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Sample records for carbamate pesticides validation

  1. Carbamate pesticide induced toxic epidermal necrolysis

    Rajendran N

    2001-09-01

    Full Text Available A 36-year-old male alleged to have consumed carbamate pesticide liquid (Baygon@ developed toxic epidermal necrolysis (TEN within twenty-four hours of intake. Though drugs have been commonly incriminated as offending agents for TEN, carbamate pesticide was found to be the causative agent in our case.

  2. CUMULATIVE EFFECTS OF ORGANOPHOSPHORUS OR CARBAMATE PESTICIDES.

    This book chapter strives to summarize the body of literature exploring the toxic interaction of organophosphorus and carbamate pesticides in mixtures. This review represents one of the only reviews of the subject that has been published within the last 20 years. Specifically, th...

  3. Photoinduced chemiluminescence determination of carbamate pesticides.

    Catalá-Icardo, M; Meseguer-Lloret, S; Torres-Cartas, S

    2016-05-11

    A liquid chromatography method with post-column photoinduced chemiluminescence (PICL) detection is proposed for the simultaneous determination of eight carbamate pesticides, namely aldicarb, butocarboxim, ethiofencarb, methomyl, methiocarb, thiodicarb, thiofanox and thiophanate-methyl. After chromatographic separation, quinine (sensitizer) was incorporated and the flow passed through an UV lamp (67 s of irradiation time) to obtain the photoproducts, which reacted with acidic Ce(iv) and provided a CL emission. The PICL method showed great selectivity for carbamate pesticides containing sulphur in their chemical structure. A solid-phase extraction process increased sensitivity (LODs ranging from 0.06 to 0.27 ng mL(-1)) and allowed the carbamate pesticides in surface and ground water samples to be determined, with recoveries in the range 87-110% (except for thiophanate-methyl, whose recoveries were between 60 and 75%). The intra- and inter-day precision was evaluated, with RSD ranging from 1.1 to 7.5% and from 2.6 to 12.3%, respectively. A discussion about the PICL mechanism is also included. PMID:27079156

  4. Wildlife mortality attributed to organophosphorus and carbamate pesticides

    Glaser, L.C.

    1995-01-01

    Organophosphorus (OP) and carbamate pesticides are used widely in agricultural and residential applications as insecticides, herbicides, fungicities. and rodenticides. This family of chemicals replaced the organochlorine pesticides banned for use in the United States in the 1970's. Unlike organochlorine pesticides, which are long-lived in the environment and cause biological damage when they accumulate in an organism's system over time. OP and carbamate pesticides are short-lived in the environment and fast-acting on their 'target pest.' Direct mortality of wildlife from organochlorine pesticides was uncommon (Hayes and Wayland 1975): however, mortality is the primary documented effect on wildlife from OP and carbamate pesticides (Grue et al. 1983). Organophosphorus and carbamate pesticide toxicity is not specific to a target 'pest,' and lethal effects are seen in nontarget organisms: birds appear to be the most sensitive class of animals affected by these pesticides. Organophosphorus and carbamate pesticides primainly affect the nervous system by inhibiting acetylcholinesterase (AChE) enzyme activity. This enzyme's main function in the nervous system is to break down the neurotransmitter acetylcholine. When AChE is altered by OP and carbamate pesticides, it cannot perform this breakdown function and acetylcholine accumulates. Acetylcholine accumulation increases nerve impulse transmission and leads to nerve exhaustion and. ultimately, failure of the nervous system. When the nervous system fails, muscles do not receive the electrical input they require to move. The respiratory muscles are the most critical muscle group affected, and respiratory paralysis is often the immediate cause of death.

  5. 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. PMID:20557892

  6. Induction of Tibial Dyschondroplasia by Carbamate and Thiocarbamate Pesticides

    Tibial dyschondroplasia (TD) is a major poultry leg problem the natural etiology of which is unknown. Certain dithiocarbamate pesticides such as tetramethyl thiuram disulfide (thiram) have been shown to induce the disease in chickens. Since many different carbamate and thiocarbamate chemicals are ...

  7. Carbamate Pesticide-Induced Apoptosis in Human T Lymphocytes

    Qing Li

    2015-04-01

    Full Text Available We previously found that carbamate pesticides induced significant apoptosis in human natural killer cells. To investigate whether carbamate pesticides also induce apoptosis in human T lymphocytes, in the present study Jurkat human T cells were treated in vitro with thiram, maneb, carbaryl or ziram. Apoptosis was determined by FITC-Annexin-V/PI staining. To explore the mechanism of apoptosis, intracellular levels of active caspase 3 and mitochondrial cytochrome-c release were determined by flow cytometry. We found that thiram, ziram, maneb and carbaryl also induced apoptosis in a time- and dose-dependent manner in the human T cells. However, the strength of the apoptosis-inducing effect differed among the pesticides, with the: thiram > ziram > maneb > carbaryl. Moreover, thiram significantly increased the intracellular level of active caspase 3 and caspase inhibitors significantly inhibited apoptosis. Thiram also significantly caused mitochondrial cytochrome-c release. These findings indicate that carbamate pesticides can induce apoptosis in human T cells, and the apoptosis is mediated by the activation of caspases and the release of mitochondrial cytochrome-c.

  8. 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.

  9. 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

    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......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...... 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...

  10. Semi disposable reactor biosensors for detecting carbamate pesticides in water.

    Suwansa-ard, Siriwan; Kanatharana, Proespichaya; Asawatreratanakul, Punnee; Limsakul, Chusak; Wongkittisuksa, Booncharoen; Thavarungkul, Panote

    2005-09-15

    Two flow-injection biosensor systems using semi disposable enzyme reactor have been developed to determine carbamate pesticides in water samples. Acetylcholinesterase was immobilized on silica gel by covalent binding. pH and conductivity electrodes were used to detect the ionic change of the sample solution due to hydrolysis of acetylcholine. Carbamate pesticides inhibited acetylcholinesterase and the decrease in the enzyme activity was used to determine these pesticides. Parameters influencing the performance of the systems were optimized to be used in the inhibition procedure. Carbofuran and carbaryl were used to test these systems. Detection limits for the potentiometric and conductimetric systems were both at 10% inhibition corresponding to 0.02 and 0.3 ppm of carbofuran and carbaryl, respectively. Both systems also provided the same linear ranges, 0.02-8.0 ppm for carbofuran, and 0.3-10 ppm for carbaryl. The analysis of pesticides was done a few times before the reactor was disposed. Percentages of inhibition obtained from different reactors were reproducible, therefore, no recalibration was necessary when changing the reactor. The biosensors were used to analyze carbaryl in water samples from six wells in a vegetable growing area. Both systems could detect the presence of carbaryl in the samples and provided good recoveries of the added carbaryl, i.e., 80-106% for the potentiometric system and 75-105% for the conductimetric system. The presence of carbaryl in water samples analyzed by the biosensors was confirmed by gas chromatography-mass spectrometric system. These biosensors do not require any sample preconcentration and are suitable for detecting pesticides in real water samples. PMID:16076434

  11. DOSE-RESPONSE MODELING FOR THE ASSESSMENT OF CUMULATIVE RISK DUE TO EXPOSURE TO N-METHYL CARBAMATE PESTICIDES

    The US EPAs N-Methyl Carbamate Cumulative Risk Assessment (NMCRA) assesses the effect on acetylcholine esterase (AChE) activity of exposure to 10 N-methyl carbamate (NMC) pesticides through dietary, drinking water, and residential exposures.

  12. Photochemical decomposition of carbamate pesticides in natural waters of northern Greece

    The photochemical decomposition of the carbamate pesticides carbofuran, carbaryl and thiram was examined in natural waters of northern Greece under the influence of solar and UV (λ > 290 nm) radiation. Different major photoproducts were detected by GC/MS. The result of continuous irradiation was almost total degradation of the pesticides examined

  13. Application of brain cholinesterase reactivation to differentiate between organophosphorus and carbamate pesticide exposure in wild birds

    Smith, M.R.; Thomas, N.J.; Hulse, C.

    1995-01-01

    Brain cholinesterase activity was measured to evaluate pesticide exposure in wild birds. Thermal reactivation of brain cholinesterase was used to differentiate between carbamate and organophosphorus pesticide exposure. Brain cholinesterase activity was compared with gas chromatography and mass spectrometry of stomach contents. Pesticides were identified and confirmed in 86 of 102 incidents of mortality from 29 states within the USA from 1986 through 1991. Thermal reactivation of cholinesterase activity was used to correctly predict carbamates in 22 incidents and organophosphates in 59 incidents. Agreement (P < 0.001) between predictions based on cholinesterase activities and GC/MS results was significant.

  14. Selective effects of carbamate pesticides on rat neuronal nicotinic acetylcholine receptors and rat brain acetylcholinesterase

    Effects of commonly used carbamate pesticides on rat neuronal nicotinic acetylcholine receptors expressed in Xenopus laevis oocytes have been investigated using the two-electrode voltage clamp technique. The potencies of these effects have been compared to the potencies of the carbamates to inhibit rat brain acetylcholinesterase. The potency order of six carbamates to inhibit α4β4 nicotinic receptors is fenoxycarb > EPTC > carbaryl, bendiocarb > propoxur > aldicarb with IC50 values ranging from 3 μM for fenoxycarb to 165 μM for propoxur and >1 mM for aldicarb. Conversely, the potency order of these carbamates to inhibit rat brain acetylcholinesterase is bendiocarb > propoxur, aldicarb > carbaryl >> EPTC, fenoxycarb with IC50 values ranging from 1 μM for bendiocarb to 17 μM for carbaryl and >>1 mM for EPTC and fenoxycarb. The α4β2, α3β4, and α3β2 nicotinic acetylcholine receptors are inhibited by fenoxycarb, EPTC, and carbaryl with potency orders similar to that for α4β4 receptors. Comparing the potencies of inhibition of the distinct subtypes of nicotinic acetylcholine receptors shows that the α3β2 receptor is less sensitive to inhibition by fenoxycarb and EPTC. The potency of inhibition depends on the carbamate as well as on a combination of α and β subunit properties. It is concluded that carbamate pesticides affect different subtypes of neuronal nicotinic receptors independently of acetylcholinesterase inhibition. This implicates that neuronal nicotinic receptors are additional targets for some carbamate pesticides and that these receptors may contribute to carbamate pesticide toxicology, especially after long-term exposure

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

    2014-01-01

    In many countries, people are becoming more concerned about pesticide residues which are present in or on food and feed products. For this reason, several methods have been developed to monitor the pesticide residue levels in food samples. In this study, a bioactive paper-based sensor was developed for detection of acetylcholinesterase (AChE) inhibitors including organophosphate and carbamate pesticides. Based on the Ellman colorimetric assay, the assay strip is composed of a paper support (1...

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

    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. -- Highlights: •Natural river biofilms showed high ability to degrade methomyl and carbofuran. •The presence of other pesticides caused certain effects on pesticide degradation. •Carbamate pesticides caused adverse effects on communities of diatoms and bacteria. •The tolerant diatoms and bacteria were found as potential pesticide-degraders. -- Biodegradation of carbamate pesticides by river biofilms

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

    Mohamed E. I. Badawy

    2014-01-01

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

  18. 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...... and cereals. The probabilistic approach was used in the assessments. Residue data obtained from the Danish monitoring programme carried out in the period 2004-2007, which included 6704 samples of fruit, vegetables and cereals, were used in the calculations. Food consumption data were obtained from...... 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...

  19. 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

  20. Role of B-esterases in assessing toxicity of organophosphorus (chlorpyrifos, malathion) and carbamate (carbofuran) pesticides to Daphnia magna.

    Barata, Carlos; Solayan, Arun; Porte, Cinta

    2004-02-10

    In this study, the cladoceran Daphnia magna was exposed to two model organophosphorous and one carbamate pesticides including malathion, chlorpyrifos and carbofuran to assess acetylcholinesterase (AChE) and carboxylesterase (CbE) inhibition and recovery patterns and relate those responses with individual level effects. Our results revealed differences in enzyme inhibition and recovery patterns among the studied esterase enzymes and pesticides. CbE was more sensitive to organophosphorous than AChE, whereas both CbE and AChE showed equivalent sensitivities to the carbamate carbofuran. Recovery patterns of AChE and CbE activities following exposure to the studied pesticides were similar with 80-100% recoveries taking place 12 and 96 h after exposure to organophosphorous and carbamates pesticides, respectively. The physiological role of AChE and CbE inhibition patterns in Daphnia was examined by using organophosphorous and carbamate compounds alone and with specific inhibitors of CbE. Under exposure to organophosphorous pesticides, survival of Daphnia juveniles was impaired at AChE inhibition levels higher than 50% whereas under exposure to the carbamate carbofuran low levels of AChE inhibition affected mortality. Inhibition of CbE by 80-90% increased toxicity to organophosphorous and carbamate pesticides by up to two- and four-fold, respectively. Our results suggest that both AChE and CbE enzymes are involved in determining toxicity of Daphnia to the studied chemicals and that AChE inhibition levels higher than 50% can be considered of environmental concern to Daphnia species. PMID:15036868

  1. 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.

  2. Biochemical and Histopathological Changes in The Rat Following Exposure to a Carbamate Pesticide

    Oxamyl is a carbamate pesticide with an oral LD50 of 5.4 mg/kg for male rats. To evaluate the subacute toxicity of the compound, two groups of male rats were dosed with 0.9 and 2.5 mg/kg/day of the pesticide, for 16 days. Toxicological evaluation included clinical chemistry and histopathological changes at the end of the study. The compound significantly altered serum alkaline phosphatase, uric acid, cholesterol, creatinine, blood urea nitrogen (BUN), serum glutamic pyruvic transaminase (SGPT and testosterone. Liver, Kidney and testicular histology revealed mild degenerative changes in the liver with the lower dose and significant degenerative changes with increased lymphocytic infiltrate with the higher dose and mild degenerative changes of the kidney with the higher dose only. Examination of the testis revealed no pathological changes at both dose levels

  3. 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. PMID:26988364

  4. 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.

  5. Benchmark Dose Analysis from Multiple Datasets: The Cumulative Risk Assessment for the N-Methyl Carbamate Pesticides

    The US EPA’s N-Methyl Carbamate (NMC) Cumulative Risk assessment was based on the effect on acetylcholine esterase (AChE) activity of exposure to 10 NMC pesticides through dietary, drinking water, and residential exposures, assuming the effects of joint exposure to NMCs is dose-...

  6. An evaluation of liquid chromatography/mass spectrometry with atmospheric pressure chemical ionization for the rapid and simultaneous measurement of carbamate pesticides and organophorus pesticides

    Liquid chromatography/mass spectrometry with an atmospheric pressure chemical ionization interface (LC/APCI/MS) is evaluated for the simultaneous determination of carbamate pesticides and organophosphorus pesticides in a single chromatographic analysis. APCI mass spectra of those compounds were obtained to study their ionization characteristics. APCI provided abundant ions such as protonated molecules and characteristic fragment ions for carbamate pesticides and organophosphorus pesticides. To evaluate the feasibility of the LC/APCI/MS for a routine quantitative analysis, the linearity and repeatability of LC/APCI/MS were examined by measuring standard solution mixtures of five carbamate pesticides and four organophosphorus pesticides over the range of 1 to 100 μg/mL. The peak areas in chromatograms of characteristic ions for those compounds showed less than 3% of variation from run to tun. The standard calibration curves for the nine pesticides show good linearity in the concentration range. The detection limits of the LC/APCI/MS system for those compounds range from 0.006 to 0.2 ng

  7. 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.

