/mass spectrometry. Although relatively hydrophilic (log KOW of 2.9), molinate did accumulate with an estimated bioconcentration factor (log BCF) of approximately 2.5. Following method validation, embryos were collected from two different Northern California salt marshes and analyzed. In field-collected embryos 18 current-use and eight organochlorine pesticides were detected including synthetic pyrethroids and organophosphate insecticides, as well as DDT and its degradates. Lipid-normalized concentrations of the pesticides detected in the field-collected crab embryos ranged from 0.1 to 4 ppm. Pesticide concentrations and profiles in crab embryos were site specific and could be correlated to differences in land-use practices. These preliminary results indicate that embryos are an effective sink for organic contaminants in the environment and have the potential to be good indicators of ecosystem health, especially when contaminant body burden analyses are paired with reproductive impairment assays.

  13. 40 CFR 158.2084 - Experimental use permit biochemical pesticides nontarget organisms and environmental fate data...

    2010-07-01

    ... pesticides nontarget organisms and environmental fate data requirements table. 158.2084 Section 158.2084 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Biochemical Pesticides § 158.2084 Experimental use permit biochemical...

  14. Comparative in vitro-in vivo percutaneous absorption of the pesticide propoxur.

    van de Sandt, J J; Meuling, W J; Elliott, G R; Cnubben, N H; Hakkert, B C

    2000-11-01

    In vitro and in vivo skin absorption of the pesticide propoxur (2-isopropoxyphenyl N-methyl carbamate, commercially Baygon(TM) and Unden (TM); log Po/w 1.56, MW 209.2) was investigated. In vivo studies were performed in rats and human volunteers, applying the test compound to the dorsal skin and the volar aspect of the forearm, respectively. In vitro experiments were carried out in static diffusion cells using viable full-thickness skin membranes (rat and human), non-viable epidermal membranes (rat and human) and a perfused-pig-ear model. Percutaneous penetration of propoxur in human volunteers was measured by analysis of its metabolite (2-isopropoxyphenol) in blood and urine; in all other studies radiolabeled propoxur ([ring-U-(14)C]propoxur) was used. In order to allow for direct comparison, experimental conditions were standardized with respect to dose (150 microg propoxur per cm(2)), vehicle (60% aqueous ethanol) and exposure time (4 h). In human volunteers, it was found that approximately 6% of the applied dose was excreted via the urine after 24 h, while the potential absorbed dose (amount applied minus amount washed off) was 23 microg/cm(2). In rats these values were 21% and 88 microg/cm(2), respectively. Data obtained in vitro were almost always higher than those obtained in human volunteers. The most accurate in vitro prediction of the human in vivo percutaneous absorption of propoxur was obtained on the basis of the potential absorbed dose. The absorbed dose and the maximal flux in viable full-thickness skin membranes correlated reasonably well with the human in vivo situation (maximal overestimation by a factor of 3). Epidermal membranes overestimated the human in vivo data up to a factor of 8, but the species-differences observed in vivo were reflected correctly in this model. The data generated in the perfused-pig-ear model were generally intermediate between viable skin membranes and epidermal membranes.

  15. Prioritizing pesticide compounds for analytical methods development

    Norman, Julia E.; Kuivila, Kathryn M.; Nowell, Lisa H.

    2012-01-01

    The U.S. Geological Survey (USGS) has a periodic need to re-evaluate pesticide compounds in terms of priorities for inclusion in monitoring and studies and, thus, must also assess the current analytical capabilities for pesticide detection. To meet this need, a strategy has been developed to prioritize pesticides and degradates for analytical methods development. Screening procedures were developed to separately prioritize pesticide compounds in water and sediment. The procedures evaluate pesticide compounds in existing USGS analytical methods for water and sediment and compounds for which recent agricultural-use information was available. Measured occurrence (detection frequency and concentrations) in water and sediment, predicted concentrations in water and predicted likelihood of occurrence in sediment, potential toxicity to aquatic life or humans, and priorities of other agencies or organizations, regulatory or otherwise, were considered. Several existing strategies for prioritizing chemicals for various purposes were reviewed, including those that identify and prioritize persistent, bioaccumulative, and toxic compounds, and those that determine candidates for future regulation of drinking-water contaminants. The systematic procedures developed and used in this study rely on concepts common to many previously established strategies. The evaluation of pesticide compounds resulted in the classification of compounds into three groups: Tier 1 for high priority compounds, Tier 2 for moderate priority compounds, and Tier 3 for low priority compounds. For water, a total of 247 pesticide compounds were classified as Tier 1 and, thus, are high priority for inclusion in analytical methods for monitoring and studies. Of these, about three-quarters are included in some USGS analytical method; however, many of these compounds are included on research methods that are expensive and for which there are few data on environmental samples. The remaining quarter of Tier 1

  16. Application of zirconium dioxide nanoparticle sorbent for the clean-up step in post-harvest pesticide residue analysis.

    Uclés, Ana; Herrera López, Sonia; Dolores Hernando, Maria; Rosal, Roberto; Ferrer, Carmen; Fernández-Alba, Amadeo R

    2015-11-01

    The use of yttria-stabilized zirconium dioxide nanoparticles as d-SPE clean-up sorbent for a rapid and sensitive liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) method for the determination of post-harvest fungicides (carbaryl, carbendazim, chlorpropham, diphenylamine, ethoxyquin, flutriafol, imazalil, iprodione, methomyl, myclobutanil, pirimiphos-methyl, prochloraz, pyrimethanil, thiabendazole, thiophanate-methyl and tolclofos-methyl) in orange and pear samples has been evaluated and validated. The sample preparation was a modification of the QuEChERS extraction method using yttria-stabilized zirconium dioxide and multi-walled carbon nanotubes (MWCNTs) nanoparticles as the solid phase extraction (d-SPE) clean-up sorbents prior to injecting the ten-fold diluted extracts into the LC system. By using the yttria-stabilized zirconium dioxide extraction method, more recoveries in the 70-120% range were obtained - thus this method was used for the validation. Quantification was carried out using a matrix-matched calibration curve which was linear in the 1-500 µg kg(-1) range for almost all the pesticides studied. The validated limit of quantification was 10 µg kg(-1) for most of the studied compounds, except chlorpropham, ethoxyquin and thiophanate-methyl. Pesticide recoveries at the 10 and 100 µg kg(-1) concentration levels were satisfactory, with values between 77% and 120% and relative standard deviations (RSD) lower than 10% (n=5). The developed method was applied for the determination of selected fungicides in 20 real orange and pear samples. Four different pesticide residues were detected in 10 of these commodities; 20% of the samples contained pesticide residues at a quantifiable level (equal to or above the LOQs) for at least one pesticide residue. The most frequently-detected pesticide residues were: carbendazim, thiabendazole and imazalil-all were below the MRL. The highest concentration found was imazalil at 1175 µg kg

  17. Pattern of pesticide storage before pesticide self-poisoning in rural Sri Lanka

    Mohamed, Fahim; Manuweera, Gamini; Gunnell, David

    2009-01-01

    -harm to help inform suicide prevention strategies such as reducing domestic access to pesticides. METHODS: The study was conducted in a district hospital serving an agricultural region of Sri Lanka. Patients who had self-poisoned with pesticides and were admitted to the adult medical wards were interviewed...

  18. 76 FR 552 - Pesticides; Availability of Pesticide Registration Notice Regarding the Residential Exposure...

    2011-01-05

    ... of the Residential Exposure Joint Venture, L.L.C. This PR Notice (PR Notice 2011-1) issued by the... AGENCY Pesticides; Availability of Pesticide Registration Notice Regarding the Residential Exposure Joint Venture AGENCY: Environmental Protection Agency (EPA). ACTION: Notice. SUMMARY: The Agency is...