  8. Comparative voltammetric study and determination of carbamate pesticide residues in soil at carbon nanotubes paste electrodes

    THOMMANDRU RAVEENDRANATH BAB

    2014-02-01

    Full Text Available In this investigation, the persistence of carbamate pesticides in soil samples was investigated. A simple and selective differential pulse adsorptive stripping voltammetry was selected for this investigation. Carbon nanotubes paste electrodes were used as working electrodes for differential pulse adsorptive stripping voltammetry and cyclic voltammetry. A symmetric study of the various operational parameters that affect the stripping response was carried out by differential pulse voltammetry. Peak currents were linear over the concentration range of 10-5 to 10-10 M with an accumulation potential of -0.6 V and a 70 s accumulation time with lower detection limits of 1.09 x 10-7 M, 1.07 × 10-7M, 1.09×10-7 M for chlorphropham, thiodicarb, aldicarb. The relative standard deviation (n=10 and correlation coefficient values were 1.15 %, 0.988; 1.13 %, 0.978; and 1.14 %, 0.987, respectively. Universal buffer with pH range 2.0 - 6.0 was used as sup­porting electrolyte. The solutions with uniform concentration (10-5 M were used in all deter­minations. Calculations were made by standard addition method.

  9. Immobilization of acetylcholinesterase via biocompatible interface of silk fibroin for detection of organophosphate and carbamate pesticides

    Xue, Rui; Kang, Tian-Fang; Lu, Li-Ping; Cheng, Shui-Yuan

    2012-06-01

    An amperometric biosensor for the detection of organophosphate and carbamate pesticides was developed based on the immobilization of acetylcholinesterase (AChE) on regenerated silk fibroin (SF) matrix by non-covalent adsorption. SF and AChE were coated sequentially on the surface of the glassy carbon electrode (GCE) which was modified with multiwall carbon nanotube (MWNTs). The obtained biosensor was denoted as AChE-SF/MWNTs/GCE. The atomic force microscopy images showed that the SF matrix provided a more homogeneous interface for the AChE immobilization. The aggregation of immobilizing AChE was therefore avoided. The cyclic voltammogram of thiocholine at this biosensor exhibited a well defined oxidation peak at 0.667 V (vs. SCE). The inhibition rate of methyl parathion to the immobilized AChE was proportional to the logarithm of the concentration of methyl parathion over the range of the concentration of methyl parathion from 3.5 × 10-6 to 2.0 × 10-3 M with a detection limit of 5.0 × 10-7 M. Similarly, the linearly response range of carbaryl was from 1.0 × 10-7 to 3.0 × 10-5 M with a detection limit of 6.0 × 10-8 M. The experimental results indicate that AChE not only can be immobilized steadily on the SF matrix, but also the bioactivity of immobilizing AChE can be preserved effectively.

  10. Immobilization of acetylcholinesterase via biocompatible interface of silk fibroin for detection of organophosphate and carbamate pesticides

    Xue Rui [College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124 (China); Kang Tianfang, E-mail: kangtf@yahoo.cn [College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124 (China); Lu Liping; Cheng Shuiyuan [College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124 (China)

    2012-06-01

    An amperometric biosensor for the detection of organophosphate and carbamate pesticides was developed based on the immobilization of acetylcholinesterase (AChE) on regenerated silk fibroin (SF) matrix by non-covalent adsorption. SF and AChE were coated sequentially on the surface of the glassy carbon electrode (GCE) which was modified with multiwall carbon nanotube (MWNTs). The obtained biosensor was denoted as AChE-SF/MWNTs/GCE. The atomic force microscopy images showed that the SF matrix provided a more homogeneous interface for the AChE immobilization. The aggregation of immobilizing AChE was therefore avoided. The cyclic voltammogram of thiocholine at this biosensor exhibited a well defined oxidation peak at 0.667 V (vs. SCE). The inhibition rate of methyl parathion to the immobilized AChE was proportional to the logarithm of the concentration of methyl parathion over the range of the concentration of methyl parathion from 3.5 Multiplication-Sign 10{sup -6} to 2.0 Multiplication-Sign 10{sup -3} M with a detection limit of 5.0 Multiplication-Sign 10{sup -7} M. Similarly, the linearly response range of carbaryl was from 1.0 Multiplication-Sign 10{sup -7} to 3.0 Multiplication-Sign 10{sup -5} M with a detection limit of 6.0 Multiplication-Sign 10{sup -8} M. The experimental results indicate that AChE not only can be immobilized steadily on the SF matrix, but also the bioactivity of immobilizing AChE can be preserved effectively.

  11. Evaluation of exposure to organophosphate, carbamate, phenoxy acid, and chlorophenol pesticides in pregnant women from 10 Caribbean countries.

    Forde, Martin S; Robertson, Lyndon; Laouan Sidi, Elhadji A; Côté, Suzanne; Gaudreau, Eric; Drescher, Olivia; Ayotte, Pierre

    2015-09-01

    Pesticides are commonly used in tropical regions such as the Caribbean for both household and agricultural purposes. Of particular concern is exposure during pregnancy, as these compounds can cross the placental barrier and interfere with fetal development. The objective of this study was to evaluate exposure of pregnant women residing in 10 Caribbean countries to the following commonly used classes of pesticides in the Caribbean: organophosphates (OPs), carbamates, phenoxy acids, and chlorophenols. Out of 438 urine samples collected, 15 samples were randomly selected from each Caribbean country giving a total of 150 samples. Samples were analyzed for the following metabolites: six OP dialkylphosphate metabolites [dimethylphosphate (DMP), dimethylthiophosphate (DMTP), dimethyldithiophosphate (DMDTP), diethylphosphate (DEP), diethylthiophosphate (DETP) and diethyldithiophosphate (DEDTP)]; two carbamate metabolites [2-isopropoxyphenol (2-IPP) and carbofuranphenol]; one phenoxy acid 2,4-dichlorophenoxyacetic acid (2,4-D); and five chlorophenols [2,4-dichlorophenol (DCP), 2,5-dichlorophenol (2,5-DCP), 2,4,5-trichlorophenol (TCP), 2,4,6-trichlorophenol (2,4,6-TCP), and pentachlorophenol (PCP)]. OP metabolites were consistently detected in ≥60% of the samples from Antigua and Barbuda, Bermuda, and Jamaica. Of the carbamate metabolites, 2-IPP was detected in seven of the 10 Caribbean countries with a detection frequency around 30%, whereas carbofuranphenol was detected in only one sample. The detection frequency for the phenoxy acid 2,4-D ranged from 20% in Grenada to a maximum of 67% in Belize. Evidence of exposure to chlorophenol pesticides was also established with 2,4-DCP by geometric means ranging from 0.52 μg L(-1) in St Lucia to a maximum of 1.68 μg L(-1) in Bermuda. Several extreme concentrations of 2,5-DCP were detected in four Caribbean countries-Belize (1100 μg L(-1)), Bermuda (870 μg L(-1)), Jamaica (1300 μg L(-1)), and St Kitts and Nevis (1400 μg L(-1

  12. Rapid and sensitive suspension array for multiplex detection of organophosphorus pesticides and carbamate pesticides based on silica–hydrogel hybrid microbeads

    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

  13. Rapid and sensitive suspension array for multiplex detection of organophosphorus pesticides and carbamate pesticides based on silica–hydrogel hybrid microbeads

    Wang, Xuan [Key Laboratory of Environmental Medicine Engineering, Ministry of Education, School of Public Health, Southeast University, Nanjing, Jiangsu (China); Mu, Zhongde; Shangguan, Fengqi [State Key Laboratory of Bioelectronics, School of Biological Science and Medical Engineering, Southeast University, Nanjing, Jiangsu (China); Liu, Ran; Pu, Yuepu [Key Laboratory of Environmental Medicine Engineering, Ministry of Education, School of Public Health, Southeast University, Nanjing, Jiangsu (China); Yin, Lihong, E-mail: lhyin@seu.edu.cn [Key Laboratory of Environmental Medicine Engineering, Ministry of Education, School of Public Health, Southeast University, Nanjing, Jiangsu (China)

    2014-05-01

    Highlights: • Silica–hydrogel hybrid microbeads were used to develop suspension array. • The results in detecting pesticides agree well with those from LC–MS/MS. • The method showed the good capability for multiplex analysis of pesticides residues. - Abstract: A technique for multiplex detection of organophosphorus pesticides and carbamate pesticides has been developed using a suspension array based on silica–hydrogel hybrid microbeads (SHHMs). The main advantage of SHHMs, which consist of both silica and hydrogel materials, is that they not only could be distinguished by their characteristic reflection peak originating from the stop-band of the photonic crystal but also have low non-specific adsorption of proteins. Using fluorescent immunoassay, the LODs for fenitrothion, chlorpyrifos-methyl, fenthion, carbaryl and metolcarb were measured to be 0.02 ng/mL, 0.012 ng/mL, 0.04 ng/mL, 0.05 ng/mL and 0.1 ng/mL, respectively, all of which are much lower than the maximum residue limits, as reported in the European Union pesticides database. All the determination coefficients for these five pesticides were greater than 0.99, demonstrating excellent correlations. The suspension array was specific and had no significant cross-reactivity with other chemicals. The results for the detection of pesticide residues collected from agricultural samples using this method agree well with those from liquid chromatography–tandem mass spectrometry. Our results showed that this simple method is suitable for simultaneous detection of these five pesticides residues in fruits and vegetables.

  14. Monitoring of N-methyl carbamate pesticide residues in water using hollow fibre supported liquid membrane and solid phase extraction

    Msagati, Titus A. M.; Mamba, Bhekie B.

    The aim of this work was to develop a method for the determination of N-methyl carbamates in water involving hollow fibre supported liquid membrane (HFSLM) and solid phase extraction (SPE) as sample preparation methods. Four N-methyl carbamate pesticides, aldicarb, carbaryl, carbofuran and methiocarb sulfoxide, were simultaneously extracted and analysed by a liquid chromatograph with a diode array detector (LC-UV/DAD) and a liquid chromatograph coupled to a ion trap quadrupole mass spectrometer (LC-ESI-MS). The high performance liquid chromatography (HPLC) separation of carabamate extracts was performed on a C18 column with water-acetonitrile as the mobile phase. The mass spectrometry analyses were carried out in the positive mode, operating under both the selected ion monitoring (SIM) and full scan modes. The solid phase recoveries of the extracts ranged between 8% and 98%, with aldicarb having the highest recoveries, followed by carbaryl, carbofuran and methiocarb had the lowest recovery. The HFSLM recovery ranged between 8% and 58% and the order of recovery was similar to the SPE trend. Factors controlling the efficiency of the HFSLM extraction such as sample pH, stripping phase pH, enrichment time, stirring speed as well as organic solvent used for entrapment of analytes, were optimised to achieve the highest enrichment factors.

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

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

    1999-01-01

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

  16. 氨基甲酸酯类农药的微色谱快速检测法%Rapid Determination of Carbamate Pesticides by Micro-chromatography

    卫海燕; 邵华

    2011-01-01

    [ Objective] To rapidly detect the carbamate pesticides by preparing a new instrument of micro-column detector with capillary effect. [ Methods ] Based on the principle of thin-layer chromatography, fixing the sorbent in the thin heating wire, using microcolumn detector to prepare a new instrument of micro-column detector, the carbamate pesticides was rapidly detected and analyzed qualitatively and quantitatively. [ Results ] The method can make qualitative and quantitative analysis of carbamate pesticides, and the minimum detection limit was 50 μg. [ Conclusion ] The method is simple, efficient , reproducible, with less reagent consumption,can be used to detect bulk carbamate pesticides samples and it is a new method for rapid pesticide poisoning filtering.%目的 利用毛细管效应建立制备微色谱柱检测器以快速检测氨基甲酸酯类农药.方法 在薄层色谱原理的基础上,通过将吸着剂固定于细加热丝上,利用毛细管效应制备微色谱柱检测器,对氨基甲酸酯类农药作出快速的定性分析.结果 该方法 可以对氨基甲酸酯类农药作出快速的定性分析,且最低检出量可达到50 μg.结论 该法操作简便,高效,重现性好,且试剂用量少,是批量氨基甲酸酯类农药样品定性检测和突发农药中毒事件现场快速筛选的一种新方法 .

  17. 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.

  18. 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 <8.2%, n=5) were achieved. The developed method was applied to the analysis of four carbamate pesticides in apple and lettuce samples, and acceptable recoveries (i.e. 87.5-106.5%) were obtained for the standard addition. PMID:27036210

  19. Age-related differences in neurotoxicity produced by organophosphorus and N-methyl carbamate pesticides

    Potential pesticide effects in infants and toddlers have received much attention in the scientific literature and the public media, including the concern for increased response to acute or shortterm exposures. Age-related differences in the acute neurotoxicity of acetylcholinest...

  20. Occurrence and Distribution of Carbamate Pesticides and Metalaxyl in Southern Ontario Surface Waters 2007-2010.

    Struger, John; Grabuski, Josey; Cagampan, Steve; Sverko, Ed; Marvin, Chris

    2016-04-01

    Surface water sampling in 2007-2010 measured the occurrence of carbamates and metalaxyl during base flow conditions and wet weather events in southern Ontario surface waters. Carbaryl, metalaxyl and pirimicarb were the most frequently detected compounds. In 2008 these three compounds were detected in over 50 % of the samples. Overall mean concentrations of carbaryl and metalaxyl over the course of the study (2007-2010) were 15 and 18 ng/L, respectively. Elevated concentrations of carbaryl (~100 to ~950 ng/L) appeared associated with wet weather (high flow) events, while highest concentrations of metalaxyl (~20-1330 ng/L) were correlated with base flow conditions. We attributed these observations as the result of runoff of carbaryl from the watershed during rain events, while metalaxyl contamination may have resulted primarily from spray drift. PMID:26754544

  1. Allergic reaction induced by dermal and/or respiratory exposure to low-dose phenoxyacetic acid, organophosphorus, and carbamate pesticides

    Several types of pesticides, such as organophosphates, phenoxyacetic acid, and carbamate have a high risk of affecting human health, causing allergic rhinitis and bronchial asthma-like diseases. We used our long-term sensitization method and a local lymph node assay to examine the allergic reactions caused by several types of pesticides. BALB/c mice were topically sensitized (9 times in 3 weeks), then challenged dermally or intratracheally with 2,4-D, BRP, or furathiocarb. One day post-challenge, the mice were processed to obtain biologic materials for use in assays of total IgE levels in serum and bronchoalveolar lavage fluid (BALF); differential cell counts and chemokine levels in BALF; lymphocyte counts and surface antigen expression on B-cells within regional lymph nodes (LNs); and, ex situ cytokine production by cells from these LNs. 2,4-D-induced immune responses characteristic of immediate-type respiratory reactions, as evidenced by increased total IgE levels in both serum and BALF; an influx of eosinophils, neutrophils, and chemokines (MCP-1, eotaxin, and MIP-1β) in BALF; increased surface antigen expression on B-cells IgE and MHC class II production) in both auricular and the lung-associated LNs; and increased Th2 cytokine production (IL-4, IL-5, IL-10, and IL-13) in both auricular and the lung-associated LN cells. In contrast, BRP and furathiocarb treatment yielded, at most, non-significant increases in all respiratory allergic parameters. BRP and furathiocarb induced marked proliferation of MHC Class II-positive B-cells and Th1 cytokines (IL-2, TNF-α, and IFN-γ) in only auricular LN cells. These results suggest that 2,4-D is a respiratory allergen and BRP and furathiocarb are contact allergens. As our protocol detected classified allergic responses to low-molecular-weight chemicals, it thus may be useful for detecting environmental chemical-related allergy.

  2. 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.

  3. Multi photon ionization mass spectrometry of carbamate pesticides, herbicides and fungicides

    Pesticides and herbicides are useful for a wide range of applications today. The determination of these substances either in the pure form or in complex matrices is of high analytical interest. Especially since these substances can by found in every day products. The combination of multi photon ionization (MUPI) and time of flight laser mass spectrometry may be a powerful tool for achieving fast well interpretable mass spectra for analytical purposes. In this paper we will discuss the mass spectra of several pesticides and herbicides accessed by MUPI-time-of-flight mass spectrometry. The influence of the laser pulse duration on the mass spectra are discussed

  4. 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%).

  5. Age-related differences in acetylcholinesterase inhibition produced by organophosphorus and N-methyl carbamate pesticides

    Introduction The concern that infants and children may be more susceptible to the toxic effects of chemicals, including pesticides, has received much attention in the scientific literature and the public media. Greater toxicity may be evident as long-term adverse outcomes, e.g.,...

  6. [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. PMID:24669707

  7. 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.

  8. 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.

  9. Validation of analytical methods for ethyl carbamate in nine food matrices.

    Ryu, Dayeon; Choi, Bogyoung; Kim, Nayoung; Koh, Eunmi

    2016-11-15

    Ethyl carbamate (EC) is formed through a reaction between ethanol and either cyanate or N-carbamyl compounds. This study aimed to develop and validate analytical methods for EC determination in nine food matrices: apple juice, soju, milk, corn oil, rice porridge, peanut butter, beef, flat fish, and sea mustard. Differences from AOAC procedure were use of d5-EC as internal standard, dilution of alcohol content, removal of lipophilic compounds by hexane, and removal of hydrophilic polysaccharides by gel-forming. Standard curves had a good linearity (R(2)>0.997) in all matrices tested. LOD and LOQ were in the range of 0.69-6.08μg/kg and 2.10-18.43μg/kg, respectively. Recovery rates ranged from 80.75 to 121.82% for intra-day and ranged from 78.84 to 116.98% for inter-day. The relative standard deviations (RSDs) were below 14%. These results indicate that the established methods can be applied to determine EC in a variety of foods. PMID:27283695

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

    Using a 23 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 μg L-1, and 17.0 and 33.0 μg L-1, respectively.

  11. Characterization of acetylcholinesterase from the brain of the Amazonian tambaqui (Colossoma macropomum) and in vitro effect of organophosphorus and carbamate pesticides.

    Assis, Caio Rodrigo Dias; Castro, Patrícia Fernandes; Amaral, Ian Porto Gurgel; Carvalho, Elba Verônica Matoso Maciel; Carvalho, Luiz Bezerra; Bezerra, Ranilson Souza

    2010-10-01

    In the present study, acetylcholinesterase (AChE) from the brain of the Amazonian fish tambaqui (Colossoma macropomum) was partially characterized and its activity was assayed in the presence of five organophosphates (dichlorvos, diazinon, chlorpyrifos, and tetraethyl pyrophosphate [TEPP]) and two carbamates (carbaryl and carbofuran) insecticides. Optimal pH and temperature were 7.0 to 8.0 and 45°C, respectively. The enzyme retained approximately 70% of activity after incubation at 50°C for 30 min. The insecticide concentration capable of inhibiting half of the enzyme activity (IC50) for dichlorvos, chlorpyrifos, and TEPP were calculated as 0.04 µmol/L, 7.6 µmol/L, and 3.7 µmol/L, respectively. Diazinon and temephos did not inhibit the enzyme. The IC50 values for carbaryl and carbofuran were estimated as 33.8 µmol/L and 0.92 µmol/L, respectively. These results suggest that AChE from the juvenile C. macropomum brain could be used as an alternative biocomponent of organophosphorus and carbamate biosensors in routine pesticide screening in the environment. PMID:20872688

  12. Summary of Validation of Multi-Pesticide Methods for Various Pesticide Formulations

    The validation of multi-pesticide methods applicable for various types of pesticide formulations is treated. In a worked-out practical example, i.e. lambda cyhalothrin, the theoretical considerations outlined in the General Guidance section are put into practice. GC conditions, selection of an internal standard and criteria for an acceptable repeatability of injections are outlined, followed by sample preparation, calibration, batch analysis and confirmation of results through comparison using different separation columns. Complete sets of data are displayed in tabular form for other pesticide active ingredients and real formulations. (author)

  13. 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

    2012-07-01

    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. PMID:22686368

  14. HPLC-MS测定白酒中氨基甲酸酯类农药残留%Determination of carbamates pesticides in liquor by HPLC/MS

    谭文渊; 袁东; 付大友; 李艳清; 王蓉

    2012-01-01

    A HPLC/MS method has been established for the determination of ten carbamates pesticides in liquor. The chromatographic conditions are as follows: Column of Phenomenex-Luna CN 100 A(250 mm×.6 mm×5 pm), and mobile phase was acetonitrile-water(20:80-80:20 within 40 minutes), flow rate was 1.0 mL/min, wavelength was 195 nm, column temperature was 25 ℃ and the injection volume was 20 μl.. MS conditions: Scanning range is 50-350 m/z, temperature of drying gas is 350 %, flow rate of drying gas is 8.0 mL/min, pressure of the evaporative gas is 275.86 kPa. The liquor samples were treated by SPE(solid phase extraction, NH2) and then concentrated by nitrogen-blow. Results showed that the standard curves of ten carbamates were linear over the quality range of 0.05-3 μg/mL, the correlation coefficient r were over 0.99. The average recovery of carbamates were 72.6%-97.6%, RSD were 2.6%-5.9%. Conclusion: this method was accurate, rapid, sensitive for the determination of carbamates pesticides in liquor by HPLC/MS.%建立了一种同时对白酒中10种氨基甲酸酯类农药残留的HPLC-MS测定方法。色谱条件:色谱柱Phenomenex-LunaCN100A(250mm×4.6mm×5μm),流动相乙腈-水(在40min内乙腈由20%变为80%),流速1.00mL/min,检测波长195nm,柱温25℃,进样量20μL。质谱条件:电喷雾离子源(ESI+源),扫描范围(m/z)为50~350,干燥气温度350℃,干燥气流速8.0mL/min,雾化气压力275.86kPa。样品制备:白酒样品用固相萃取处理后,氮吹浓缩,乙腈定容至2mL。结果表明,10种氨基甲酸酯类农药残留在0.05~3μg范围积线性关系良好,相关系数R2〉0.99。平均回收率在72.6%和97.6%,RSD在2.6%~5.9%之间。结论:方法灵敏度高、操作简便、结果准确,可用于酒样中痕量农药残留的含量测定。

  15. Determination of 7 carbamate pesticides in water by solid phase extraction-gas chromatography%固相萃取-气相色谱法测定水中7种氨基甲酸酯农药

    周伦敏; 陆昱养; 何云亚

    2013-01-01

    目的:建立应用气相色谱-氮磷检测器结合固相萃取测定水中7种氨基甲酸酯农药的方法.方法:水样经ENVI-Carb固相萃取柱富集,以二氯甲烷+丙酮(1+1)洗脱,采用DB-1701毛细管柱和氮磷检测器进行检测.结果:7种氨基甲酸酯农药在DB-1701毛细管柱上均能得到很好分离,回收率在82.0%~101.5%,相对标准偏差为2.9%~10.5%.结论:本方法简便、快速、灵敏,可用于水中氨基甲酸酯农药的检测.%Objective:To establish a method for determination of 7 carbamate pesticides in water by gas chromatography-nitrogen phosphorus detector combined with solid-phase extraction.Methods:The target pesticides in water samples were enrichmented with ENVI-Carb solid phase extraction column,and eluted with dichloromethane and acetone(1 + 1),and separated with DB-1701 capillary column and detected with GC-NPD.Results:Seven carbamate pesticides could be well separated,the recovery rates were 82.0% ~ 101.5%,with the relative standard deviation of 2.9% ~ 10.5%.Conclusion:This method was simple,rapid and sensitive and it can be applied for analysis of carbamate pesticides in water.

  16. Rapid Determination of Organic Phosphorus and Carbamate Pesticides in Samples%样品中有机磷与氨基甲酸酯类农药快速检测方法的建立

    卫海燕; 邵华

    2011-01-01

    目的 建立现场快速筛选区分有机磷农药和氨基甲酸酯类农药的方法.方法 在薄层色谱原理基础上,利用毛细管效应制备微色谱柱检测仪,检测2类农药.结果 该方法可以对有机磷农药和氨基甲酸酯类农药作出快速的定性分析,且最低检出量可达到10 μg.结论 该法操作简便,高效,重现性好,且试剂用量少,是批量农药样品定性检测和突发农药中毒事件现场快速筛选的一种新方法.%[Objective]To establish the method for rapid filtering organophosphorus pesticides and carbamate pesticides.[Methods]Based on the principle of thin-layer chromatography, the micro-column detector was prepared by using capillary effect, and was used to detect 2 kinds of pesticides.[Results]The method could make qualitative and quantitative analysis of organophosphorus peaticides and carbamate pesticides, and the minimum detection limit was 10 μg.[Conclusion]The method is simple, efficient, reproducible, with less reagent consumption, and it is a new method for qualitative detection of bulk samples of pesticides and rapid pesticide poisoning filtering in emergency incident.

  17. Applicability of a carbamate insecticide multiresidue method for determining additional types of pesticides in fruits and vegetables.

    Krause, R T; August, E M

    1983-03-01

    Several fruits and vegetables were fortified at a low (0.02-0.5 ppm) and at a high (0.1-5 ppm) level with pesticides and with a synergist, and recoveries were determined. Analyses were performed by using 3 steps of a multiresidue method for determining N-methylcarbamates in crops: methanol extraction followed by removal of plant co-extractives by solvent partitioning and chromatography with a charcoal-silanized Celite column. Eleven compounds were determined by using a high performance liquid chromatograph equipped with a reverse phase column and a fluorescence detector. Twelve additional compounds were determined by using a gas-liquid chromatograph equipped with a nonpolar packed column and an electron capture or flame photometric detector. Recoveries of 10 pesticides (azinphos ethyl, azinphos methyl, azinphos methyl oxygen analog, carbaryl, carbofuran, naphthalene acetamide, naphthalene acetic acid methyl ester, napropamide, phosalone, and phosalone oxygen analog) and the synergist piperonyl butoxide, which were determined by high performance liquid chromatography, averaged 100% (range 86-117) at the low fortification level and 102% (range 93-115) at the high fortification level. Quantitative recovery of naphthalene acetamide through the method required that an additional portion of eluting solution be passed through the charcoal column. Recoveries of 7 additional pesticides (dimethoate, malathion, methyl parathion, mevinphos, parathion, phorate oxygen analog, and pronamide), which were determined by gas-liquid chromatography (GLC), averaged 108% (range 100-120) at the low fortification level and 107% (range 99-122) at the high fortification level. DDT, diazinon, dieldrin, phorate, and pirimiphos ethyl, which were determined by GLC, were not quantitatively recovered. PMID:6853408

  18. UPLC-MS/MS测定中药材中19种氨基甲酸酯农药残留量%Determination of Nineteen Carbamate Pesticides in Chinese Medicinal Materials by UPLC-MS/MS

    张燕; 杨钊; 金红宇; 孙磊; 李欣荣; 吴爱英

    2011-01-01

    OBJECTIVE To establish a method for the determination of 19 carbamate pesticides in Chinese medicinal materials by UPLC triple-quadrupole tandem mass spectrometer.METHODS The samples were determinated by multi-reactions monitoring (MRM) technology.The separation was performed on a Waters ACQUITY UPLC (R) BEH C18 column with acetonitrile -0.1% formic acid ( 1:1 ) with a flow rate of 0.2 mL min-1.Ion mode was set as ESI+.RESULTS The standard curves of the 19 carbamate pesticides showed good linearity over the concentration range of 1.0 - 100 μg · L-1 (r =0.994 7 -0.999 7), respectively.The LODs of 19 carbamate pesticides were in the range of 0.02 - 0.46 μg · L- 1 and the average recoveries were 73.2% - 119.7% at three levels.CONCLUSION The method is rapid, sensitive and suitable for the determination of 19 carbamate pesticides in Chinese medicinal materials.%目的 建立测定中药材中19种氨基甲酸酯农药残留量的超高效液相-串联四级杆质谱方法.方法 多反应监测模式测定,以Waters ACQUITY UPLC(R) BEH C18进行分离,乙腈-0.1%甲酸溶液(1:1),流速:0.2 mL·min-1.离子化模式:ESI+.结果 19种农药测定的线性范围在1.0~100.0 μg·L-1之间,r分别在0.994 7~0.999 7之间,检出质量浓度分别在0.02~0.46μg·L-1之间,3个水平的回收率分别在73.2%~119.7%之间.结论 该方法快速、准确、灵敏,可用于中药材中氨基甲酸酯类农药残留的测定.

  19. 2010年杭州市蔬菜有机磷和氨基甲酸酯农药残留状况分析%Analysis of organophosphorus and carbamate pesticide residues in vegetables collected from Hangzhou in 2010

    何良兴; 张瓅文; 李燕

    2011-01-01

    目的:了解杭州市蔬菜农药残留情况,为蔬菜质量安全的监管和控制工作提供科学依据.方法:采集蔬菜样品446577批次,测定有机磷和氨基甲酸酯农药残留量,并对结果进行分析总结.结果:蔬菜年均农药超标率为0.09%,残留农药以有机磷为主,不同品种蔬菜的超标率与超标农药类型都不同,杭州本地与外地蔬菜农药超标率没有显著不同.结论:杭州市蔬菜农药残留水平较低,质量安全状况良好,但禁用农药还需要进一步加强监管.%Objective: To investigate the conditions of organophosphorus and carbamate pesticide residues in vegetables in Hangzhou in order to provide the basis for surveillance and control of vegetables safety. Methods: The total 446,577 samples of vegetables were collected and their residues of organophosphorus and carbamate were measured. At last, the results were analysised and summaried. Results: The disqualification rate of vegetables is 0.09%. The organophosphorus is the main pesticide residues. The disqualification rate and the type of pesticide residues varies in different kinds of vegetables. There's no difference in the disqualification rate of vegetables between Hangzhou and other places. Conclusion: The level of pesticide residues is low,and vegetable quality of Hangzhou is good, but supervision and administration on the forbidden pesticides should be strengthened.

  20. 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. PMID:27362399

  1. 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.