  19. Biosensor technology for pesticides--a review.

    Verma, Neelam; Bhardwaj, Atul

    2015-03-01

    Pesticides, due to their lucrative outcomes, are majorly implicated in agricultural fields for crop production enhancement. Due to their pest removal properties, pesticides of various classes have been designed to persist in the environment over a longer duration after their application to achieve maximum effectiveness. Apart from their recalcitrant structure and agricultural benefits, pesticides also impose acute toxicological effects onto the other various life forms. Their accumulation in the living system may prove to be detrimental if established in higher concentrations. Thus, their prompt and accurate analysis is a crucial matter of concern. Conventional techniques like chromatographic techniques (HPLC, GC, etc.) used for pesticides detection are associated with various limitations like stumpy sensitivity and efficiency, time consumption, laboriousity, requirement of expensive equipments and highly trained technicians, and many more. So there is a need to recruit the methods which can detect these neurotoxic compounds sensitively, selectively, rapidly, and easily in the field. Present work is a brief review of the pesticide effects, their current usage scenario, permissible limits in various food stuffs and 21st century advancements of biosensor technology for pesticide detection. Due to their exceptional performance capabilities, easiness in operation and on-site working, numerous biosensors have been developed for bio-monitoring of various environmental samples for pesticide evaluation immensely throughout the globe. Till date, based on sensing element (enzyme based, antibody based, etc.) and type of detection method used (Electrochemical, optical, and piezoelectric, etc.), a number of biosensors have been developed for pesticide detection. In present communication, authors have summarized 21st century's approaches of biosensor technology for pesticide detection such as enzyme-based biosensors, immunosensors, aptamers, molecularly imprinted polymers, and

  20. Chromogenic platform based on recombinant Drosophila melanogaster acetylcholinesterase for visible unidirectional assay of organophosphate and carbamate insecticide residues

    Han Zheng [Institute for Agri-food Standards and Testing Technology, Shanghai Academy of Agricultural Sciences, 1018 Jinqi Road, Shanghai 201403 (China); Chi Chensen [School of Life Science and Biotechnology, Bor Luh Food Safety Center, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (China); Bai Bing; Liu Gang; Rao Qinxiong [Institute for Agri-food Standards and Testing Technology, Shanghai Academy of Agricultural Sciences, 1018 Jinqi Road, Shanghai 201403 (China); Peng Shaojie [Institute of Shanghai Food and Drug Supervision, 615 Liuzhou Road, Shanghai 200233 (China); Liu Hong [Shanghai Municipal Center for Disease Control and Prevention, 1380 Zhongshan West Road, Shanghai 200336 (China); Zhao Zhihui [Institute for Agri-food Standards and Testing Technology, Shanghai Academy of Agricultural Sciences, 1018 Jinqi Road, Shanghai 201403 (China); Zhang Dabing [School of Life Science and Biotechnology, Bor Luh Food Safety Center, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (China); Wu Aibo, E-mail: wuaibo@saas.sh.cn [Institute for Agri-food Standards and Testing Technology, Shanghai Academy of Agricultural Sciences, 1018 Jinqi Road, Shanghai 201403 (China)

    2012-03-30

    Highlight: Black-Right-Pointing-Pointer A visible chromogenic platform for rapid analysis of OP and CM insecticide residues was developed. Black-Right-Pointing-Pointer The assay has the capabilities of both qualitative measurement and quantitative analysis. Black-Right-Pointing-Pointer The sensitivity, capabilities of resisting interferences and storage stability were desirable. Black-Right-Pointing-Pointer Matrix effects were acceptable and detection performance was satisfactory in real application. - Abstract: In this study we propose a chromogenic platform for rapid analysis of organophosphate (OP) and carbamate (CM) insecticide residues, based on recombinant Drosophila melanogaster acetylcholinesterase (R-DmAChE) as enzyme and indoxyl acetate as substrate. The visible chromogenic strip had the advantages identical to those of commonly used lateral flow assays (LFAs) with utmost simplicity in sample loading and result observation. After optimization, depending on the color intensity (CI) values, the well-established assay has the capabilities of both qualitative measurement via naked eyes and quantitative analysis by colorimetric reader with the desirable IC{sub 50} values against the tested six insecticides (0.06 {mu}g mL{sup -1} of carbofuran, 0.28 {mu}g mL{sup -1} of methomyl, 0.03 {mu}g mL{sup -1} of dichlorvos, 31.6 {mu}g mL{sup -1} of methamidophos, 2.0 {mu}g mL{sup -1} of monocrotophos, 6.3 {mu}g mL{sup -1} of omethoate). Acceptable matrix effects and satisfactory detection performance were confirmed by in-parallel LC-MS/MS analysis in different vegetable varieties at various spiked levels of 10{sup -3} to 10{sup 1} {mu}g g{sup -1}. Overall, the testified suitability and applicability of this novel platform meet the requirements for practical use in food safety management and environmental monitoring, especially in the developing world.

  1. [Simultaneous determination of ethyl carbamate and chloropropanols in flavorings by gas chromatography-triple quadrupole tandem mass spectrometry].

    Xu, Xiaomin; He, Huali; Ruan, Yudi; Huang, Baifen; Zhang, Jingshun; Cai, Zengxuan; Ren, Yiping

    2013-11-01

    A simultaneous determination method for ethyl carbamate (EC) and chloropropanols (3-monochloropropane-1, 2-diol (3-MCPD) and 2-monochloropropane-1, 3-diol (2-MCPD)) in flavorings was developed by gas chromatography-triple quadrupole tandem mass spectrometry (GC-MS/MS). After spiked with internal standard, the sample was extracted by matrix solid-phase dispersion extraction technique with an Extrelut NT column. Hexane was used to wash the fat soluble matrix interferences and then an ethyl acetate-ethyl ether (20: 80, v/v) mixture was added to elute the analytes. The concentrated extract was detected by GC-MS/MS in multiple reaction monitoring (MRM) mode. The limits of detection (LODs) were 2, 5 and 5 microg/kg for EC, 3-MCPD and 2-MCPD, respectively. The linear ranges were 5 - 1 000 microg/kg (r = 0.9997), 10-1000 microg/kg (r = 0.999 1) and 10-1000 microg/kg (r = 0.999 5) for EC, 3-MCPD and 2-MCPD, respectively. In soy sauce, yellow rice wine, salami sauce and flavoring of instant noodle matrices, the recoveries (RSDs, n = 7) in MRM mode at the levels of 20, 100 and 400 microg/kg were 87.7%-104% (4.3%-10.7%), 90.1%-109% (2.6%-10.2%), and 90.9%-103% (3.0%-9.5%), respectively. EC, 3-MCPD and 2-MCPD were found in some real samples of the soy sauce, wine and flavoring of instant noodle. EC or 3-MCPD was found in some of the salami samples. The method is accurate, fast and suitable for the simultaneous determination of EC, 3-MCPD and 2-MCPD in flavorings.

  2. [Rapid Detection of Trace Dimethoate Pesticide Residues Based on Colorimetric Spectroscopy].

    Li, Wen; Sun, Ming; Li, Min-zan; Sun, Hong

    2015-07-01

    In order to detect dimethoate pesticide residues rapidly and safely, a feasible method based on colorimetric spectroscopy was developed. Because dimethoate is one of organophosphorus pesticides containing sulfur, its sulfenyl can react with Pd2+ to produce a yellow complex named palladium sulfide. PdCl2 was used as the color agent, which was dissolved in acetic acid instead of the common concentrated hydrochloric acid. The dimethoate solution was prepared by dissolving the commercial pesticides into distilled water at different concentrations. The pesticide samples were reacted with the same amount of PdC2 solution respectively. The absorbance spectra of the samples after coloring reaction were measured in the region of 300-900 nm by a spectrophotometer. The result showed that the effect of using acetic acid instead of concentrated hydrochloric acid was not only safe but also preferable, and 0.5 mg x kg(-1) was the minimum concentration of the pesticide that could be distinguished in the spectra. The result met the pesticide residue detecting requirements of part fruits and vegetables in the national standard GB2763-2012 regulations. Further studies on random 40 dimethoate samples from 0.5 to 88 mg x kg(-1) were carried out. Thirty samples were randomly selected to establish the training model and remaining 10 samples were used to test the model. The preprocessing methods were carried on the spectrum data such as normalization and smoothing to get a better effect through comparison their prediction results with the correlation coefficient (r) and the root mean square error of cross-validation (RMSEP). The principal component analysis (PCA) method and partial least squares (PLS) method were used to establish prediction models respectively in the different wave ranges. By calculating the correlation coefficient of dimethoate samples in 350-900 nm the maximum of 0.9572 was obtained at wavelength 458 nm, so 453-463 and 400-600 nm were selected as feather regions

  3. 40 CFR 158.2170 - Experimental use permit data requirements-microbial pesticides.

    2010-07-01

    ... requirements-microbial pesticides. 158.2170 Section 158.2170 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Microbial Pesticides § 158.2170 Experimental use permit data requirements—microbial pesticides. (a) For all microbial pesticides. (1)...

  4. Watershed Regressions for Pesticides (WARP) models for predicting stream concentrations of multiple pesticides

    Stone, Wesley W.; Crawford, Charles G.; Gilliom, Robert J.

    2013-01-01

    Watershed Regressions for Pesticides for multiple pesticides (WARP-MP) are statistical models developed to predict concentration statistics for a wide range of pesticides in unmonitored streams. The WARP-MP models use the national atrazine WARP models in conjunction with an adjustment factor for each additional pesticide. The WARP-MP models perform best for pesticides with application timing and methods similar to those used with atrazine. For other pesticides, WARP-MP models tend to overpredict concentration statistics for the model development sites. For WARP and WARP-MP, the less-than-ideal sampling frequency for the model development sites leads to underestimation of the shorter-duration concentration; hence, the WARP models tend to underpredict 4- and 21-d maximum moving-average concentrations, with median errors ranging from 9 to 38% As a result of this sampling bias, pesticides that performed well with the model development sites are expected to have predictions that are biased low for these shorter-duration concentration statistics. The overprediction by WARP-MP apparent for some of the pesticides is variably offset by underestimation of the model development concentration statistics. Of the 112 pesticides used in the WARP-MP application to stream segments nationwide, 25 were predicted to have concentration statistics with a 50% or greater probability of exceeding one or more aquatic life benchmarks in one or more stream segments. Geographically, many of the modeled streams in the Corn Belt Region were predicted to have one or more pesticides that exceeded an aquatic life benchmark during 2009, indicating the potential vulnerability of streams in this region.