  2. Study on carbamate pesticides by capillary electrophoresis with laser-induced fluorescence detection%CE-LIF在氨基甲酸酯类农药研究中的应用

    杨玉林; 赵晓寅; 赵文杰; 周天舒

    2012-01-01

    用毛细管电泳激光诱导荧光检测法(CE-LIF),对灭除威(XMC)、混杀威(2,3,5-trime-thacarb)和灭虫威(mercaptodimethur)等3种氨基甲酸酯类农药进行了研究.在碱性条件下,氨基甲酸酯类农药水解产生甲胺并与荧光衍生试剂4-氯-7-硝基-2,1,3-苯并二唑(NBD-Cl)发生衍生化反应,产物经毛细管电泳激光诱导荧光检测法测定.对影响水解、衍生以及毛细电泳分离的因素如缓冲液酸度、浓度和衍生试剂的浓度等进行了详细讨论;在最佳条件下,3种农药的检出限分别可达3.0×10-9、1.0×10-9和3.0×10-9 mol/L,并测定了它们的水解速率常数及活化能.该方法不仅可对氨基甲酸酯类农药进行测定,同时也可用于对这类农药的一些理化常数的测定.%A sensitive and rapid capillary electrophoresis method with laser-induced fluorescence detection (CE-LIF) was developed for the determination of carbamate pesticides (including (3,5-dimethylphenyl) N-methylcarbamate (XMC), and mercaptodimethur). In alkaline solution, carbamate was hydrolyzed to methylamine, which can be derivatized by 4-chloro-7-nitrobenzo-2-oxa-1,3-diazole (NBD-C1) and detected by CE-LIF. Several parameters which influence the hydrolysis, derivatization and electrophoresis separation, such as pH, concentration of buffer solution and concentration of NBD-C1, were investigated. The detection limits of the three carbamates were 3. 0×10-9, 1. 0 ×10-9 and 3. 0 ×10-9 mol/L, respectively. The proposed method was successfully employed to determine the rate constants and activation energies for carbamates hydrolysis.

  3. Pesticides

    ... rodents, noxious weeds, and insects. Pesticides help prevent crop loss and, potentially, human disease. According to the ... pesticides. DO NOT mix pesticides. DO NOT set traps or place bait in areas where children or ...

  4. Overall and class-specific scores of pesticide residues from fruits and vegetables as a tool to rank intake of pesticide residues in United States: A validation study.

    Hu, Yang; Chiu, Yu-Han; Hauser, Russ; Chavarro, Jorge; Sun, Qi

    2016-01-01

    Pesticide residues in fruits and vegetables are among the primary sources of pesticide exposure through diet, but the lack of adequate measurements hinder the research on health effects of pesticide residues. Pesticide Residue Burden Score (PRBS) for estimating overall dietary pesticide intake, organochlorine pesticide score (OC-PRBS) and organophosphate pesticide score (OP-PRBS) for estimating organochlorine and organophosphate pesticides-specific intake, respectively, were derived using U.S. Department of Agriculture Pesticide Data Program data and National Health and Nutrition Examination Survey (NHANES) food frequency questionnaire data. We evaluated the performance of these scores by validating the scores against pesticide metabolites measured in urine or serum among 3,679 participants in NHANES using generalized linear regression. The PRBS was positively associated with a score summarizing the ranks of all pesticide metabolites in a linear fashion (p for linear trend vegetables with high vs. low pesticide residues, respectively (p for trend vegetables (p for trend 0.07) than from less contaminated Fruits and vegetables (p for trend 0.63), although neither of the associations achieved statistical significance. The PRBS and the class-specific scores for two major types of pesticides were significantly associated with pesticide biomarkers. These scores can reasonably rank study participants by their pesticide residue exposures from fruits and vegetables in large-scale environmental epidemiological studies. PMID:27128714

  5. Carbamates toxicity in farmers and its assesment through biochemical parameters

    Prevalent environmental toxicity of various chemical group of pesticides and their effects leading towards increasing morbidity and mortality in the farmers is of great concerned. In this situation the biochemical biomarkers are regarded as meaningful tools for monitoring toxic end points. This work was aimed to assess the toxic impacts of carbamates through some biochemical parameters and useful validity of these biomarkers was also observed. Present results reveal inhibition of cholinesterase activity by 46% whereas bilirubin, urea and creatinine levels in serum were increased and sugar values was decreased at highly significant level (p<0.001). Urine urobilinogen concentration found raised significantly at high level (p<0.001) while protein, urea creatinine and sugar values in urine of the farmers seen non-significant. This study concluded that the selected biochemical parameters can be used as biomarkers to assess the significant toxic effects in the exposed populations. (author)

  6. Principles of Single-Laboratory Validation of Analytical Methods for Testing the Chemical Composition of Pesticides

    Underlying theoretical and practical approaches towards pesticide formulation analysis are discussed, i.e. general principles, performance characteristics, applicability of validation data, verification of method performance, and adaptation of validated methods by other laboratories. The principles of single laboratory validation of analytical methods for testing the chemical composition of pesticides are outlined. Also the theoretical background is described for performing pesticide formulation analysis as outlined in ISO, CIPAC/AOAC and IUPAC guidelines, including methodological characteristics such as specificity, selectivity, linearity, accuracy, trueness, precision and bias. Appendices I–III hereof give practical and elaborated examples on how to use the Horwitz approach and formulae for estimating the target standard deviation towards acceptable analytical repeatability. The estimation of trueness and the establishment of typical within-laboratory reproducibility are treated in greater detail by means of worked-out examples. (author)

  7. UPLC -MS/MS determination of carbamate pesticides in traditional Chinese medicine%超高效液相色谱-串联质谱法测定中草药中氨基甲酸酯类农药残留量

    李娜; 刘磊; 邵辉; 李辉; 张玉婷; 宋海菲; 郭永泽

    2011-01-01

    目的:结合固相萃取技术,克服了中草药样品中复杂的基质干扰问题,建立超高效液相色谱-串联质谱( UPLC - MS/MS)法检测中药材中15种氨基甲酸酯类杀虫剂的残留量.方法:样品中残留的农药经乙腈提取,PSA固相萃取柱净化后,采用UPLC - MS/MS法进行测定.结果:15种农药在其各自的浓度范围内,线性关系良好,相关系数在0.995 ~0.999之间.在定量限(LOQ)、5倍定量限和10倍定量限3个添加浓度水平,平均加标回收率在61.8% ~98.1%之间;RSD在1.8% ~ 14.8%之间.结论:该方法操作简便,净化效果好,灵敏度高,可为中药材中氨基甲酸酯类杀虫剂污染状况调查提供检测方法支持.%Objective:An ultra performance liquid chromatography - tandem mass spectrometric method was developed for the determination of 15 carbamate pesticides in traditional Chinese medicine. Method:Pesticides were extracted with acetonitrile,cleaned up by PSA solid phase extraction column,and then analyzed by UPLC -MS/MS. Result:The standard calibration curves for 15 carbamate pesticides showed high correlation coefficient (0.995 -0. 999) over their respective concentration range. The average recovery of 15 carbamate pesticides at the three fortification levels ( LOQ,5 LOQ and 10 LOQ) was between 61. 8% and 98. 1% with the relative standard deviation between 1. 8% and 14. 8%. Conclusion:It was indicated that the method developed in this study is easier,more sensitive and has a better purification effect. So,this method can be further applied to investigate the contamination status of traditional Chinese medicine by the carbamate pesticides.

  8. 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.

  9. PSA分散固相萃取液相色谱柱后衍生荧光法测定蔬菜和水果中的13种氨基甲酸酯%Study on determination of thirteen carbamate pesticides in vegetables and fruits by HPLC with post-column derivatization and fluorescence detection after PSA dispersive solid-phase extraction cleanup

    于彦彬; 谭丕功; 曲璐璐; 王学松

    2009-01-01

    建立了PSA分散固相萃取净化, 液相色谱柱后衍生荧光法测定蔬菜和水果中13种氨基甲酸酯农药的分析方法. 在建立的测定条件下, 13种氨基甲酸酯的含量与峰面积之间成线性关系, 相关系数大于0.994, 保留时间的相对标准偏差在0.03%~0.22%之间, 检测下限在2.00~2.28 μg/kg范围内. 西瓜、杏、茄子及胡萝卜中13种氨基甲酸酯的平均回收率在71.7%~110%之间, 相对标准偏差在0.68%~15%之间, 分析结果优于氨基柱固相萃取法.%Determination of thirteen carbamate pesticides residues in vegetables and fruits by HPLC with PSA dispersive solid-phase extraction cleanup and post-column derivatization fluorescence detection is developed. Under the optimal determination conditions, the detection limits of thirteen carbamate pesticides are in the range of 2.00~2.28 jug/kg. There is a good linear relationship in the content range of determination. The correlation coefficients of thirteen carbamate pesticides are more than 0.99. The relative standard deviations of retention time are in the range of 0.03%~0.22% . It is simpler in sample handling by PSA dispersive solid-phase extraction than by NH2 column solid-phase extraction. There are little interference in matrix, and high quality results are obtained. The spiked average recoveries of thirteen carbamate pesticide residues ranged from 71.7%~110% with RSDs of 0.68%~15% for watermelon, apricot, eggplant and carrot, The results are very satisfactory.

  10. DETERMINATION OF CARBAMATE PESTICIDE RESIDUES IN WHEAT USING MATRIX SOLID-PHASE DISPERSION EXTRACTION AND LIQUID CHROMATOGRAPHY%基质固相分散萃取-液相色谱法测定小麦中多种氨基甲酸酯农药残留的研究

    吴丽华; 田忙雀; 杨勤元

    2011-01-01

    研究了C18基质固相分散萃取(MSPDE),高效液相色谱-柱后衍生-荧光检测器测定小麦中6种氨基甲酸酯农药的方法.通过对色谱条件、基质固相分散材料的选择及其与样品的比例、洗脱条件以及加标回收率进行试验,建立和优化了小麦中6种氨基甲酸酯农药的MSPDE-HPLC-FLD多残留分析方法.结果显示,该方法对小麦样品中6种氨基甲酸酯农药的回收率为82.1%~94.0%,变异系数≤3.54%,方法的最低检出限为0.009 2~0.038 mg/kg.研究证明,基质固相分散萃取-液相色谱-柱后衍生方法简便、快速、准确、灵敏、节省样品和有机溶剂,可满足小麦中多种氨基甲酸酯农药残留同时检测的需要.%We studied a method for determining 6 kinds of carbamate pesticides in wheat using C18 matrix solid-phase dispersion extraction (MSPDE), high performance liquid chromatography, post-column derivation technique and fluorescence detector. Through the tests of the chromatographic conditions, the selection of matrix solid-phase dispersion material and the ratio of matrix solid-phase dispersion to the sample, the elution conditions and the standard recovery, we established and optimized the MSPDE-HPLC-FLD multi-residue analysis method for determining 6 kinds of carbamate pesticides in wheat. The results showed that the yield of the 6 kinds of carbamate pesticides in wheat reached 82.1% to 94.0 %, the coefficient of variation was equal to or less than 3.54 %, and the lowest detection limit was 0.009 2 to 0.038 0 mg/kg. It is testified that the method is simple, rapid, accurate, sensitive, and saving of samples and organic solvent, and can meet the requirement for simultaneously determining multiple kinds of carbamate pesticides in wheat.

  11. Method development and validation for the determination of pesticides in green coffee by gas chromatography

    This study describes the implementation and validation of a multiresidue methodology for the determination of organochlorine, organophosphorus and pyrethroids pesticides in green coffee. Pesticides residues were extracted from green samples with an acetone-water (2:1) mixture followed by ethyl acetate cyclohexane (1:1) partitioning. The clean up steps include gel permeation chromatography and mini column chromatography using silica gel. Final determination was carried out by high-resolution gas chromatography with a pulsed split less injection mode and simultaneous detection by μ-ECD and NPD coupled in parallel. The methodology is specific, selective precise and accurate. Recoveries of majority of pesticides from spiked samples range from 70 to 110% at fortification levels of 0.038 mg/kg-1.536 mg/kg with limit of quantitation between 0.011 mg/kg and 0.100 mg/kg

  12. Development and validation of a basin scale model PCPF-1@SWAT for simulating fate and transport of rice pesticides

    The objective of this study was to develop, verify, and validate a new GIS-based model for simulating the fate and transport of rice pesticides in river basins. A plot scale model simulating pesticide fate and transport in rice paddies (PCPF-1) was incorporated into the Soil and Water Assessment To...

  13. (BOSC) DOSE-RESPONSE MODELING FOR THE ASSESSMENT OF CUMULATIVE RISK DUE TO EXPOSURE TO N-METHYL CARBAMATE PRESTICIDES

    THE US EPA'S N-METHYL CARBAMATE CUMULATIVE RISK ASSESSMENT (NMCRA) ASSESSES THE EFFECT ON ACETYLCHOLINE ESTERASE (AChE) ACTIVITY OF EXPOSURE TO 10 N-METHLY CARBAMATE (NMC)PESTICIDES THROUGH DIETARY, DRINKING WATER, AND RESIDENTIAL EXPOSURES. THESE DATA THUS INFORM, BUT DO NOT COM...

  14. Organophosphorus and carbamate insecticide poisoning.

    Vale, Allister; Lotti, Marcello

    2015-01-01

    Both organophosphorus (OP) and carbamate insecticides inhibit acetylcholinesterase (AChE), which results in accumulation of acetylcholine (ACh) at autonomic and some central synapses and at autonomic postganglionic and neuromuscular junctions. As a consequence, ACh binds to, and stimulates, muscarinic and nicotinic receptors, thereby producing characteristic features. With OP insecticides (but not carbamates), "aging" may also occur by partial dealkylation of the serine group at the active site of AChE; recovery of AChE activity requires synthesis of new enzyme in the liver. Relapse after apparent resolution of cholinergic symptoms has been reported with OP insecticides and is termed the intermediate syndrome. This involves the onset of muscle paralysis affecting particularly upper-limb muscles, neck flexors, and cranial nerves some 24-96 hours after OP exposure and is often associated with the development of respiratory failure. OP-induced delayed neuropathy results from phosphorylation and subsequent aging of at least 70% of neuropathy target esterase. Cramping muscle pain in the lower limbs, distal numbness, and paresthesiae are followed by progressive weakness, depression of deep tendon reflexes in the lower limbs and, in severe cases, in the upper limbs. The therapeutic combination of oxime, atropine, and diazepam is well established experimentally in the treatment of OP pesticide poisoning. However, there has been controversy as to whether oximes improve morbidity and mortality in human poisoning. The explanation may be that the solvents in many formulations are primarily responsible for the high morbidity and mortality; oximes would not be expected to reduce toxicity in these circumstances. even if given in appropriate dose. PMID:26563788

  15. 动态微波辅助萃取法快速萃取苹果中8种氨基甲酸酯类农药%Rapid extraction of carbamate pesticides from apple on dynamic microwave-assisted extraction

    刘密兰; 曾庆磊; 丁兰; 金海燕

    2014-01-01

    目的:建立一种绿色的动态微波辅助快速萃取法结合高效液相色谱-串联质谱法测定苹果中8种氨基甲酸酯类农药的方法。方法以水为萃取溶剂,利用动态微波辅助萃取法对苹果中氨基甲酸酯类农药进行快速萃取;通过两步固相萃取法对所获得的萃取物进行净化和富集;采用高效液相色谱-串联质谱法对目标化合物进行测定。结果实验中对影响动态微波辅助萃取和固相萃取效率的实验条件进行了优化,最优的实验条件为:萃取剂为纯水;微波萃取功率为600 W;微波萃取时间为10 min;萃取剂流速为1.0 mL/min;固相萃取洗脱剂为2 mL的乙醇。8种氨基甲酸酯类农药在8.0~800 ng/g范围内成线性关系,相关系数为0.994~0.999;检出限为1.1~4.2 ng/g;方法的加标(8.0 ng/g)回收率为71%~90%。结论该方法可以用于苹果中氨基甲酸酯类农药的快速检测。%Objective A green and fast sample pretreatment method was proposed for determination of 8 carbamate pesticides from apple. Methods The 8 carbamate pesticides in apple samples were extracted by dynamic microwave-assisted extraction with water as extraction solvent. The extract obtained was purified by two steps SPE. Finally, the extract was injected into the LC-MS/MS system for analysis. The parameters which could affect the extraction efficiency were optimized. Results The optimized extraction conditions were observed at water as extraction solvent; 600 W of microwave forward power; extraction time, 10 min;extraction solvent flow-rate, 1.0 mL/min; 2 mL ethanol as the elution solvent of SPE. The linearity ranges of the proposed method from 8.0 to 800 ng/g were obtained and the correlation coefficient were 0.994~0.999. The limits of detection for the eight carbamate pesticides were in the range of 1.1~4.2 ng/g. The recoveries of the eight carbamate pesticides for the spiked samples (8.0 ng/g) were in the range of 71

  16. 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

  17. Validation of a residue method to determine pesticide residues in cucumber by using nuclear techniques

    In this study, a multi-residue method using ethyl acetate for extraction and gel permeation chromatography for clean-up was validated to determine chlorpyrifos, malathion and dichlorvos in cucumber by gas chromatography. For this purpose, homogenized cucumber samples were fortified with pesticides at 0.02 0.2, 0.8 and 1 mg/kg levels. The efficiency and repeatability of the method in extraction and cleanup steps were performed using 14C-carbaryl by radioisotope tracer technique. 14C-carbaryl recoveries after the extraction and cleanup steps were between 92.63-111.73 % with a repeatability of 4.85% (CV) and 74.83-102.22 % with a repeatability of 7.19% (CV), respectively. The homogeneity of analytical samples and the stability of pesticides during homogenization were determined using radio tracer technique and chromatographic methods, respectively.

  18. Adaptation and validation of the TLC detection methods in determination of pesticide residues in grain

    This work was performed to investigate the possibilities of applying prescribed TLC detection methods in combination with GPC cleanup procedure in grains as alternative methods to gas and high performance liquid chromatography for pesticide residue analyses. The MDQ, RF and RRf values of marker and selected compounds were close to those reported in the basic method. The recoveries and reproducibility of the method obtained with wheat and rice samples in our laboratory were within the limits specified by the Codex GLs on method validation. The recoveries determined by GC analyses were practically the same which confirms the accuracy of TLC detection. (author)

  19. 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

    2016-01-01

    International audience 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...

  20. Determination of Carbamate Pesticides Residues in Vegetables by High Performance Liquid Chromatography Coupled with Tandem Mass Spectrometry%高效液相色谱-串联质谱法测定蔬菜中氨基甲酸酯类农药残留

    周长朋; 杨丽君; 徐成钢; 时文春; 王静

    2011-01-01

    A high performance liquid chromatography-tandem mass spectrometric (HPLC-MS/MS) method was developed for the determination of 5 carbamate pesticides, including aldicarb, aldicarbsulfoxide, aldicarbsulfone, carbofuran and 3-hydroxycarbofuran in products of vegetables. Homogenized samples were extracted with acetonitrle. The extracts were dehydrated with sodium sulphate anhydrous. The extract layer was concentrated in 40°C by vacuum rotary steam to 1. 0 mL,and dried by nitrogen flowing,then redissolved in 0. 1% formic acid issolution. Identification of 5 carbamate pesticides was achieved by electospray ionization tandem mass spectrometry in positive mode using multiple reaction monitoring (MRM) and quantification analysis was performed with matrix-matched standard calibration. The results indicated that, under the optimal conditions, the calibration curves showed good linearity for 5 carbamate pesticides over the concentration range of 5. 0 - 100 jug/kg. Detection limits were 5. 0 μg/kg. The mean recoveries varied from 61. 3% to 123% at three spiked levels of 5. 0,10 and 20 μg/kg. The RSDs were less than 15%. This method is sensitive and reproducible,and suitable for the routine determination of 5 carbamate pesticides residues in vegetables.%建立了高效液相色谱-串联质谱(HPLC-MS/MS)法同时测定蔬菜中涕灭威、涕灭威砜、涕灭威亚砜、克百威、三羟基克百威5种氨基甲酸酯类农药残留的方法.样品均质后,经乙腈提取,无水硫酸钠脱水.提取液40℃减压旋蒸浓缩至1.0mL,氮气吹干后,0.1%甲酸水溶解定容;采用高效液相色谱-串联质谱电喷雾多反应监测模式检测.实验结果表明,5种氨基甲酸酯类农药在5.0~100 μg/kg范围内线性关系良好.检出限均为5.0μg/kg.6种空白基质样品中5.0、10、20 μg/kg 3水平的加标回收率为61.30%~123%,相对标准偏差均在15%以内.该方法操作简单、灵敏度高、重现性好,可用于蔬菜中5种氨

  1. Rapid determination of 8 urinary carbamate pesticides by liquid chromatography-tandem mass spectrometry%尿中8种氨基甲酸酯类农药快速测定的液相色谱-串联质谱法

    刘华良; 王媛; 朱宝立

    2015-01-01

    目的 建立尿中8种氨基甲酸酯类农药同时测定的方法.方法 尿样用乙腈沉淀蛋白后,用液相色谱-串联质谱法进行测定,外标法定量,其中色谱柱采用C18超高效液相色谱柱,流动相为甲醇与乙酸铵溶液梯度淋洗,质谱采集方式为多反应监测.结果 样品中氨基甲酸酯类农药的线性范围为20~800 μg/L,当添加浓度为20、200、800 μg/L时,回收率为61.0%~121%,相对标准偏差为1.7%~5.5%.结论 该检测方法各项指标均符合GBZT 210.5-2008《职业卫生标准制定指南第5部分:生物材料中化学物质测定方法》的要求,适用于中毒患者尿中8种氨基甲酸酯类农药的同时检测.%Objective To establish a method for simultaneously determining the urinary concentrations of 8 carbamate pesticides.Methods After being purified by acetonitrile precipitation,urine samples were transferred to a liquid chromatography-tandem mass spectrometry system,and the concentrations of 8 carbamate pesticides were determined by external standard method.A C18 column was used for ultra-high-performance liquid chromatography;methanol/ammonium acetate solution was used as the mobile phase for gradient elution;the mass spectrometer was operated in a multi-reaction monitoring mode.Results The calibration curves were linear when the urinary concentrations of these carbamate pesticides were 20~800 μg/L,and the recovery rates were 61.0%~121% at spiked levels of 20,200 and 800 μg/L,with a relative standard deviation of 1.7%~5.5%.Conclusion This determination method meets the Guide for establishing occupational health standards-part 5:Determination methods of chemicals in biological materials,and can be used for simultaneous determination of 8 carbamate pesticides in the urine of poisoning patients.

  2. Development, validation and determination of multiclass pesticide residues in cocoa beans using gas chromatography and liquid chromatography tandem mass spectrometry.

    Zainudin, Badrul Hisyam; Salleh, Salsazali; Mohamed, Rahmat; Yap, Ken Choy; Muhamad, Halimah

    2015-04-01

    An efficient and rapid method for the analysis of pesticide residues in cocoa beans using gas and liquid chromatography-tandem mass spectrometry was developed, validated and applied to imported and domestic cocoa beans samples collected over 2 years from smallholders and Malaysian ports. The method was based on solvent extraction method and covers 26 pesticides (insecticides, fungicides, and herbicides) of different chemical classes. The recoveries for all pesticides at 10 and 50 μg/kg were in the range of 70-120% with relative standard deviations of less than 20%. Good selectivity and sensitivity were obtained with method limit of quantification of 10 μg/kg. The expanded uncertainty measurements were in the range of 4-25%. Finally, the proposed method was successfully applied for the routine analysis of pesticide residues in cocoa beans via a monitoring study where 10% of them was found positive for chlorpyrifos, ametryn and metalaxyl. PMID:25442595

  3. Investigation into the validity of extrapolation in setting maximum residue levels for pesticides in crops of similar morphology.

    Reynolds, S L; Fussell, R J; MacArthur, R

    2005-01-01

    Field trials were initiated to investigate if extrapolation procedures, which were adopted to limit costs of pesticide registration for minor crops, are valid. Three pairs of crops of similar morphology; carrots/swedes, cauliflower/calabrese (broccoli) and French beans/edible-podded peas; were grown in parallel at four different geographical locations within the UK. The crops were treated with both systemic and non-systemic pesticides under maximum registered use conditions, i.e. the maximum permitted application rates and the minimum harvest intervals. Once mature, the crops were harvested and analysed for residues of the applied pesticides. The limits of quantification were in the range 0.005-0.02 mg kg(-1). Analysis of variance and bootstrap estimates showed that in general, the mean residue concentrations for the individual pesticides were significantly different between crop pairs grown on each site. Similarly, the mean residue concentrations of most of the pesticides in each crop across sites were significantly different. These findings demonstrate that the extrapolations of residue levels for most of the selected pesticide/crop combinations investigated; chlorfenvinphos and iprodione from carrots to swedes; carbendazim, chlorpyrifos, diflubenzuron and dimethoate from cauliflower to calabrese; and malathion, metalaxyl and pirimicarb from French beans to edible-podded peas; appear invalid. PMID:15895609

  4. Research on detection method of pesticides residues of organic phosphorus and carbamate in vegetables and fruits%蔬菜、水果中16种有机磷和氨基甲酸酯农药残留检测方法研究

    郝宁

    2012-01-01

    [ Objective]To establish a method for rapidly detecting 16 kinds of pesticides residues of organic phosphorus and carba-mate in vegetables and fruits [Methods] The detection was conducted by applying gas chromatography with quartz capillary, by u-sing nitrogen-phosphorus detector with high sensitivity and through extracting sample by acetonitrile and acetone. [ Results] the linear ranges of organophosphorus pesticides were 5. 0-1 000. 0 μg/kg, r>0. 999 0. The lowest determination limit was 0. 1- 0. 5 μg/kg, the recoveries were 66.0% -84.0% , and RSD was 4. 8% -9.5% [ Conclusion] This method can determine organic phosphorus and carbamate pesticides simultaneously in vegetables and fruits. It has the characteristics of high sensitivity, good separating effect, high recovery rate, small variance coefficient and low determination limit.%目的 建立一种快速测定蔬菜、水果中有机磷和氨基甲酸酯16种农药残留的方法.方法 应用石英毛细管气相色谱法,利用高灵敏氮磷检测器,用乙腈和丙酮提取样品进行检测.结果 该方法检测16种农药残留的线性范围为5.0~1 000.0 μg/kg,相关系数≥0.9990,最低检出浓度为0.1~0.5 μg/kg,样品加标回收率为66.0%~84.0%,RSD为4.8%~9.5%.结论 该方法能同时测定蔬菜、水果中的有机磷和氨基甲酸酯类农药,具有灵敏度高、分离效果好、回收率高、变异系数小、检出限低的特点.

  5. 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. PMID:26513561

  6. Validation of thin-layer chromatographic methods for pesticide residue analysis. Results of the coordinated research projects 1996-2002

    Thin-layer chromatography (TLC) has a long history, but has been used only to a limited extent in pesticide residue analytical laboratories since gas liquid chromatography (GLC) and high performance liquid chromatography (HPLC) became readily available. Recent developments in the quality of plate coating and detection systems, as well as in extraction and cleanup methods have revived interest in TLC. The combination of these procedures with rigid quality control has created a niche for TLC in laboratories working in compliance with ISO 17025 or GLP. The Joint FAO/IAEA Division of Nuclear Techniques in Food and Agriculture recognized the importance of testing pesticide residues, especially in countries with limited resources. A coordinated research programme (CRP) was initiated for investigating the application of TLC detection methods to complement the instrumental techniques in pesticide residue analysis. An initial technical contract provided proof of the concept and elaborated the basic procedures, including a substantial database of retention factors and minimum detectable quantities of pesticides. To satisfy the demands from the eligible laboratories, two similar projects were started in 1997 and 1998. The titles of the projects were as follows: (i) Validation of Thin-layer Chromatographic Screening Methods for Pesticide Residue Analysis; and (ii) Alternative Methods to Gas and High Performance Liquid Chromatography for Pesticide Residue Analysis in Grain. Scientists from 18 countries participated in the above noted two projects. The major tasks of this programme were to adapt the methods, check the repeatability and reproducibility of Rf values, the minimum detectable quantities (MDQ) and apply the methods for determining various pesticide residues in representative matrices. Furthermore, they have extended the methods to other pesticides and commodities of interest in their countries and validated the methods elaborated. This TECDOC includes the most

  7. Validation of a method for the determination of 120 pesticide residues in apples and cucumbers by LC-MS/MS.

    Ramadan, Gouda; Al Jabir, Muna; Alabdulmalik, Najat; Mohammed, Ali

    2016-05-01

    Most countries have clearly defined regulations governing the use of pesticides in agricultural activity. The application of pesticides in agriculture usually leads to a residual amount of these pesticides on food products such as fruit and vegetables. The presence of pesticide residues on these foods destined for human consumption may pose food safety risks to consumers. To protect consumers, national authorities have established maximum limits for pesticide residues in foods. These limits can only be enforced if there are methods available to detect and monitor their concentrations in the applicable food products. To support the enforcement of this legislation, we have developed a multi-residue liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the analysis of 120 pesticide residues in apples and cucumbers which has been validated and implemented in the routine monitoring and surveillance programme for these pesticides. In this method, apple and cucumber samples are extracted using the QuEChERS method (quick, easy, cheap, effective, rugged, and safe) and the extracts were analyzed directly by LC-MS/MS. The mean recoveries at three different concentrations of 0.01 µg/g , 0.05 µg/g, and 0.1 µg/g over the analytical range varied between 70 and 120%. The repeatability of the method expressed as %RSD was less than 20%. The limit of detection (LOD) of the method ranged between 0.0014 and 0.0110 µg/g for apples and between 0.0012 and 0.0075 µg/g for cucumbers. The limit of quantification (LOQ) of the method was 0.01 µg/g for apples and cucumbers. The method has been used for the analysis of over 600 apple and 550 cucumber samples over the past two years. Copyright © 2016 John Wiley & Sons, Ltd. PMID:27443204

  8. Survey of ethyl carbamate in fermented foods sold in the United Kingdom in 2004.

    Hasnip, Sarah; Crews, Colin; Potter, Nicholas; Christy, Julie; Chan, Danny; Bondu, Thomas; Matthews, Wendy; Walters, Barry; Patel, Krishna

    2007-04-01

    Results are presented of a survey of fermented foods and beverages sold in the United Kingdom for levels of ethyl carbamate (urethane) carried out to expand the range of food types sold in the United Kingdom for which data regarding ethyl carbamate are available. Samples were analyzed by in-house validated methods, which included measurement uncertainty estimates. The samples comprised 75 fermented liquids (beers, wines, fortified wines, spirits, liqueurs, soy sauces, and vinegars) and 25 fermented solid foods (cheeses, yogurts, soybean products, sauerkraut, yeast extract, olives, and Christmas pudding). Ethyl carbamate was not detected in the beers or the cider. Wines contained between 11 and 24 microg/kg and sake between 81 and 164 microg/kg. Fortified wines contained ethyl carbamate at levels between 14 and 60 microg/kg. Only two of five liqueurs contained ethyl carbamate. Most soy sauces and vinegars did not contain ethyl carbamate. No ethyl carbamate was detected in cheeses, yogurts, olives, or soybean-based products. Single samples of sauerkraut, yeast extract, and Christmas pudding contained low levels (29, 41, and 20 microg/kg ethyl carbamate, respectively). PMID:17328558

  9. 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.

  10. 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...