  5. Validating the importance of two acetylcholinesterases in insecticide sensitivities by RNAi in Pardosa pseudoannulata, an important predatory enemy against several insect pests.

    Meng, Xiangkun; Li, Chunrui; Bao, Haibo; Fang, Jichao; Liu, Zewen; Zhang, Yixi

    2015-11-01

    The pond wolf spider (Pardosa pseudoannulata) is an important predatory enemy against several insect pests and showed relative different sensitivities to organophosphate and carbamate insecticides compared to insect pests. In our previous studies, two acetylcholinesterases were identified in P. pseudoannulata and played important roles in insecticide sensitivities. In order to understand the contributions of the two acetylcholinesterases to insecticide sensitivities, we firstly employed the RNAi technology in the spider. For a suitable microinjection RNAi method, the injection site, injection volume and interference time were optimized, which then demonstrated that the injection RNAi method was applicable in this spider. With the new RNAi method, it was revealed that both Pp-AChE1 and Pp-AChE2, encoded by genes Ppace1 and Ppace2, were the targets of organophosphate insecticides, but Pp-AChE1 would be more important. In contrast, the carbamate acted selectively on Pp-AChE1. The results showed that Pp-AChE1 was the major catalytic enzyme in P. pseudoannulata and the major target of organophosphate and carbamate insecticides. In a word, an RNAi method was established in the pond wolf spider, which further validated the importance of two acetylcholinesterases in insecticide sensitivities in this spider.

  6. [EXPERIMENTAL GROUNDS ON POSSIBILITY TO MAKE AND TO USE PREDICTION MODELS OF PESTICIDES DESIGN STANDARD IN THE WATER OF PONDS USED FOR HOUSEHOLD AND DRINKING WATER SUPPLY].

    Vavrinevych, O P; Omel'chuk, S T

    2015-01-01

    Taking into account the fact that current calculation methods for substantiation of standards in the water of water reservoirs valid in Ukraine are outdated the aim of our research was to scientifically substantiate the possibility to make and to use prediction models of pesticides design standard in the water of ponds used for household and drinking water supply. Array of experimentally substantiated and approved to use in Ukraine maximum allowable concentrations (MAC) of organic pesticides active ingredients in the water was analyzed (n = 201). Analysis of dependence between MAC value of pesticides in the water and its physical and chemical properties, indices of ecotoxicological hazard and persistency in the water was carried out using correlation and regression analysis methods. Twelve regression equations to establish design value of pesticides MAC in the water were proposed on the grounds of performed analysis. The results of reliability testing of proposed procedure on pesticides design tentatively allowable levels (TAL) in the water indicate on needs to apply the least value of TAL obtained in the process of calculations using proposed equations. It was proved that mathematical models proposed for prediction of pesticide design standard in the water are adequate and significant by Fisher's test (P water for new pesticides.

  7. HER-2/neu and CD117 (c-kit overexpression in patients with pesticide exposure and extensive stage small cell lung carcinoma (ESSCLC

    Potti Anil

    2005-06-01

    Full Text Available Abstract Background The rate of detection of HER-2/neu and CD117 (c-kit overexpression in small cell lung cancer (SCLC has varied widely; between 5–35% and 21–70% respectively. Methods To evaluate the relationship between pesticide exposure and HER-2/neu and CD117 overexpression in extensive stage SCLC (ESSCLC, we identified patients with ESSCLC and assessed pesticide exposure using a predetermined questionnaire. An exposure index (hours/day × days/year × years ≥ 2400 hours was considered as 'exposed.' HER-2/neu overexpression was evaluated on archival tissue using the DAKO Hercep test, and CD117 testing was performed using immunohistochemistry (A4052 polyclonal antibody. Results 193 ESSCLC patients were identified. Pesticide exposure data could be obtained on 174 patients (84 females and 109 males with a mean age of 68.5 years. 53/174 (30.4% revealed HER-2/neu overexpression. 54/174 (31.03% specimens showed CD117 overexpression by IHC. On multivariate analysis, HER-2/neu overexpression was associated with diminished survival (p neu overexpression and 47/121 (38.8% patients without overexpression had exposure to pesticides (odds ratio: 5.38; p Conclusion Pesticide exposure affects HER-2/neu but not CD117 overexpression. Future studies are needed to determine specific pesticide(s/pesticide components that are responsible for HER-2/neu overexpression in ESSCLC, and to validate our findings in other solid tumors that overexpress HER-2/neu.

  8. Emission of pesticides into the air

    Van Den, Berg; Kubiak, R.; Benjey, W.G.; Majewski, M.S.; Yates, S.R.; Reeves, G.L.; Smelt, J.H.; Van Der Linden, A. M. A.

    1999-01-01

    During and after the application of a pesticide in agriculture, a substantial fraction of the dosage may enter the atmosphere and be transported over varying distances downwind of the target. The rate and extent of the emission during application, predominantly as spray particle drift, depends primarily on the application method (equipment and technique), the formulation and environmental conditions, whereas the emission after application depends primarily on the properties of the pesticide, soils, crops and environmental conditions. The fraction of the dosage that misses the target area may be high in some cases and more experimental data on this loss term are needed for various application types and weather conditions. Such data are necessary to test spray drift models, and for further model development and verification as well. Following application, the emission of soil fumigants and soil incorporated pesticides into the air can be measured and computed with reasonable accuracy, but further model development is needed to improve the reliability of the model predictions. For soil surface applied pesticides reliable measurement methods are available, but there is not yet a reliable model. Further model development is required which must be verified by field experiments. Few data are available on pesticide volatilization from plants and more field experiments are also needed to study the fate processes on the plants. Once this information is available, a model needs to be developed to predict the volatilization of pesticides from plants, which, again, should be verified with field measurements. For regional emission estimates, a link between data on the temporal and spatial pesticide use and a geographical information system for crops and soils with their characteristics is needed.

  9. Integrated microwave processing system for the extraction of organophosphorus pesticides in fresh vegetables.

    Wu, Lijie; Song, Ying; Hu, Mingzhu; Xu, Xu; Zhang, Hanqi; Yu, Aimin; Ma, Qiang; Wang, Ziming

    2015-03-01

    A simple and efficient integrated microwave processing system (IMPS) was firstly assembled and validated for the extraction of organophosphorus pesticides in fresh vegetables. Two processes under microwave irradiation, dynamic microwave-assisted extraction (DMAE) and microwave-accelerated solvent elution (MASE), were integrated for simplifying the pretreatment of the sample. Extraction, separation, enrichment and elution were finished in a simple step. The organophosphorus pesticides were extracted from the fresh vegetables into hexane with DMAE, and then the extract was directly introduced into the enrichment column packed with active carbon fiber (ACF). Subsequently, the organophosphorus pesticides trapped on the ACF were eluted with ethyl acetate under microwave irradiation. No further filtration or cleanup was required before analysis of the eluate by gas chromatography-mass spectrometry. Some experimental parameters affecting extraction efficiency were investigated and optimized, such as microwave output power, kind and volume of extraction solvent, extraction time, amount of sorbent, elution microwave power, kind and volume of elution solvent, elution solvent flow rate. Under the optimized conditions, the recoveries were in the range of 71.5-105.2%, and the relative standard deviations were lower than 11.6%. The experiment results prove that the present method is a simple and effective sample preparation method for the determination of pesticides in solid samples.

  10. Hypervalent iodine(iii)-promoted N-incorporation into N-aryl vinylogous carbamates to quinoxaline diesters: access to 1,4,5,8-tetraazaphenanthrene.

    Sagar, A; Vidaycharan, Shinde; Shinde, Anand H; Sharada, Duddu S

    2016-04-26

    A novel oxidative N-incorporation strategy for synthesis of quinoxaline diesters under metal-free conditions is described for the first time. The mild reaction conditions allow for this transformation via the formation of two C(sp(2))-N bonds utilizing cheaply available NaN3 as the N-atom source. N-Aryl vinylogous carbamates in this study undergo azidation at enamino C(sp(2))-H selectively. The robustness of this strategy is further demonstrated by the synthesis of a valuable 1,4,5,8-tetraazaphenanthrene derivative using a mild and convenient approach.

  11. Distribution of ace-1R and resistance to carbamates and organophosphates in Anopheles gambiae s.s. populations from Côte d'Ivoire

    Ahoua Alou Ludovic P

    2010-06-01

    Full Text Available Abstract Background The spread of pyrethroid resistance in Anopheles gambiae s.s. is a critical issue for malaria vector control based on the use of insecticide-treated nets. Carbamates and organophosphates insecticides are regarded as alternatives or supplements to pyrethroids used in nets treatment. It is, therefore, essential to investigate on the susceptibility of pyrethroid resistant populations of An. gambiae s.s. to these alternative products. Methods In September 2004, a cross sectional survey was conducted in six localities in Côte d'Ivoire: Toumbokro, Yamoussoukro, Toumodi in the Southern Guinea savannah, Tiassalé in semi-deciduous forest, then Nieky and Abidjan in evergreen forest area. An. gambiae populations from these localities were previously reported to be highly resistant to pyrethroids insecticides. Anopheline larvae were collected from the field and reared to adults. Resistance/susceptibility to carbamates (0.4% carbosulfan, 0.1% propoxur and organophosphates (0.4% chlorpyrifos-methyl, 1% fenitrothion was assessed using WHO bioassay test kits for adult mosquitoes. Then, PCR assays were run to determine the molecular forms (M and (S, as well as phenotypes for insensitive acetylcholinesterase (AChE1 due to G119S mutation. Results Bioassays showed carbamates (carbosulfan and propoxur resistance in all tested populations of An. gambiae s.s. In addition, two out of the six tested populations (Toumodi and Tiassalé were also resistant to organophosphates (mortality rates ranged from 29.5% to 93.3%. The M-form was predominant in tested samples (91.8%. M and S molecular forms were sympatric at two localities but no M/S hybrids were detected. The highest proportion of S-form (7.9% of An. gambiae identified was in sample from Toumbokro, in the southern Guinea savannah. The G119S mutation was found in both M and S molecular forms with frequency from 30.9 to 35.2%. Conclusion This study revealed a wide distribution of insensitive

  12. New EPA Guidance for Testing Pesticides Will Reduce Animal Testing

    EPA is issuing guidance for requesting waivers of acute dermal toxicity testing requirements for pesticide formulations, which will lead to fewer animal tests for acute dermal toxicity for pesticides.

  13. Avoid Counterfeit Pesticide Products for Dogs and Cats

    EPA is aware of counterfeit pet pesticides designed to look like legitimately registered pesticide products. The information on this page is intended to help consumers avoid unregistered pet products.

  14. 75 FR 62387 - Pesticide Product Registrations; Conditional Approval

    2010-10-08

    ... AGENCY Pesticide Product Registrations; Conditional Approval AGENCY: Environmental Protection Agency (EPA...., to conditionally register the pesticide products Paladin Technical, Paladin, and Paladin EC... provisions of section 3(c)(7)(C) of the Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA),...

  15. Pesticide use knowledge and practices: a gender differences in Nepal.

    Atreya, Kishor

    2007-06-01

    It is important to understand gender difference on pesticide use knowledge, attitude and practices for identifying pesticide risks by gender and to recommend more gender-sensitive programs. However, very few studies have been conducted so far in Nepal. This study, thus, interviewed a total of 325 males and 109 females during 2005 to assess gender differences on pesticide use knowledge, attitude and practices. More than 50% females had never been to school and only Pest Management (IPM). Almost all males and females did not smoke, drink and eat during pesticides application and also believed that pesticides are harmful to human health, livestock, plant diversity and their environment. However, there were gender differences on household decision on pesticides to be used (phigher risk due to lower level of pesticide use safety and awareness. It is strongly recommended to initiate gender-sensitive educational and awareness activities, especially on pesticide use practices and safety precautions.

  16. Metabolism of pesticides after dermal exposure to amphibians

    Understanding how pesticide exposure to non-target species influences toxicity is necessary to accurately assess the ecological risks these compounds pose. Aquatic, terrestrial, and arboreal amphibians are often exposed to pesticides during their agricultural application resultin...

  17. [A model study of pesticide biodegradation in soil].

    Bieganska, J

    2007-01-01

    This study addresses the efficiency of microbial preparations to degrade pesticide residues in soil. A method to degrade pesticides DNOC and pendimethalin using Pseudomonas and Arthrobacter bacteria with a fertilizer is described.

  18. A multi-residue method for the determination of pesticides in tea using multi-walled carbon nanotubes as a dispersive solid phase extraction absorbent.

    Hou, Xue; Lei, Shaorong; Qiu, Shiting; Guo, Lingan; Yi, Shengguo; Liu, Wei

    2014-06-15

    A modified QuEChERS (quick, easy, cheap, effective, rugged and safe) method using multi-walled carbon nanotubes (MWCNTs) as a dispersive solid phase extraction (d-SPE) absorbent was established for analysis of 78 pesticide residues in tea. A 6 mg MWCNT sample was selected as the optimised amount based on the distribution of pesticide recoveries and clean-up efficiency from 6 mL acetonitrile extracts. The matrix effects of the method were evaluated and matrix-matched calibration was recommended. The method was validated employing gas chromatography coupled to tandem mass spectrometry (GC-MS/MS) at the spiked concentration levels of 0.05, 0.1 and 0.15 mg kg(-1). For most of the targeted pesticides, the percent recoveries range from 70% to 120%, with relative standard deviations (RSDs) absorbent with excellent cleanup efficiency, which could be widely applied for the analysis of pesticide residues.

  19. Refined methodology for the determination of neonicotinoid pesticides and their metabolites in honey bees and bee products by liquid chromatography-tandem mass spectrometry (LC-MS/MS).

    Kamel, Alaa

    2010-05-26

    An analytical method was refined for the extraction and determination of neonicotinoid pesticide residues and their metabolites in honey bees and bee products. Samples were extracted with 2% triethylamine (TEA) in acetonitrile (ACN) followed by salting out, solid phase extraction (SPE) cleanup, and detection using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The method was validated in triplicate at three fortification concentrations in each matrix. Good recoveries were observed for most analytes and ranged between 70 and 120% with relative standard deviations between replicates of pesticides and ranged between 0.2 and 15 ng/g for the neonicotinoid metabolites. This refined method provides lower detection limits and improved recovery of neonicotinoids and their metabolites, which will help researchers evaluate subchronic effects of these pesticides, address data gaps related to colony collapse disorder (CCD), and determine the role of pesticides in pollinator decline.

  20. Compound specific isotope analysis of organophosphorus pesticides.

    Wu, Langping; Yao, Jun; Trebse, Polonca; Zhang, Ning; Richnow, Hans H

    2014-09-01

    Compound-specific isotope analysis (CSIA) has been established as a tool to study the environmental fate of a wide range of contaminants. In this study, CSIA was developed to analyse the stable carbon isotope signatures of the widely used organophosphorus pesticides: dichlorvos, omethoate and dimethoate. The linearity of the GC-C-IRMS system was tested for target pesticides and led to an acceptable isotope composition within the uncertainty of the instrument. In order to assess the accuracy of the developed method, the effect of the evaporation procedure on measured carbon isotope composition (δ(13)C) values was studied and showed that concentration by evaporation of solvents had no significant isotope effect. The CSIA was then applied to investigate isotope fractionation of the hydrolysis and photolysis of selected pesticides. The carbon isotope fractionation of tested pesticides was quantified by the Rayleigh model, which revealed a bulk enrichment factor (ε) of -0.2±0.1‰ for hydrolysis of dichlorvos, -1.0±0.1‰ and -3.7±1.1‰ for hydrolysis and photolysis of dimethoate respectively. This study is a first step towards the application of CSIA to trace the transport and degradation of organophosphorus pesticides in the environment.

  1. The establishment and evaluation of near infrared universal model to determinate the effective ingredient content in pesticide rapidly

    Yan Mei Xiong; Xiang Zhong Song; Chang Zhou Chen; Hong Ping Lin; Guo Tang; Yue Huang; Jia Duan; Shun Geng Min

    2012-01-01

    A near infrared universal quantitative analysis model was established to determinate the effective ingredient content in pesticide EC (hikernalisation) by the PLS (partial least squares) algorithm,the model predictive ability was evaluated by the external inspection method.The model was established among samples containing the same active ingredient from five different companies,and the model determination coefficient R2 and RMSECV (root mean square error of cross validation) were 0.9997 and 0.0223,respectively,the relative error between predicted value and chemical value of the testing set samples was between -2.71% and 3.36%,which indicated that the method to determinate the effective ingredient content in pesticide EC by the established universal model can meet the need of pesticide market monitoring.

  2. Multiclass method for pesticides quantification in honey by means of modified QuEChERS and UHPLC-MS/MS.

    Tette, Patrícia Amaral Souza; da Silva Oliveira, Fabiano Aurélio; Pereira, Elba Nathália Corrêa; Silva, Gilsara; de Abreu Glória, Maria Beatriz; Fernandes, Christian

    2016-11-15

    Bee products can be produced in an environment contaminated by pesticides that can be transported by honey bees to the hive and incorporated into the honey. Therefore, rapid and modern methods to determine pesticide residues in honey samples are essential to guarantee consumers' health. In this study, a simple multiresidue method for the quantification of 116 pesticides in honey is proposed. It involves the use of a modified QuEChERS procedure followed by UHPLC-MS/MS analysis. The method was validated according to the European Union SANCO/12571/2013 guidelines. Acceptable values were obtained for the following parameters: linearity, limit of detection (0.005mg/kg) and limit of quantification (0.010 and 0.025mg/kg), trueness (for the four tested levels the recovery assays values were between 70 and 120%), intermediate precision (RSDhoney samples from five states of Brazil.