  11. 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)

    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

  12. 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. PMID:27153296

  13. Development and validation of a cellular biosensor detecting pesticide residues in tomatoes.

    Flampouri, Kelly; Mavrikou, Sophie; Kintzios, Spiridon; Miliadis, George; Aplada-Sarlis, Pipina

    2010-03-15

    Two of the most important categories of pesticides used in agricultural practice are organophosphates and dithiocarbamates. Their extensive and inappropriate use has rendered their reliable monitoring at trace levels more and more necessary. This study presents the construction of a rapid and sensitive cellular biosensor test based on the measurement of changes of the cell membrane potential of immobilized cells, according to the working principle of the Bioelectric Recognition Assay (BERA). The cells were immobilized by entrapment in a sodium alginate bead and directly applied in different pesticide dilutions and agricultural samples. The pesticides used were the organophosphate insecticide diazinon and the dithiocarbamate fungicide propineb. Two different cell types, N2a (neuroblastoma) and Vero (fibroblast) were used as the biosensory elements in order to investigate their differential response against the pesticides. In this way, we hoped to increase the selectivity of the assay. Based on the observed patterns of response, we demonstrate that the sensor can be used for the qualitative and, in some concentrations, quantitative detection of the pesticides with a high degree of reproducibility. The lowest detected concentration was 3nM. Finally, for the investigation of the effects of different pesticides on the accumulation of cytosolic Ca(2+), we conducted a fluorescent assay on N2a cells treated with tomato sample extracts, which were replicates of the E.U. proficiency test sample. The tomato samples were either organically grown or contained 14 different pesticides. The experimental results showed a higher increase of the intracellular Ca(2+) concentration in cells treated with non-organic samples compared to the cells treated with organic samples. PMID:20152413

  14. Validation of a methodology multi-residue for the determination of pesticides residuals in strawberry (fragraria spp.) by gas chromatography

    This study describes the validation of multi-residue analytical methodology for the simultaneous determination of 19 organ chlorine, organophosphorus and organ nitrogen pesticides in strawberry. Pesticides residues were extracted from strawberry samples with ethyl acetate, the extracts were cleaned-up by GPC, the quantitative analysis was carried out by high resolution gas chromatography (GC) with a pulsed splitless injection mode and simultaneous detection by m-ECD and NPD coupled in parallel. The methodology is specific, selective, and accurate and robust the calibration curves in matrix matched analytical standards show linearity over the concentration range of 0.04-5.00 mg/kg with limits of detection and quantitation between 0.007-0.5 mg/kg and 0.01-1.00 mg/kg respectively. The recovery experiments yielding averages between 80-110% for most of the pesticides. The distribution of analyze in the laboratory sample was evaluated and it was found its homogeneity. The methodology was applied in field samples and was mainly found Captan residues below MRL

  15. [Acute poisoning by pesticides in children].

    Leveau, P

    2016-07-01

    Acute pesticide poisoning in children is rare but potentially serious. Some clinical patterns (toxidromes) are suggestive of the drug class: cholinergic crisis for organophosphate or carbamate insecticides; neurological syndrome for rodenticides; digestive and respiratory syndrome for herbicides. Treatment is symptomatic and only a few patients are treated with an antidote: atropine and pralidoxime for organophosphate insecticides, vitamin K for anticoagulant rodenticides. PMID:27266642

  16. Pesticides and inner-city children: exposures, risks, and prevention.

    Landrigan, P J; Claudio, L; Markowitz, S B; Berkowitz, G S; Brenner, B L; H. Romero; Wetmur, J G; Matte, T D; Gore, A.C.; Godbold, J H; Wolff, M S

    1999-01-01

    Six million children live in poverty in America's inner cities. These children are at high risk of exposure to pesticides that are used extensively in urban schools, homes, and day-care centers for control of roaches, rats, and other vermin. The organophosphate insecticide chlorpyrifos and certain pyrethroids are the registered pesticides most heavily applied in cities. Illegal street pesticides are also in use, including tres pasitos (a carbamate), tiza china, and methyl parathion. In New Yo...

  17. 液相色谱-串联质谱法测定植物源性食品中16种氨基甲酸酯类农药及其代谢物%Determination of 16 carbamate pesticides and metabolite residues in plant-derived foodstuffs by high pressure liquid chromatography-tandem mass spectrometry

    王敬; 陈瑞春; 郭春海; 窦彩云

    2013-01-01

    目的:建立液相色谱-串联质谱法测定植物源性食品中16种氨基甲酸酯类农药及其代谢物(涕灭威、涕灭威亚砜、涕灭威砜、灭害威、恶虫威、甲萘威、克百威、乙霉威、仲丁威、茚虫威、异丙威、灭多威、速灭威、杀线威、抗蚜威和残杀威)残留量的方法。方法样品用0.1%冰醋酸-乙腈提取,提取液经过滤、浓缩后用石墨化炭黑/氨基固相萃取柱净化,采用多反应监测(multi-reaction monitoring, MRM)正离子扫描模式进行准确的定性和定量分析。结果16种氨基甲酸酯类农药在5~500 ng/mL浓度范围内均呈良好线性。16种农药在苹果、菠菜、山药、大米、大豆和生姜6种基质中的检出限和定量下限为2.0µg/kg和5.0µg/kg,在低、中、高3个水平的加标回收率为71.0%~108.0%之间, RSDs (relative standard deviations)为2.03%~11.30%。结论该方法简单快速,其灵敏度、准确度和精密度均能满足农药残留分析的要求。%Objective To establish a high pressure liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method for determination 16 kinds of carbamate pesticides and their metabolites (aldicarb, al-dicarb-sulfoxide, aldicarb-sulfone, aminocarb, bendicarb, carbaryl, carbofuran, diethofencarb, fenobucarb, in-doxacarb, isoprocarb, methomyl, metolcarb, oxamyl, pirimicarb and propoxur) in plant-derived foodstuffs. Methods Samples were extracted with 0.1%formic acid-acetonitrile solution. After concentrated, the solution was cleaned up with solid-phase extraction (SPE) column of envi-Carb/NH2, the mode of multi-reaction moni-toring positive ion scanning was adopted for both the quantitative and qualitative analyses. Results Calibra-tion curves showed a good linearity over the range of 5~500 ng/mL. The limits of detection (LOD) were 2.0 µg/kg and the limits of quantification (LOQ) were 5.0 µg/kg for all the 16 pesticides spiked in apple, spinach, Chinese yam, rice, soybean and ginger

  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

    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

  19. 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

    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−1 for 77% of the pesticides investigated. • Successful identification at 0.01 mg kg−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 (MSE). 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−1. For screening, the detection was based on one diagnostic ion (in most cases the protonated molecule). Overall, at the 0.01 mg kg−1 level, 89% of the 2620 fortifications made were detected. The screening detection limit for individual pesticides was 0.01 mg kg−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−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−1 level, respectively. Insufficient sensitivity for the second ion was the main reason for the inability to

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

    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

  1. 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.

  2. Types of pesticides and determination of their residues

    The pesticide is any material or component used to protect from pests. Its toxic effect is related to the chemical structure, which can be divided into 3 types : 1- Metal pesticides : Sulphur, cupper, zinc, mercury; 2- Vegetal pesticides : advanced and less toxic to the general health; 3- Synthetic organo pesticides : organo chlorine, organophosphorous, carbamate and pyrethroids. Pesticides in the soil undergo biological dissociation according to their concentration and chemical structure. High concentration of the pesticides in the soil may lead to fertility decrease due to destruction of micro-organisms by the pesticides. Many methods are used to analyze the residues of pesticides in plant or soil : 1- Chromatographic methods : Gas chromatography, gas liquid chromatography and high performance liquid chromatography; 2- Spectroscopy methods : spectrophotometer and mass spectrometer; 3- Isotopic methods : based on tracers technique which is the most sensitive and accurate method and can estimate minor amounts of the pesticides. (author)

  3. Carbamic acid and carbamate formation in NH{3}:CO{2} ices - UV irradiation versus thermal processes

    Bossa, J. B.; Theulé, P.; Duvernay, F.; Borget, F.; Chiavassa, T.

    2008-12-01

    Context: We study carbamic acid [ NH{2}COOH] and ammonium carbamate [ NH{2}COO-] [ NH{4}+] formation in interstellar ice analogs. Aims: We demonstrate how carbamic acid [ NH{2}COOH] and ammonium carbamate [ NH{2}COO-] [ NH{4}+] can be formed from both thermal reactions and energetic photons in an NH{3}:CO{2} ice mixture. Methods: Infrared and mass spectroscopy are used to monitor NH{3}:CO{2} ice mixture evolution during both warming and VUV photon irradiation. Results: Carbamic acid and ammonium carbamate can be produced thermally in a 1:1 ratio from NH{3} and CO{2} above 80 K. They can be also formed in a 28:1 ratio by less efficient processes such as energetic photons. Our study and its results provide fresh insight into carbamic acid formation in interstellar ices. Conclusions: We demonstrate that care is required to separate irradiation-induced reactivity from purely thermal reactivity in ices in which ammonia and carbon dioxide are both present. From an interstellar chemistry point of view, carbamic acid and ammonium carbamate are readily produced from the ice mantle of a typical interstellar grain and should therefore be a detectable species in molecular clouds.

  4. 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. PMID:26041247

  5. 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...

  6. Pesticide residue determination in vegetables from western China applying gas chromatography with mass spectrometry.

    Qin, Guofu; Zou, Keting; Li, Yongbo; Chen, Yan; He, Fengrui; Ding, Guirong

    2016-09-01

    In this study,an effort has been made to evaluate the pesticide residues in vegetables from western China. Fifty-one pesticides, including organophosphorus, organochlorine, carbamate and pyrethroid, were detected in 369 commonly used vegetables by GC-MS. Concentrations of organophosphorus pesticides were detected ranging from 0.0008 to 18.8200 mg/kg, among which organophosphorus pesticide concentrations exceeded their maximum residue levels (MRLs) in five samples. Carbamate and organochlorine pesticides were determined to have concentrations in the range of 0.0012-0.7928 mg/kg. The residual concentrations of carbamate pesticides in six samples and organochlorine pesticides in four samples exceeded their MRLs. The residual concentrations of five pyrethroid pesticides were within the range of 0.0016-6.0827 mg/kg and the pyrethroid residues in two samples exceeded their MRLs. The results revealed that pesticide residues in 70.73% of the vegetables samples were not detected, while in the rest of vegetables there were one or more pesticide residues and some even exceeded their MRLs, which would threaten the health of consumers. Our work provides significant information for the food safety regulations to control the excessive use of some pesticides on those kinds of vegetables from western China. Copyright © 2016 John Wiley & Sons, Ltd. PMID:26864471

  7. Development, validation, and uncertainty measurement of multi-residue analysis of organochlorine and organophosphorus pesticides using pressurized liquid extraction and dispersive-SPE techniques.

    Sanyal, Doyeli; Rani, Anita; Alam, Samsul; Gujral, Seema; Gupta, Ruchi

    2011-11-01

    Simple and efficient multi-residue analytical methods were developed and validated for the determination of 13 organochlorine and 17 organophosphorous pesticides from soil, spinach and eggplant. Techniques namely accelerated solvent extraction and dispersive SPE were used for sample preparations. The recovery studies were carried out by spiking the samples at three concentration levels (1 limit of quantification (LOQ), 5 LOQ, and 10 LOQ). The methods were subjected to a thorough validation procedure. The mean recovery for soil, spinach and eggplant were in the range of 70-120% with median CV (%) below 10%. The total uncertainty was evaluated taking four main independent sources viz., weighing, purity of the standard, GC calibration curve and repeatability under consideration. The expanded uncertainty was well below 10% for most of the pesticides and the rest fell in the range of 10-20%. PMID:21210211

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

    Alicia Viviana Veglia

    2000-01-01

    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.

  9. 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.

  10. 40 CFR 721.2025 - Substituted phenylimino carbamate derivative.

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted phenylimino carbamate... Specific Chemical Substances § 721.2025 Substituted phenylimino carbamate derivative. (a) Chemical... as a substituted phenylimino carbamate derivative (PMN P-91-487) is subject to reporting under...

  11. 21 CFR 520.434 - Chlorphenesin carbamate tablets.

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Chlorphenesin carbamate tablets. 520.434 Section... Chlorphenesin carbamate tablets. (a) Specifications. Each tablet contains 400 milligrams of chlorphenesin carbamate. (b) Sponsor. See No. 000009 in § 510.600(c) of this chapter. (c) Conditions of use in...

  12. Antimicrobial Pesticides

    ... US EPA US Environmental Protection Agency Search Search Pesticides Share Facebook Twitter Google+ Pinterest Contact Us You are here: EPA Home » Pesticides » Antimicrobial Pesticides Antimicrobial Pesticides News and Highlights Disinfection Hierarchy Workshop - October 7 ...

  13. Phthalates, Pesticides, and Bisphenol-A Exposure and the Development of Nonoccupational Asthma and Allergies: How Valid Are the Links?

    Kwak, Eun Soo; Just, Allan; Whyatt, Robin; Miller, Rachel L.

    2009-01-01

    Phthalates, pesticides, and bisphenol-A (BPA) are three groups of chemicals, implicated in endocrine disruption and commonly found in the local environment, that have been implicated in the pathogenesis of asthma and allergies [1-3]. Multiple observational studies have demonstrated an association between exposure to phthalates and the development of asthma and allergies in humans. Associations with exposure to pesticides and BPA and the development of respiratory disease are less clear. Howev...

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

    Kesavachandran C; Pathak M; Fareed M; Bihari V; Mathur N; Srivastava A

    2009-01-01

    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 inves...

  15. Effect of in vitro estrogenic pesticides on human oestrogen receptor α and β mRNA levels

    Theander Grünfeld, Heidi; Bonefeld-Jørgensen, Eva Cecilie

    2004-01-01

    , endosulfan, dieldrin, and tolchlofos-methyl, whereas no significant effect of the carbamate pesticides on the ERβ mRNA level was observed. This study demonstrated that organochlor and organophosphorous pesticides possess the ability to interfere with the ERα and ERβ mRNA steady state levels....

  16. High-performance liquid chromatography multiresidue method for the determination of N-methyl carbamates in fruit and vegetable juices.

    Sánchez-Brunete, Consuelo; Albero, Beatriz; Tadeo, José Luis

    2004-11-01

    A rapid multiresidue method has been developed for the analysis of N-methylcarbamate insecticides (oxamyl, methomyl, propoxur, carbofuran, carbaryl, and methiocarb) in fruit and vegetable juices. The method is based on the adsorption of the N-methyl carbamates in Florisil and the subsequent extraction of pesticides using a low volume of acetone. Residue levels in juice were determined by reversed-phase high-performance liquid chromatography with fluorescence detection after postcolumn derivatization. The separation of carbamates is performed on a C8 column with water-methanol as mobile phase. Recovery studies were performed at 500-, 100-, and 10-ng/ml fortification levels, and average recoveries obtained for carbamates ranged from 79 to 109%, with relative standard deviations between 1.4 and 9.9%. The method was found to be linear over the range assayed from 10 to 1,000 ng/ml, and the detection limits for carbamates varied from 0.8 to 1.9 ng/ml. PMID:15553643

  17. Validation of a multi-residue method for the determination of residuals pesticides in cabbage (Brassica Oleracea var. Capitata) for gases chromatography

    This study describes the validation of a multi-residue method for the determination of most used organo chlorine, organophosphorus and organonitrogen pesticides in cabbage in the Cundinamarca Department (Colombia). The extraction process includes blending of small sample quantity with ethyl acetate in presence of Na2SO4 and NaHCO3, filtration and concentration. The clean up steps include GPC and mini-column chromatography using silica gel. Final determination was carried out by gas chromatography with: pulsed splitless injection, HP-5 capillary column, and a parallel detection system with micro electron capture detection (μ - ECD) and Nitrogen-Phosphorus Detection (NPD). The methodology is specific, selective, accurate and robust. Recovery values of majority of pesticides were in the range 70-120% at spiking levels ranging 0.05-10.73 mg/kg. Limits of detection were less than 0.10 mg/kg for most of the studied compounds. The distribution of the analyses in the laboratory sample was evaluated and it was found its homogeneity. The evaluation of pesticide residues was made in a specific area of municipality of Madrid-Cundinamarca, (Colombia). No residues of the studied analyses were founded

  18. Determination of seventeen polar/thermolabile pesticides in apples and apricots by liquid chromatography/mass spectrometry.