  3. Procedures for Removal of Pesticides from the Environment

    Đokić, M.; Bilandžić, N.; Briški, F.

    2012-01-01

    Pesticides are widely used in food production, and it is believed that more than 1000 types of pesticides are in use. Organochlorines and organophosphorous pesticides are used in large quantities due to their efficacy and low cost. These persistent organic pollutants remain in the soil, silt, and sediment long after application, and enter into watercourses, finding their way directly into the food chain. Today, the following procedures are used to remove pesticides from polluted localities: l...

  4. Public Health Implications of Pesticide Residues in Meat

    Jadhav V.J. and Waskar V.S.

    2011-01-01

    Use of pesticides in India began in 1948 when DDT was imported for malaria control and BHC for locust control. Since then various synthetic pesticides are used for protection of crops and public health. The persistence nature of some of these pesticides led to their accumulation in animal tissues and subsequently causes human dietary exposure to these pesticides through consumption of animal products viz. meat, milk, eggs and seafoods. Scientific evidence suggest that even such low dose but l...

  5. 77 FR 75082 - Notice of Receipt of Several Pesticide Petitions Filed for Residues of Pesticide Chemicals in or...

    2012-12-19

    ... environmental justice issues, the Agency seeks information on any groups or segments of the population who, as a... ingredient in pesticide formulations for a packaging film for unit dose packaging of pesticides and...

  6. 76 FR 2110 - Notice of Receipt of a Pesticide Petition Filed for Residues of Pesticide Chemicals in or on...

    2011-01-12

    ...This notice announces the Agency's receipt of an initial filing of a pesticide petition proposing the establishment or modification of regulations for residues of pesticide chemicals in or on various...

  7. Estimation of agricultural pesticide use in drainage basins using land cover maps and county pesticide data

    Nakagaki, Naomi; Wolock, David M.

    2005-01-01

    A geographic information system (GIS) was used to estimate agricultural pesticide use in the drainage basins of streams that are studied as part of the U.S. Geological Survey?s National Water-Quality Assessment (NAWQA) Program. Drainage basin pesticide use estimates were computed by intersecting digital maps of drainage basin boundaries with an enhanced version of the National Land Cover Data 1992 combined with estimates of 1992 agricultural pesticide use in each United States county. This report presents the methods used to quantify agricultural pesticide use in drainage basins using a GIS and includes the estimates of atrazine use applied to row crops, small-grain crops, and fallow lands in 150 watersheds in the conterminous United States. Basin atrazine use estimates are presented to compare and analyze the results that were derived from 30-meter and 1-kilometer resolution land cover and county pesticide use data, and drainage basin boundaries at various grid cell resolutions. Comparisons of the basin atrazine use estimates derived from watershed boundaries, county pesticide use, and land cover data sets at different resolutions, indicated that overall differences were minor. The largest potential for differences in basin pesticide use estimates between those derived from the 30-meter and 1-kilometer resolution enhanced National Land Cover Data 1992 exists wherever there are abrupt agricultural land cover changes along the basin divide. Despite the limitations of the drainage basin pesticide use data described in this report, the basin estimates provide consistent and comparable indicators of agricultural pesticide application in surface-water drainage basins studied in the NAWQA Program.

  8. In Vitro Studies of Neurotoxic Substances

    1985-12-31

    less neurotoxic to mammals and, in the case of pesticides, more toxic to insects . Validated in vitro test systems developed specifically for the...1974, Johnson (11) reported that phosphinates behaved like carbamates and sulphonates against NTE, inhibiting it but not causing OPIDN. p It has been

  9. 29 CFR 1440.1 - Arbitration of pesticide data disputes.

    2010-07-01

    ... 29 Labor 4 2010-07-01 2010-07-01 false Arbitration of pesticide data disputes. 1440.1 Section 1440... ARBITRATION OF PESTICIDE DATA DISPUTES § 1440.1 Arbitration of pesticide data disputes. (a) Persons requesting... in writing to the appropriate American Arbitration Association Regional Office. Such requests...

  10. From pesticides to genetically modified plants : history, economics and politics

    Zadoks, J.C.; Waibel, H.

    2000-01-01

    Two technologies of crop protection are compared, crop protection by pesticides and by Genetically Modified Plants (GMPs). The history of pesticides provides lessons relevant to the future of GMPs; (1) high pesticide usage is counter-productive, (2) the technology requires intensive regulation and (

  11. 42 CFR 84.1156 - Pesticide respirators; performance requirements; general.

    2010-10-01

    ... resistance will be measured in the facepiece, mouthpiece, hood, or helmet of a pesticide respirator mounted... allowable resistance requirements for pesticide respirators are as follows: Maximum Resistance Type of... 42 Public Health 1 2010-10-01 2010-10-01 false Pesticide respirators; performance...

  12. 40 CFR 158.100 - Pesticide use patterns.

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Pesticide use patterns. 158.100... DATA REQUIREMENTS FOR PESTICIDES How To Use Data Tables § 158.100 Pesticide use patterns. (a) General use patterns. There are six broad use categories used in the data tables. The six broad...

  13. Recognition and Management of Pesticide Poisonings. Third Edition.

    Morgan, Donald P.

    This manual aids health professionals in recognizing and treating pesticide poisonings. Suggested treatments are appropriate for implementation in the small hospitals and clinics which usually receive the victims of pesticide poisoning. Classes of compounds covered include: (1) organophosphate cholinesterase-inhibiting pesticides; (2) carbamate…

  14. 75 FR 35805 - Pesticide Product Registrations; Conditional Approvals

    2010-06-23

    ... applications from Monsanto Company, 800 North Lindbergh Boulevard, St. Louis, MO 63167, to register pesticide... announced that Monsanto Company had submitted applications to register pesticide products containing the new... comment opposed granting Monsanto Company rights to produce, sell, or manufacture pesticide...

  15. Toxicity Studies on "840 Biologic Pesticide"

    2002-01-01

    [Objective] "840 Biologic Pesticide" is a very effective biologic pesticide. It consists of Abamectin and celastrus angulatus. Toxicity study was aimed to provide scientific toxicological basis. [Methods] The acute toxicity test,Ames test,micronucleus test and testicle chromosome aberration test were done. [Results] The acute toxicity of single dose of "840 Biologic Pesticide" showed that acute oral LD50 for female and male rats are 4 300 and 4 280 mg/kg,and for female and male mice are 2 330 and 5 110 mg/kg,respectively. The dermal LD50 was >2 000 mg/kg for female and male rats. The mutagenesis studies indicated that Ames test,micronucleus test and testicle chromosome aberration test were negative. [Conclusion] Tested pesticidc belongs to low toticity grade.

  16. Assessing the Potential Content of Ethyl Carbamate in White, Red, and Rosé Wines as a Key Factor for Pursuing Urea Degradation by Purified Acid Urease.

    Cerreti, Martina; Fidaleo, Marcello; Benucci, Ilaria; Liburdi, Katia; Tamborra, Pasquale; Moresi, Mauro

    2016-07-01

    The ethyl carbamate (EC) content of a wine after a given temperature-time storage was theoretically predicted from the potential concentration of ethyl carbamate (PEC), as determined via an accelerated EC formation test. Such information was used to decide whether an enzymatic treatment was needed to reduce the wine urea level before bottling/aging. To this end, 6 white, red, and rosé wines, manufactured in Italy as such or enriched with urea, were tested for their PEC content either before or after enzymatic treatment using a purified acid urease preparation derived from Lactobacillus fermentum. The treatment was severely affected by the total phenolic content (TP) of the wine, the estimated pseudo-first-order kinetic rate constant for NH3 formation reducing by a factor of approximately 2000 as the TP increased from 0 to 1.64 g L(-1) . Such a sensitivity to TP was by far greater than that pertaining to a killed cell-based enzyme preparation used previously. Urea hydrolysis was successful at reducing EC concentration in wines with low levels of TP and other EC precursors.

  17. Co(II), Ni(II) and Cu(II) complexes of methyl-5-(Phenylthio) benzimidazole-2-carbamate: Molecular structures, spectral and DFT calculations

    Mansour, Ahmed M.; El Bakry, Eslam M.; Abdel-Ghani, Nour T.

    2016-05-01

    [Co(FBZ)2(H2O)]·2NO3·0.5H2O (1), [Ni(FBZ)2X2]·zH2O (X = Cl​-, z = 0.5 (2) and X = CH3COO-, z = 1 (3)) and [Cu(FBZ)2(H2O) (NO3)]·NO3·1.5H2O (4) (FBZ = methyl-5-(Phenylthio) benzimidazole-2-carbamate; Fenbendazole) complexes were synthesized and characterized by elemental analysis, thermal, IR, EPR, UV-Vis, magnetic and conductance measurements. Geometry optimization, molecular electrostatic potential maps and natural bond orbital analysis were carried out at DFT/B3LYP/6-31G∗ level of theory. FBZ behaves as a neutral bidentate ligand via the pyridine-type nitrogen of the benzimidazole moiety and the carbamate group. Three-step ionization with pKa values of 3.38, 4.06 and 10.07 were reported for FBZ. The coordination of FBZ to the metal ions led to an increase in the antibacterial activity against the tested Staphylococcus aureus and Escherichia coli bacteria.

  18. A mutant beta-tubulin confers resistance to the action of benzimidazole-carbamate microtubule inhibitors both in vivo and in vitro.

    Foster, K E; Burland, T G; Gull, K

    1987-03-16

    The mutant BEN210 of Physarum polycephalum is highly resistant to a number of benzimidazole carbamate agents, including methylbenzimidazole-2-yl-carbamate and parbendazole. The resistance is conferred by the benD210 mutation in a structural gene for beta-tubulin. This mutant allele encodes a beta-tubulin with novel electrophoretic mobility. We have used this strain to determine whether the mutant beta-tubulin is used in microtubules and whether this usage permits microtubule polymerisation in the presence of drugs both in vivo and in vitro. In vitro assembly studies of tubulin purified from the mutant strain have shown that microtubules are formed both in the absence of drugs and in all drug concentrations tested (up to 50 microM parbendazole). In contrast, the assembly of microtubules from wild-type tubulin in vitro is totally inhibited by 2-5 microM parbendazole. Thus the resistance of BEN210 to parbendazole observed in vivo has been reproduced in vitro using tubulin purified from the mutant strain. Electrophoretic analysis of the microtubules formed in vitro has shown that both the wild-type and the mutant beta-tubulin are incorporated into the microtubules and that the proportion of mutant to wild-type beta-tubulin appears to remain constant with increasing drug concentration. This is the first demonstration of a single mutation in a tubulin structural gene causing an altered function of the gene product in vitro.

  19. Human plasma concentrations of herbicidal carbamate molinate extrapolated from the pharmacokinetics established in in vivo experiments with chimeric mice with humanized liver and physiologically based pharmacokinetic modeling.

    Yamashita, Masanao; Suemizu, Hiroshi; Murayama, Norie; Nishiyama, Sayako; Shimizu, Makiko; Yamazaki, Hiroshi

    2014-10-01

    To predict concentrations in humans of the herbicidal carbamate molinate, used exclusively in rice cultivation, a forward dosimetry approach was carried out using data from lowest-observed-adverse-effect-level doses orally administered to rats, wild type mice, and chimeric mice with humanized liver and from in vitro human and rodent experiments. Human liver microsomes preferentially mediated hydroxylation of molinate, but rat livers additionally produced molinate sulfoxide and an unidentified metabolite. Adjusted animal biomonitoring equivalents for molinate and its primary sulfoxide from animal studies were scaled to human biomonitoring equivalents using known species allometric scaling factors and human metabolic data with a simple physiologically based pharmacokinetic (PBPK) model. The slower disposition of molinate and accumulation of molinate sulfoxide in humans were estimated by modeling after single and multiple doses compared with elimination in rodents. The results from simplified PBPK modeling in combination with chimeric mice with humanized liver suggest that ratios of estimated parameters of molinate sulfoxide exposure in humans to those in rats were three times as many as general safety factor of 10 for species difference in toxicokinetics. Thus, careful regulatory decision is needed when evaluating the human risk resulting from exposure to low doses of molinate and related carbamates based on data obtained from rats.

  20. Pesticides and respiratory symptoms among farmers

    Faria Neice Müller Xavier

    2005-01-01

    Full Text Available OBJECTIVE: Despite the intensive use of pesticides in agriculture there are few studies assessing the risk of respiratory conditions from this exposure. The study aimed at quantifying the prevalence of respiratory symptoms among farmers and evaluating its relationship with occupational use of pesticides and the prevalence of respiratory symptoms. METHODS: A cross-sectional study was conducted among 1,379 farmers from two municipalities of Southern Brazil in 1996. Frequency and type of chemical exposure and pesticide poisoning were recorded for both sexes. All subjects aged 15 years or older with at least 15 weekly hours of agricultural activity were interviewed. An adapted questionnaire developed by the American Thoracic Society was used for the assessment of respiratory symptoms. Multivariate logistic regression analysis was carried out. RESULTS: More than half (55% of interviewees were male. The prevalence of asthma symptoms was 12% and chronic respiratory disease symptoms was 22%. Higher odds ratios for both asthma (OR=1.51; 95% CI: 1.07-2.14 and chronic respiratory disease (OR=1.34; 95% CI 1.00-1.81 symptoms were found in women. Logistic regression analysis identified associations between many forms of exposure to pesticides and increased respiratory symptoms. Occurrence of pesticide poisoning was associated with higher prevalence of asthma symptoms (OR=1.54; 95% CI: 1.04-2.58 and chronic respiratory disease symptoms (OR=1.57; 95% CI: 1.08-2.28. CONCLUSIONS: In spite of causality limitations, the study results provide evidence that farming exposure to pesticides is associated with higher prevalence of respiratory symptoms, especially when the exposure is above two days per month.

  1. Suspected poisoning of domestic animals by pesticides.

    Caloni, Francesca; Cortinovis, Cristina; Rivolta, Marina; Davanzo, Franca

    2016-01-01

    A retrospective study was carried out by reviewing all suspected cases of domestic animal poisoning attributed to pesticides, reported to the Milan Poison Control Centre (MPCC) between January 2011 and December 2013. During this period, pesticides were found to be responsible for 37.3% of all suspected poisoning enquiries received (815). The most commonly species involved was the dog (71.1% of calls) followed by the cat (15.8%), while a limited number of cases involved horses, goats and sheep. Most cases of exposure (47.1%) resulted in mild to moderate clinical signs. The outcome was reported in 59.9% of these cases, with death occurring in 10.4% of them. Insecticides (40.8%) proved to be the most common group of pesticides involved and exposure to pyrethrins-pyrethroids accounted for the majority of calls. According to the MPCC data, there has been a decrease in the number of suspected poisonings cases attributed to pesticides that have been banned by the EU, including aldicarb, carbofuran, endosulfan and paraquat. In contrast, there has been an increase of suspected poisoning cases attributed to the neonicotinoids, imidacloprid and acetamiprid, probably due to their widespread use in recent years. Cases of suspected poisoning that involved exposure to rodenticides accounted for 27.6% of calls received by the MPCC and anticoagulant rodenticides were the primary cause of calls, with many cases involving brodifacoum and bromadiolone. Herbicides were involved in 14.2% of calls related to pesticides and glyphosate was the main culprit in cases involving dogs, cats, horses, goats and sheep. As far as exposure to molluscicides (11.5%) and fungicides (5.9%), most of the cases involved dogs and the suspected poisoning agents were metaldehyde and copper compounds respectively. The data collected are useful in determining trends in poisoning episodes and identifying newly emerging toxicants, thus demonstrating the prevalence of pesticides as causative agents in animal

  2. Application of SPE-HPLC-DAD and SPE-TLC-DAD to the determination of pesticides in real water samples.

    Tuzimski, Tomasz

    2008-10-01

    Planar chromatography with diode array scanning (TLC-DAD) and high-performance chromatography with diode array detection (HPLC-DAD) were used to screen water samples for pesticides. Pesticides were enriched from lake water samples by SPE on C18/SDB-1, C18, C18 Polar Plus and cyanopropyl (CN) cartridges. The recovery rates were high for all extraction materials except for all pesticides on CN cartridges, for which the values were lower. SPE was used not only for preconcentration of analytes but also for their fractionation. The analytes were eluted first with methanol and then with dichloromethane. Methanol eluates were analysed by HPLC-DAD, the dichloromethane eluates with TLC-DAD. The method was validated for precision, repeatability and accuracy. The calibration plots were linear between 0.1 and 50.0 microg/mL for all pesticides, the correlation coefficients, r, were between 0.9992 and 1.000 as determined by HPLC-DAD. In the TLC experiments, the best fit for the calibration lines was found when the calibration data were analysed using a second-degree polynomial regression. Calibration plots lay between 0.1 and 17 microg/spot for all pesticides, the correlation coefficients, r, were between 0.9974 and 0.9997 determined by TLC-DAD. The LOD was between 0.04 and 0.65 microg/spot (TLC-DAD) and between 0.02 and 3.68 microg/mL (HPLC-DAD).

  3. UV-MALDI mass spectrometric quantitation of uracil based pesticides in fruit soft drinks along with matrix effects evaluation.