    Zrostlíková, Jitka; Hajslová, Jana; Kovalczuk, Tomás; Stĕpán, Radim; Poustka, Jan

    2003-01-01

    A simple liquid chromatography/mass spectrometry (LC/MS) approach for the determination of widely used representatives of polar/thermolabile pesticides in fruits was developed and validated. The group of pesticides comprised benzimidazoles and azoles (carbendazim, thiabendazole, imazalil, propiconazole, prochloraz, epoxiconazole, flusilazole, tebuconazole, bitertanol); N-methylcarbamates (carbaryl, carbofuran, methiocarb); and phenylureas and benzoylphenylureas (linuron, diflubenzuron, triflumuron, teflubenzuron, flufenoxuron). Matrixes (apple, apricot) were extracted with acetonitrile and crude extracts were cleaned up by solid-phase extraction (SPE) using either mixed cation exchange or hydrophilic lipophilic balance cartridges. LC separation of pesticides was performed on a reversed-phase column, Discovery C18. Electrospray ionization and ion trap MS/MS detection were applied. For most pesticides, overall recoveries ranged from 75 to 122%, and repeatability (as relative standard deviation) from 5 repetitive determinations of recovery ranged from 3 to 21%. Carbofuran was the only compound for which recovery was not satisfactory due to its loss in the SPE cleanup step. Limits of detection were 0.1-3 microg/kg for benzimidazole and azole fungicides and carbamate insecticides. For urea insecticides, detection limits were slightly higher (3-10 microg/kg). PMID:12852583

  19. 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

  20. 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

    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......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...

  1. Amino Acid Carbamates As Prodrugs Of Resveratrol

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

    2015-01-01

    Resveratrol (3, 5, 4′-trihydroxy-trans-stilbene), a plant polyphenol, has important drug-like properties, but its pharmacological exploitation in vivo is hindered by its rapid transformation via phase II conjugative metabolism. One approach to bypass this problem relies on prodrugs. We report here the synthesis, characterization, stability and in vivo pharmacokinetic behaviour of prodrugs of resveratrol in which the OH groups are engaged in an N-monosubstituted carbamate ester (-OC(O)NHR) lin...

  2. Amino Acid Carbamates As Prodrugs Of Resveratrol.

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

    2015-01-01

    Resveratrol (3, 5, 4'-trihydroxy-trans-stilbene), a plant polyphenol, has important drug-like properties, but its pharmacological exploitation in vivo is hindered by its rapid transformation via phase II conjugative metabolism. One approach to bypass this problem relies on prodrugs. We report here the synthesis, characterization, stability and in vivo pharmacokinetic behaviour of prodrugs of resveratrol in which the OH groups are engaged in an N-monosubstituted carbamate ester (-OC(O)NHR) linkage with a natural amino acid (Leu, Ile, Phe, Thr) to prevent conjugation and modulate the physicochemical properties of the molecule. We also report a convenient, high-yield protocol to obtain derivatives of this type. The new carbamate ester derivatives are stable at pH 1, while they undergo slow hydrolysis at physiological pH and hydrolyse with kinetics suitable for use in prodrugs in whole blood. After administration to rats by oral gavage the isoleucine-containing prodrug was significantly absorbed, and was present in the bloodstream as non-metabolized unaltered or partially deprotected species, demonstrating effective shielding from first-pass metabolism. We conclude that prodrugs based on the N-monosubstituted carbamate ester bond have the appropriate stability profile for the systemic delivery of phenolic compounds. PMID:26463125

  3. 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. PMID:25882424

  4. Vinyl carbamate epoxide, a major strong electrophilic, mutagenic and carcinogenic metabolite of vinyl carbamate and ethyl carbamate (urethane).

    Park, K K; Liem, A; Stewart, B C; Miller, J A

    1993-03-01

    Vinyl carbamate epoxide (VCO) was found to possess strong electrophilic, mutagenic and carcinogenic activities. It reacted with water at 37 degrees C and pH 7.4 (phosphate buffer) to form glycolaldehyde and several related reducing compounds; none of these products were mutagenic for Salmonella typhimurium TA1535. Under these conditions VCO had a half-life (determined chemically and mutagenically) of approximately 10.5 min. This half-life was progressively lowered by increasing concentrations of chloride ion (liver, serum and isotonic levels). This ion reacted with VCO to form chloroacetaldehyde. VCO also reacted with other nucleophiles such as glutathione, DNA and its constituent guanine and adenine bases. The purine adducts formed by VCO in DNA in vitro and in vivo were released by weak acid treatment and consisted of 7-(2'-oxoethyl)guanine and N2,3-ethenoguanine as major products with 1,N6-ethenoadenine as a minor product. VCO was a strong direct mutagen in Salmonella typhimurium TA1535 and TA100 but was only weakly active in the TA98 mutant. VCO was a stronger initiator of carcinogenesis in the skin of CD-1 mice and in the liver of infant male B6C3F1 mice than its metabolic precursors vinyl carbamate (VC) and ethyl carbamate (EC). Unlike VC and EC, VCO was a strong complete carcinogen in the skin of CD-1 mice and induced papillomas and carcinomas following repetitive administration of sub-ulcerogenic doses. VCO also exhibited some carcinogenic activity in the lungs of mice and in the s.c. and mammary tissue of female Sprague-Dawley rats. These data and those from other recent studies support the conclusion that VCO is a major strong electrophilic, mutagenic and carcinogenic metabolite of EC and VC in the mouse. PMID:8453720

  5. Chemoselective Synthesis of Carbamates using CO2 as Carbon Source.

    Riemer, Daniel; Hirapara, Pradipbhai; Das, Shoubhik

    2016-08-01

    Synthesis of carbamates directly from amines using CO2 as the carbon source is a straightforward and sustainable approach. Herein, we describe a highly effective and chemoselective methodology for the synthesis of carbamates at room temperature and atmospheric pressure. This methodology can also be applied to protect the amino group in amino acids and peptides, and also to synthesize important pharmaceuticals. PMID:27376902

  6. 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,...

  7. 76 FR 34200 - Land Disposal Restrictions: Revision of the Treatment Standards for Carbamate Wastes

    2011-06-13

    ... Standards for Carbamate Wastes AGENCY: Environmental Protection Agency. ACTION: Proposed rule. SUMMARY: The...) treatment standards for hazardous wastes from the production of carbamates and carbamate commercial chemical... carbamate wastes must be treated to meet numeric concentration limits before they can be land...

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

    Md. Shakhaoat Hossain; Md. Alamgir Hossain; Md. Abdur Rahman; Md Mainul Islam; Md Atiqur Rahman; Tanveer Mehedi Adyel

    2013-01-01

    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 comm...

  9. QuEChERS GC-MS validation and monitoring of pesticide residues in different foods in the tomato classification group.

    Ramírez Restrepo, Andrés; Gallo Ortiz, Andrés Fernando; Hoyos Ossa, Duvan Esteban; Peñuela Mesa, Gustavo Antonio

    2014-09-01

    The objective of this study was to validate (SANCO/12495/2011 and NTC-ISO/IEC 17025) multi-residue multi-class methods using QuEChERS sample preparation and GC-MS for the analysis of regulated pesticides in tomatoes (Solanum lycopersicum), tamarillos (Solanum betaceum) and goldenberries (Physalis peruviana). These Latin American products are representative and widely produced in Antioquia (Colombia). Sample preparation followed the UNE-EN 15662 method (150 mg MgSO4, 25mg primary secondary amines and 25mg of octadecylsiloxane for cleanup; graphitized carbon black was added for tomatoes). Extracts were injected using a programmed temperature-vaporizing injector. The residues were validated over a range from 0.02 mg/kg to 0.20 mg/kg, with 24 analytes validated in tomatoes, 33 in tamarillos and 28 in goldenberries. An initial risk assessment was enabled by monitoring 24 samples in the municipalities of El Peñol, Marinilla and San Vicente Ferrer. Risks were found for tomatoes, but no significant risks were found for tamarillos or goldenberries. PMID:24731326

  10. 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.

  11. 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

  12. Pesticides residues in water treatment plant sludge: validation of analytical methodology using liquid chromatography coupled to Tandem mass spectrometry (LC-MS/MS)

    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)

  13. Radiotracer Approaches to Carbamate Insecticide Toxicology

    Methylcarbamates constitute one of the major groups of insecticides. Many unresolved problems in their toxicology may be readily approached with radiotracer studies. Dimethylcarbamates have been prepared with carbonyl-C14-labelling and methylcarbamates withmethyl-, carbonyl-and ring-labelling utilizing carbon-14. The pharmacological action of these.compounds presumably results from acetylcholinesterase inhibition and may involve carbamylation. Reaction of carbonyl- or methyl-labelled carbamates with purified cholinesterase or other esterases would allow a critical examination of this carbamylation reaction and the ease of spontaneous and induced reactivation or decarbamylation. The physiological significance of cholinesterase inhibition might be examined by administering acetate-C14 and analysis for radiolabelled acetylcholine accumulation in nervous tissue, or by utilizing acetyl-C14-choline as the substrate for in vitro determination of the degree of cholinesterase inhibition in tissues of poisoned animals with minimal dilution of the inhibitors and enzymes during analysis. Some progress has been made with radiolabelled materials in investigating the metabolism of carbamate insecticides. Sevin (1-naphthyl methylcarbamate) has been most extensively studied along with its potential hydrolysis products. The assumption that the metabolism of Sevin involves an initial hydrolysis and then further decomposition of the fragments was not supported by carbon-14 studies. The major detoxification mechanism in mammals, and probably also in insects, results from initial oxidative attack on the carbamate by the microsomes in the presence of reduced nicotinamide-adenine dinucleotide phosphate. Sevin is rapidly metabolized in mammals, but the fate of certain of the fragments has not been resolved. Some of the metabolites appear in the milk of lactating animals. One step in the metabolism appears to be formation of the N-methylol derivative. Preliminary studies on the metabolism

  14. Mechanism of action of organophosphorus and carbamate insecticides.

    Fukuto, T R

    1990-01-01

    Organophosphorus and carbamate insecticides are toxic to insects and mammals by virtue of their ability to inactivate the enzyme acetylcholinesterase. This review addresses the mechanism of inhibition of acetylcholinesterase by organophosphorus and carbamate esters, focusing on structural requirements necessary for anticholinesterase activity. The inhibition of acetylcholinesterase by these compounds is discussed in terms of reactivity and steric effects. The role of metabolic activation or d...

  15. Comprehensive screening study of pesticide degradation via oxidation and hydrolysis.

    Chamberlain, Evelyn; Shi, Honglan; Wang, Tongwen; Ma, Yinfa; Fulmer, Alice; Adams, Craig

    2012-01-11

    This comprehensive study focused on the reactivity of a set of 62 pesticides via oxidization by free chlorine, monochloramine, chlorine dioxide, hydrogen peroxide, ozone, and permanganate; photodegradation with UV(254); and hydrolysis at pH 2, 7, and 12. Samples were analyzed using direct injection liquid chromatography-mass spectrometry detection or gas chromatography-electron capture detection after liquid-liquid extraction. Many pesticides were reactive via hydrolysis and/or chlorination and ozonation mechanisms under typical drinking water treatment conditions, with less reactivity exhibited on average for chlorine dioxide, monochloramine, hydrogen peroxide, and UV(254). The pyrazole and organophosphorous pesticides were most reactive in general, whereas carbamates and others were less reactive. The screening study provides guidance for the pesticide/oxidation systems that are most likely to lead to degradates in water treatment and the environment. PMID:22141915

  16. Physicochemical studies of the carbamate-CO2-solvent system

    The formation of carbamate from CO2 and the various amine solutions has been investigated for the purpose of elucidating the structure of the species generated in the reaction. The amine solutions used were 1 and 2 molar solutions of di-n-butylamine (DNBA) in triethylamine (TEA), pure DNBA and pure TEA. It has been found that the nonaqueous solvent participates in the formation of carbamate in 1 and 2M-DNBA/TEA solutions as a proton acceptor in DNBA-carbamate formation. However, due to the high concentration of the solutions and the basicities of the amines, a significant amount of DNBA which does not form the DNBA-carbamate anion is also found to be participating as a proton acceptor. Pure TEA absorbs only 1/60 of the absorption by pure DNBA. The extent of TEA participation in the CO2-absorption process other than as a proton acceptor in DNBA-carbamate is negligible. The formation of carbamic acid and zwitterion have been found unlikely. 7 tables, 15 figs

  17. Development and validation of a multiresidue method for the determination of neonicotinoid and macrocyclic lactone pesticide residues in milk, fruits, and vegetables by ultra-performance liquid chromatography/MS/MS.

    Kamel, Alaa; Qian, Yaorong; Kolbe, Elizabeth; Stafford, Charles

    2010-01-01

    A multiresidue method was developed and validated for the determination of 13 neonicotinoid pesticides and metabolites, and nine macrocyclic lactone pesticides and veterinary drugs using SPE and ultra-performance liquid chromatography/MS/MS. The method was validated in milk, orange, spinach, apple, plum, watermelon, green bean, zucchini, broccoli, strawberry, grape, and tomato by analyzing replicates of residue-free control samples fortified with a mixture of 22 target analytes at three concentration levels. The recoveries of the analytes from the fortified matrixes were mostly within 70-120%, except for some of the neonicotinoid metabolites. The LOD values varied by analyte and matrix and ranged between 0.001-2 ng/g. The developed method was successful in combining two widely different classes of compounds into a single analysis. PMID:20480883

  18. Organic Pesticide Ingredients

    ... Control a pest Integrated Pest Management What are pesticides? Herbicides Disinfectants Fungicides Insecticides Natural and Biological Pesticides ... Other types of pesticides Disponible en español Organic Pesticide Ingredients Organic foods are not necessarily pesticide-free. ...

  19. Pesticides and Human Health

    ... Control a pest Integrated Pest Management What are pesticides? Herbicides Disinfectants Fungicides Insecticides Natural and Biological Pesticides ... Rodenticides Other types of pesticides Disponible en español Pesticides and Human Health Pesticides have a specific purpose ...

  20. 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.

  1. Pesticide Movement

    Pesticides generally include herbicides, insecticides and fungicides that play an important role in maintaining worldwide food and fiber production by controlling weeds that compete for water and nutrients or by eliminating pests that reduce yields. In the future, the role of pesticides and fertili...