    Ivanova, Bojidarka; Spiteller, Michael

    2014-02-01

    This study focused on the development of the accurate and precise quantitative method for the determination of pesticides bromacil (1), terbacil (2), lenacil (3), butafenacil (4) and flupropacil (5) in fruit based soft drinks. Three different types of drinks are bought from market; huddled orange fruit drink (100%) (I), red-oranges (II) and multivitamin drink containing strawberry, orange, banana and maracuja (III). Samples were analyzed "with" and "without" pulp utilizing LC-ESI (or APCI) MS/MS, HPLC-ESI-(or APCI)-MS/MS and UV-MALDI-Orbitrap-MS methods. The effect of high complexity of the food matrix on the analysis was discussed. Study focuses on the advantages of the UV-MALDI-Orbitrap-MS method compared to the traditionally involved GC alone or hybrid methods such as GC-MS and LC-MS/MS for quantification of pesticides in water and soft drinks. The developed method included the techniques performed for validation, calibration and standardization. The target pesticides are widely used for the treatment of citrus fruits and pineapples, but for soft drink products, there are still no clear regulations on pesticide residues limits. The matrix effects in the analysis of fruit drinks required implementation of the exact standard reference material corresponds to the variety of food matrices. This paper contributed to the broad analytical implementation of the UV-MALDI-Orbitrap-MS method in the quality control and assessment programs for monitoring of pesticide contamination in fruit based sodas.

  4. Alignment validation

    ALICE; ATLAS; CMS; LHCb; Golling, Tobias

    2008-09-06

    The four experiments, ALICE, ATLAS, CMS and LHCb are currently under constructionat CERN. They will study the products of proton-proton collisions at the Large Hadron Collider. All experiments are equipped with sophisticated tracking systems, unprecedented in size and complexity. Full exploitation of both the inner detector andthe muon system requires an accurate alignment of all detector elements. Alignmentinformation is deduced from dedicated hardware alignment systems and the reconstruction of charged particles. However, the system is degenerate which means the data is insufficient to constrain all alignment degrees of freedom, so the techniques are prone to converging on wrong geometries. This deficiency necessitates validation and monitoring of the alignment. An exhaustive discussion of means to validate is subject to this document, including examples and plans from all four LHC experiments, as well as other high energy experiments.

  5. SANSMIC Validation.

    Weber, Paula D.; Rudeen, David Keith; Lord, David L.

    2014-08-01

    SANSMIC is solution mining software that was developed and utilized by SNL in its role as geotechnical advisor to the US DOE SPR for planning purposes. Three SANSMIC leach modes - withdrawal, direct, and reverse leach - have been revalidated with multiple test cases for each mode. The withdrawal mode was validated using high quality data from recent leach activity while the direct and reverse modes utilized data from historical cavern completion reports. Withdrawal results compared very well with observed data, including the location and size of shelves due to string breaks with relative leached volume differences ranging from 6 - 10% and relative radius differences from 1.5 - 3%. Profile comparisons for the direct mode were very good with relative leached volume differences ranging from 6 - 12% and relative radius differences from 5 - 7%. First, second, and third reverse configurations were simulated in order to validate SANSMIC over a range of relative hanging string and OBI locations. The first-reverse was simulated reasonably well with relative leached volume differences ranging from 1 - 9% and relative radius differences from 5 - 12%. The second-reverse mode showed the largest discrepancies in leach profile. Leached volume differences ranged from 8 - 12% and relative radius differences from 1 - 10%. In the third-reverse, relative leached volume differences ranged from 10 - 13% and relative radius differences were %7E4 %. Comparisons to historical reports were quite good, indicating that SANSMIC is essentially the same as documented and validated in the early 1980's.

  6. Applicability and modelling of nanofiltration and reverse osmosis for remediation of groundwater polluted with pesticides and pesticide transformation products

    Madsen, Henrik Tækker; Søgaard, Erik Gydesen

    2014-01-01

    The main body of research on pesticide removal with membranes has looked at pesticides used for pest control, but during transport from surface to groundwater aquifers, pesticides are transformed. Therefore the real polluting compounds are often transformation products, and this vastly increases ...

  7. PESTLCI – A PESTICIDE DISTRIBUTION MODEL FOR LCA

    Birkved, Morten; Hauschild, Michael Zwicky

    and assessment of pesticide applications. The report therefore starts with a review of the work reported by the CAPER project as described in / / in order to locate new methods amenable for: 1. Handling of pesticide screening in LCA 2. Distribution modelling of pesticides in LCA 3. Evaluation of human exposure...... in LCA Following the review of existing methods, a number of modifications and new modules are developed and integrated into the existing method for pesticide distribution modelling to arrive at PESTLCI. Finally, PESTLCI is tested on three pesticide applications and the results compared to the results...

  8. Pesticide Exposure, Safety Issues, and Risk Assessment Indicators

    Christos A. Damalas

    2011-05-01

    Full Text Available Pesticides are widely used in agricultural production to prevent or control pests, diseases, weeds, and other plant pathogens in an effort to reduce or eliminate yield losses and maintain high product quality. Although pesticides are developed through very strict regulation processes to function with reasonable certainty and minimal impact on human health and the environment, serious concerns have been raised about health risks resulting from occupational exposure and from residues in food and drinking water. Occupational exposure to pesticides often occurs in the case of agricultural workers in open fields and greenhouses, workers in the pesticide industry, and exterminators of house pests. Exposure of the general population to pesticides occurs primarily through eating food and drinking water contaminated with pesticide residues, whereas substantial exposure can also occur in or around the home. Regarding the adverse effects on the environment (water, soil and air contamination from leaching, runoff, and spray drift, as well as the detrimental effects on wildlife, fish, plants, and other non-target organisms, many of these effects depend on the toxicity of the pesticide, the measures taken during its application, the dosage applied, the adsorption on soil colloids, the weather conditions prevailing after application, and how long the pesticide persists in the environment. Therefore, the risk assessment of the impact of pesticides either on human health or on the environment is not an easy and particularly accurate process because of differences in the periods and levels of exposure, the types of pesticides used (regarding toxicity and persistence, and the environmental characteristics of the areas where pesticides are usually applied. Also, the number of the criteria used and the method of their implementation to assess the adverse effects of pesticides on human health could affect risk assessment and would possibly affect the characterization

  9. Kinetic Modelling of Pesticidal Degradation and Microbial Growth in Soil

    LIUDUO-SEN; WANGZONG-SHENG; 等

    1994-01-01

    This paper discusses such models for the degradation kinetics of pesticides in soil as the model expressing the degradation rate as a function of two varables:the pesticide concentration and the number of pesticide degrading microorganisms,the model expressing the pesticide concentration as explicit or implicit function of time ,and the model exprssing the pesticide loss rate constants as functions of temperature,These models may interpret the degradation curves with an inflection point.A Kinetic model describing the growth processes of microbial populations in a closed system is reported as well.

  10. Way toward "dietary pesticides": molecular investigation of insecticidal action of caffeic acid against Helicoverpa armigera.

    Joshi, R S; Wagh, T P; Sharma, N; Mulani, F A; Sonavane, U; Thulasiram, H V; Joshi, R; Gupta, V S; Giri, A P

    2014-11-12

    Bioprospecting of natural molecules is essential to overcome serious environmental issues and pesticide resistance in insects. Here we are reporting insights into insecticidal activity of a plant natural phenol. In silico and in vitro screening of multiple molecules supported by in vivo validations suggested that caffeic acid (CA) is a potent inhibitor of Helicoverpa armigera gut proteases. Protease activity and gene expression were altered in CA-fed larvae. The structure-activity relationship of CA highlighted that all the functional groups are crucial for inhibition of protease activity. Biophysical studies and molecular dynamic simulations revealed that sequential binding of multiple CA molecules induces conformational changes in the protease(s) and thus lead to a significant decline in their activity. CA treatment significantly inhibits the insect's detoxification enzymes, thus intensifying the insecticidal effect. Our findings suggest that CA can be implicated as a potent insecticidal molecule and explored for the development of effective dietary pesticides.

  11. Influence of different disease control pesticide strategies on multiple pesticide residue levels in apple

    Poulsen, Mette Erecius; Naef, A.; Gasser, S.;

    2009-01-01

    % of European Maximum Residue Levels (EU MRL) and that the number of residues present at levels above 0.01 mg kg(-1) should be limited to a maximum of four. The strategies fulfilled the requirement to use combinations of different active substances in order to prevent the emergence of resistance to pesticides......Seven pesticide application strategies were investigated to control apple scab (Venturia inaequalis) and powdery mildew (Podosphaera leucotricha) and, at the same time.. fulfil the new quality standards implemented by some German retailers. These demand that pesticide residues should be below 80....... The trials were conducted at two sites in Switzerland, in 2007, and all strategies and applications were in accordance with actual practice. Four replicates of apple samples from each strategy were then analysed for pesticide residues. The incidence of infection with apple scab and powdery mildew were...

  12. Modelling the fate of pesticides in paddy rice-fish pond farming system in Northern Vietnam

    Lamers, M.; Nguyen, N.; Streck, T.

    2012-04-01

    During the last decade rice production in Vietnam has tremendously increased due to the introduction of new high yield, short duration rice varieties and an increased application of pesticides. Since pesticides are toxic by design, there is a natural concern on the possible impacts of their presence in the environment on human health and environment quality. In North Vietnam, lowland and upland rice fields were identified to be a major non-point source of agrochemical pollution to surface and ground water, which are often directly used for domestic purposes. Field measurements, however, are time consuming, costly and logistical demanding. Hence, quantification, forecast and risk assessment studies are hampered by a limited amount of field data. One potential way to cope with this shortcoming is the use of process-based models. In the present study we developed a model for simulating short-term pesticide dynamics in combined paddy rice field - fish pond farming systems under the specific environmental conditions of south-east Asia. Basic approaches and algorithms to describe the key underlying biogeochemical processes were mainly adopted from the literature to assure that the model reflects the current standard of scientific knowledge and commonly accepted theoretical background. The model was calibrated by means of the Gauss-Marquardt-Levenberg algorithm and validated against measured pesticide concentrations (dimethoate and fenitrothion) during spring and summer rice crop season 2008, respectively, of a paddy field - fish pond system typical for northern Vietnam. First simulation results indicate that our model is capable to simulate the fate of pesticides in such paddy - fish pond farming systems. The model efficiency for the period of calibration, for example, was 0.97 and 0.95 for dimethoate and fenitrothion, respectively. For the period of validation, however, the modeling efficiency slightly decreased to 0.96 and 0.81 for dimethoate and fenitrothion

  13. From greenhouse gas to feedstock: formation of ammonium carbamate from CO{sub 2} and NH{sub 3} in organic solvents and its catalytic conversion into urea under mild conditions

    Barzagli, F.; Mani, F.; Peruzzini, M. [University of Florence, Florence (Italy). Dept. of Chemistry

    2011-07-01

    The capture of carbon dioxide by ammonia in both aqueous and non-aqueous solutions was investigated at atmospheric pressure and 273 K under different operating conditions. The CO{sub 2} capture is fast and efficient ranging between 78 and 99%, depending on both the NH{sub 3} concentration and the solvent nature. The precipitation of solid mixtures of ammonium bicarbonate, ammonium carbonate and ammonium carbamate occurred in ethanol-water solution. Selective precipitation of ammonium carbamate was achieved by reacting gaseous CO{sub 2} and NH{sub 3} in anhydrous ethanol, 1-propanol or N,N-dimethylformamide (DMF) in a flow reactor that operates in continuous. In the second step of the process, the pure ammonium carbamate is used to produce urea with good yield (up to 54% on carbamate basis) at 393-413 K in the presence of inexpensive Cu(II) and Zn(II) catalysts. The yield of urea depends on several factors including the catalyst, the reaction temperature and the reaction time. Identification and quantification of urea in the reaction mixtures was obtained by analysis of its {sup 13}C NMR spectrum. A preliminary mechanistic interpretation of the catalytic reaction is also briefly presented and commented.

  14. Removal of pesticides from white and red wines by microfiltration.

    Doulia, Danae S; Anagnos, Efstathios K; Liapis, Konstantinos S; Klimentzos, Demetrios A

    2016-11-05

    The aim of this work is the investigation of microfiltration in removing pesticides from a white and a red Greek wine. Six membranes with pore size 0.45μm were investigated. Two mixtures of 23 and 9 pesticides, and single pesticide solutions were added in the wine. The pesticides tested belong to 11 chemical groups. Solid phase extraction (SPE) followed by gas chromatography (GC) with electron capture detector (ECD) were performed to analyze pesticide residues of the filtered fortified wine. Distinct behavior was exhibited by each membrane. Cellulose acetate and cellulose nitrate showed higher mean pesticide removal for both wines, followed by polyethersulfone, regenerated cellulose, and polyamides. The filtration effectiveness was correlated to the membrane type and to the pesticide chemical structure and properties (octanol-water partition coefficient, water solubility) and compared for the wines tested. In most cases, the more hydrophobic pesticides (pyrethroids and aldrin) showed higher removal from red wine than white wine. Adsorption on membranes was increased by increasing hydrophobicity and decreasing hydrophilicity of organic pesticide molecule. The removal of each pesticide from its single solution was generally higher than that from its mixtures, allowing the estimation of the antagonistic and synergistic effects of pesticides in the mixtures.

  15. Assessing pesticide exposure of the aquatic environment in tropical catchments

    Weiss, Frederik; Zurbrügg, Christian; Eggen, Rik; Castillo, Luisa; Ruepert, Clemens; Stamm, Christian

    2015-04-01

    Today, pesticides are intensively used in agriculture across the globe. Worldwide about 2.4×106 tons of pesticides are used annually on 1.6×109 ha of arable land. This yields a global average use of pesticides of 1.53 kg ha-1 year-1. Available data suggest that the use in the agricultural sector will continue to grow. Recently it was estimated that within the last decade, the world pesticide market increased by 93% and the Brazilian market alone by 190%. Though pesticides are intensively used in many low and middle income countries (LAMICs), scientifically sound data of amounts and types of pesticide use and the resulting impact on water quality are lacking in many of these countries. Therefore it is highly relevant to: i) identify risk areas where pesticides affect environmental health, ii) understand the environmental behavior of pesticides in vulnerable tropical ecosystems; and iii) develop possible mitigation options to reduce their exposure to ecosystems and humans. Here we present a project that will focus on assessing pesticide exposure of the aquatic environment and humans in tropical catchments of LAMICs. A catchment in the Zarcero province in Costa Rica will be the test case. Pesticide exposure will be assessed by passive sampling. In order to cover a broad range of compounds of possible use, two sampling devices will be used: SDB membranes for collecting polar compounds and silicon sheets for accumulating apolar pesticides. Extracts will be subsequently analysed by GC-MSMS and LC-HRMS.

  16. Pesticide contamination of Tenebrio molitor (Coleoptera: Tenebrionidae) for human consumption.

    Houbraken, Michael; Spranghers, Thomas; De Clercq, Patrick; Cooreman-Algoed, Margot; Couchement, Tasmien; De Clercq, Griet; Verbeke, Sarah; Spanoghe, Pieter

    2016-06-15

    The use of pesticides contributes to the productivity and the quality of the cultivated crop. A large portion of the agricultural produce is not consumed as it is not an edible part or the quality of the product is too low. This waste of agricultural produce can be valorised as a substrate for the production of certain insects for human consumption. However, pesticides applied on the plants might accumulate during the life cycle of the insects fed on the waste materials and may cause a health risk to humans consuming the insects. Pesticide residues in larvae of the yellow mealworm, Tenebrio molitor, were investigated. We monitored the accumulation of pesticides in the larvae upon consumption of contaminated fresh produce. An increased uptake rate by the insects was found for pesticides with higher Kow-values. Excretion of pesticides by the insect was inversely related to the log(Kow) values of the pesticides.

  17. The role of private pesticide vendors in preventing access to pesticides for self-poisoning in rural Sri Lanka

    Weerasinghe, Manjula; Pearson, Melissa; Peiris, Ravi;

    2014-01-01

    In 15% to 20% of self-poisoning cases, the pesticides used are purchased from shops just prior to ingestion. We explored how pesticide vendors interacted with customers at risk of self-poisoning to identify interventions to prevent such poisonings. Two strategies were specifically discussed......: selling pesticides only to farmers bearing identity cards or customers bearing pesticide 'prescriptions'. Vendors reported refusing to sell pesticides to people thought to be at risk of self-poisoning, but acknowledged the difficulty of distinguishing them from legitimate customers; vendors also stated...

  18. 77 FR 12731 - Thiamethoxam; Pesticide Tolerances

    2012-03-02

    ... the docket index available at http://www.regulations.gov . Although listed in the index, some... pesticide exposure assessment can be found at http://www.epa.gov/oppefed1/models/water/index.htm . Based on... anemia as well as leukopenia characterized by reductions in neutrophils, lymphocytes and monocytes;...

  19. 78 FR 8407 - Endosulfan; Pesticide Tolerance

    2013-02-06

    ... AGENCY 40 CFR Part 180 Endosulfan; Pesticide Tolerance AGENCY: Environmental Protection Agency (EPA). ACTION: Order reestablishing tolerance. SUMMARY: EPA has granted an objection to the timing of the revocation of the tolerance for endosulfan on tea. The objection was filed by the Chamber of ] Commerce...

  20. 77 FR 42654 - Trifloxystrobin; Pesticide Tolerance

    2012-07-20

    ... AGENCY 40 CFR Part 180 Trifloxystrobin; Pesticide Tolerance AGENCY: Environmental Protection Agency (EPA). ACTION: Final rule. SUMMARY: This regulation establishes a tolerance for residues of trifloxystrobin in or on artichoke, globe. Bayer CropScience requested these tolerances under the Federal Food,...