  2. 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. PMID:27396650

  3. Characterization of human cytochrome P450 induction by pesticides.

    Abass, Khaled; Lämsä, Virpi; Reponen, Petri; Küblbeck, Jenni; Honkakoski, Paavo; Mattila, Sampo; Pelkonen, Olavi; Hakkola, Jukka

    2012-03-29

    Pesticides are a large group of structurally diverse toxic chemicals. The toxicity may be modified by cytochrome P450 (CYP) enzyme activity. In the current study, we have investigated effects and mechanisms of 24 structurally varying pesticides on human CYP expression. Many pesticides were found to efficiently activate human pregnane X receptor (PXR) and/or constitutive androstane receptor (CAR). Out of the 24 compounds tested, 14 increased PXR- and 15 CAR-mediated luciferase activities at least 2-fold. While PXR was predominantly activated by pyrethroids, CAR was, in addition to pyrethroids, well activated by organophosphates and several carbamates. Induction of CYP mRNAs and catalytic activities was studied in the metabolically competent, human derived HepaRG cell line. CYP3A4 mRNA was induced most powerfully by pyrethroids; 50 μM cypermethrin increased CYP3A4 mRNA 35-fold. CYP2B6 was induced fairly equally by organophosphate, carbamate and pyrethroid compounds. Induction of CYP3A4 and CYP2B6 by these compound classes paralleled their effects on PXR and CAR. The urea herbicide diuron and the triazine herbicide atrazine induced CYP2B6 mRNA more than 10-fold, but did not activate CAR indicating that some pesticides may induce CYP2B6 via CAR-independent mechanisms. CYP catalyzed activities were induced much less than the corresponding mRNAs. At least in some cases, this is probably due to significant inhibition of CYP enzymes by the studied pesticides. Compared with human CAR activation and CYP2B6 expression, pesticides had much less effect on mouse CAR and CYP2B10 mRNA. Altogether, pesticides were found to be powerful human CYP inducers acting through both PXR and CAR. PMID:22310298

  4. [Formation of ethyl carbamate in umeshu (plum liqueur)].

    Suzuki, K; Kamimura, H; Ibe, A; Tabata, S; Yasuda, K; Nishijima, M

    2001-12-01

    Samples of umeshu, a Japanese plum liqueur made from unripe plums, shochu and crystal sugar, were stored under fluorescent light, in the dark and in the refrigerator. The amount of ethyl carbamate formed in umeshu exposed to light or room temperature was larger than that in the dark or at low temperature. The amount of ethyl carbamate formed in umeshu to which cyanide had been added was larger than that in the absence of added cyanide. Thus, the amount of ethyl carbamate formed in the umeshu was increased by not only light and higher temperature, but also cyanide. Samples of model alcoholic beverages were stored under various conditions using red, yellow and blue cellophanes. The amount of ethyl carbamate formed in the model alcoholic beverage with blue cellophane was larger than in the cases of red and yellow cellophanes. It was found that the amount of ethyl carbamate formed in the model alcoholic beverage was increased by light in the wavelength range of 375-475 nm. PMID:11875819

  5. 76 FR 34147 - Land Disposal Restrictions: Revision of the Treatment Standards for Carbamate Wastes

    2011-06-13

    ... carbamates (61 FR 15583). These treatment standards were based on data for similar wastes for which EPA... CFR 268.48. EPA promulgated numeric treatment standards for these carbamate wastes in 1994 (59 FR... UHC carbamates. As a result, EPA promulgated an emergency rule in 1996 (61 FR 43924, August 26,...

  6. 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...

  7. NMDA antagonists exert distinct effects in experimental organophosphate or carbamate poisoning in mice

    Organophosphate (OP) and carbamate acetylcholinesterase (AChE) inhibitors produce seizures and lethality in mammals. Anticonvulsant and neuroprotective properties of N-methyl-D-aspartate (NMDA) antagonists encourage the investigation of their effects in AChE inhibitor-induced poisonings. In the present study, the effects of dizocilpine (MK-801, 1 mg/kg) or 3-((RS)-2-carboxypiperazin-4-yl)-propyl-1-phosphonic acid (CPP, 10 mg/kg), alone or combined with muscarinic antagonist atropine (1.8 mg/kg), on convulsant and lethal properties of an OP pesticide dichlorvos or a carbamate drug physostigmine, were studied in mice. Both dichlorvos and physostigmine induced dose-dependent seizure activity and lethality. Atropine did not prevent the occurrence of convulsions but decreased the lethal effects of both dichlorvos and physostigmine. MK-801 or CPP blocked or attenuated, respectively, dichlorvos-induced convulsions. Contrariwise, NMDA antagonists had no effect in physostigmine-induced seizures or lethality produced by dichlorvos or physostigmine. Concurrent pretreatment with atropine and either MK-801 or CPP blocked or alleviated seizures produced by dichlorvos, but not by physostigmine. Both MK-801 and CPP co-administered with atropine enhanced its antilethal effects in both dichlorvos and physostigmine poisoning. In both saline- and AChE inhibitor-treated mice, no interaction of the investigated antidotes with brain cholinesterase was found. The data indicate that both muscarinic ACh and NMDA receptor-mediated mechanisms contribute to the acute toxicity of AChE inhibitors, and NMDA receptors seem critical to OP-induced seizures

  8. Occurrence of pesticides from coffee crops in surface water

    Márcio Ribeiro Vianna Neto

    2013-04-01

    Full Text Available The excessive amount of pesticides applied in agricultural areas may reach surface water, thereby contaminating it. Thus, the main purpose of this study was to investigate the presence of pesticides used in a sub-basin headwater with coffee crops, situated in the Dom Corrêa district, Manhuaçu, Minas Gerais. The region of study is a great producer of coffee. Crops occupy steep areas and are situated close to surface water bodies. In this study, four sample collection points were selected in streams as well as a point in the distribution network and two points in the water treatment station (raw and treated water a total of seven points. The samples were collected in rainy and dry seasons. Organochlorines, organophosphates, pyrethroids, carbamates and triazoles pesticides were identified by liquid and gas chromatography analysis with tandem mass spectrometry. The occurrence of pesticides was more evident in the rainy season. A total of 24 distinct pesticides were detected. At least one pesticide was identified in 67% of the samples collected during the rainy season and in 21% of the samples collected during drought. Many pesticides detected in water are not regulated in Brazilian legislation regarding potability.

  9. Pesticides and cancer: insights into toxicoproteomic-based findings.

    George, Jasmine; Shukla, Yogeshwer

    2011-11-18

    Humans are often exposed to a variety of pollutants that contribute to an individual's risk for diseases including cancer. Animal, cell cultures and epidemiological lines of evidence demonstrate that exposure to various environmental pollutants including pesticides are associated with increasing frequency of cancers. Organophosphates, organochlorines, carbamates, pyrethroids, the major groups of pesticides, have been reported to be carcinogenic in various models. However, the results of these studies are still controversial, nevertheless, their mechanism of action is clear. Therefore, new strategies in toxicological research are needed for efficient screening for adverse effects of pesticides on complex living systems. Biomarkers can be employed to identify causal associations and to make better quantitative and qualitative estimates of those associations at relevant levels of exposure. This will enable us to deepen our understanding of mechanism behind their carcinogenic potential. Deciphering the associations between pesticide exposure and cancer, following toxicoproteomics application, will be useful in the development of potential predictive biomarkers of pesticide induced carcinogenicity. Therefore, the thrust of this article was to review the risk of cancer due to pesticide exposure and significant toxicoproteomic-based studies conducted so far, to identify the novel molecules as possible biomarkers for cancer following pesticide exposure. PMID:21989265

  10. Monitoring of pesticide residues in vegetarian diet.

    Kumari, Beena; Kathpal, T S

    2009-04-01

    Samples (28) of complete vegetarian diet consumed from morning till night i.e. tea, milk, breakfast, lunch, snacks, dinner, sweet dish etc. were collected from homes, hostels and hotels periodically from Hisar and analysed for detecting the residues of organochlorine, synthetic pyrethriod, organophosphate and carbamate insecticides. The estimation was carried out by using multi-residue analytical technique employing gas chromatograph (GC)-electron capture detector and GC-nitrogen phosphorous detector systems equipped with capillary columns. The whole diet sample was macerated in a mixer grinder and a representative sample in duplicate was analyzed for residues keeping the average daily diet of an adult to be 1,300 g. On comparing the data, it was found that actual daily intake (microgram/person/day) of lindane in two and endosulfan in four samples exceeded the acceptable daily intake. Residues of other pesticides in all the diet samples were lower than the acceptable daily intake (ADI) of the respective pesticides. The study concluded that although all the diet samples were found contaminated with one or the other pesticide, the actual daily intake of only a few pesticides was higher than their respective ADI. More extensive study covering other localities of Haryana has been suggested to know the overall scenario of contamination of vegetarian diet. PMID:18386151

  11. Growth and characterization of organic single crystal benzyl carbamate

    Bala Solanki, S. Siva; Perumal, Rajesh Narayana; Suthan, T.; Bhagavannarayana, G.

    2015-10-01

    Benzyl carbamate single crystal is grown by a solution and vertical Bridgman technique for the first time. The cell parameters and morphologies are assessed from single crystal X-ray diffraction analysis. High resolution X-ray diffraction analysis indicates the crystalline perfection of the grown benzyl carbamate crystal. Fourier Transforms Infrared spectroscopy study has been applied to arrive at the different functional groups. Thermo gravimetric analysis and differential scanning calorimetry are used to study its thermal behavior. The microhardness test is carried out and the load dependent hardness is measured.

  12. Comparative MO investigation of hindered rotation and thermal decomposition of carbamates and thiocarbamates

    Investigation of hindered rotation in carbamates reveals the high flexibility and ionic character of the C-N bond as compared to common amides. This flexibility decreases in the case of thiocarbamates. The mechanism of activation of carbamates has been explored. Computations have proven the possibility of formation of an intramolecular H-bond in carbamates and thiocarbamates. This intramolecular H-bond is formed immediately after protonation of the carbamate. The possibility of formation of zwitterions as intermediates in the decomposition of carbamic and dithiocarbamic acids is discussed. (Auth.)

  13. 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.

  14. Vapor Pressure, Vaporization Enthalpy, Standard Enthalpy of Formation and Standard Entropy of n-Butyl Carbamate

    Zuoxiang Zeng⁎; Zhihong Yang; Weilan Xue⁎; Xiaonan Li

    2014-01-01

    The vapor pressures of n-butyl carbamate were measured in the temperature range from 372.37 K to 479.27 K and fitted with Antoine equation. The compressibility factor of the vapor was calculated with the Virial equation and the second virial coefficient was determined by the Vetere model. Then the standard enthalpy of vaporization for n-butyl carbamate was estimated. The heat capacity was measured for the solid state (299.39–324.2 K) and liquid state (336.65–453.21 K) by means of adiabatic calorimeter. The standard en-thalpy of formationΔfHϴ[crystal (cr),298.15 K] and standard entropy Sϴ(crystal,298.15 K) of the sub-stance were calculated on the basis of the gas-phase standard enthalpy of formationΔfHϴ(g,298.15 K) and gas-phase standard entropy Sϴ(g,298.15 K), which were estimated by the Benson method. The results are acceptable, validated by a thermochemical cycle.

  15. What Is a Pesticide?

    ... Twitter Google+ Pinterest Contact Us Basic Information about Pesticide Ingredients Pesticide products contain both "active" and "inert" ingredients: What is a Pesticide? A pesticide is any substance or mixture of ...

  16. GC/MIP/AED method for pesticide residue determination in fruits and vegetables.

    Ting, K C; Kho, P

    1991-01-01

    This research describes the results of a gas chromatography/microwave induced plasma/atomic emission detection (GC/MIP/AED) method performed on a Hewlett-Packard 5921A system for pesticide residue analysis in fruits and vegetables. A total of 6 experiments were conducted: (1) sensitivity and linearity studies for elements S, P, Cl, and N by analyzing dursban; (2) a study of instrument response to Cl concentration in pesticide molecules; (3) organochlorinated pesticide recoveries; (4) organophosphate pesticide recoveries; (5) carbamate pesticide recoveries; and (6) investigation of metallic pesticides with plictran and vendex as standards. The rank according to sensitivity and linearity was found to be as follows: S-181 greater than P-178 greater than Cl-479 greater than N-174. Instrument response to the concentration of chlorine atoms in the pesticide molecule was linear, with a correlation coefficient of 0.89. Recoveries of organochlorinated pesticides were 91.7-109.3%, with the exception of citrus, whose recovery was affected by coeluting interferences. Organophosphate recoveries were 73.2% or higher, except for the cygon oxygen analog, which degraded in the GC system under all circumstances. Carbamate recoveries were inconsistent quantitatively; however, the information generated from elements N and S were useful for qualitative confirmation of other methods, such as LC postcolumn derivatization analysis. Overall, the GC/MIP/AED method is powerful for qualitative confirmation in pesticide residue analysis. The instrument's capability of acquiring multi-elements (Cl and P) selectively and accurately is an alternative method for organochlorinated and organophosphate pesticide residue analyses. In addition, the GC/MIP/AED system is easy to use, simple to maintain, and its chromatograms can be interpreted by any chromatography analyst without much prior training. PMID:1757425

  17. A Novel Approach for Evaluating Carbamate Mixtures for Dose Additivity

    Two mathematical approaches were used to test the hypothesis ofdose-addition for a binary and a seven-chemical mixture ofN-methyl carbamates, toxicologically similar chemicals that inhibit cholinesterase (ChE). In the more novel approach, mixture data were not included in the ana...

  18. Multi-Analyte Separation Methods for HPLC Determination of the Active Ingredients of Pesticides

    The practical quality control of selected pesticides, such as carbamates, organophosphorous compounds, phthalimides, pyrethroids, with HPLC is described. Detailed descriptions are given of materials and methods used, including sample preparation and HPLC operating conditions. The relationship between pH value of the HPLC eluent and the logPow is discussed, illustrated by chromatograms, graphics and tables. The results are also compared with those elaborated by. E. Dudar and presented above. (author)

  19. 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

  20. Examining pyrethroids, carbamates and neonicotenoids in fish, water and sediments from the Indus River for potential health risks.

    Jabeen, Farhat; Chaudhry, Abdul Shakoor; Manzoor, Sadia; Shaheen, Tayybah

    2015-02-01

    This 3 × 3 factorial study assessed pyrethroids, carbamates and neonicotenoids groups of pesticides in replicated samples of three fish species from low (S1, reference), medium (S2) and heavy (S3) polluted sites receiving agricultural run-offs around the Indus River. Water and sediment samples from the same sites were also analysed for these pesticides by using high-performance liquid chromatography. Out of nine investigated pesticides, only three pesticides (deltamethrin, carbofuran and cypermethrin) were detected in fish and sediment samples. Deltamethrin in Cyprinus carpio ranged from 0.490 to 0.839 μg/g, mostly exceeding 0.5 μg/g as the maximum residual limit suggested by FAO-WHO, whereas it ranged from 0.214 to 0.318 μg/g in the sampled sediments. The carbofuran concentrations were 0.0425-0.066 and 0.613-0.946 μg/g in Labeo rohita and Channa marulius muscles respectively and 0.069-0.081 μg/g in the corresponding sediment samples. These values were either higher or lower than the maximum limit (0.1 μg/g) as suggested by FAO-WHO. Conversely, the cypermethrin concentration ranged from 0.141 to 0.174 in Ch. marulius and 0.183-0.197 μg/g in sediments which were both below the FAO-WHO maximum limit of 2 μg/g. No pesticide residues were detected in water from these sampling sites. Most selected physicochemical variables were within the acceptable range of World Health Organization for the water quality for aquatic life. The detected pesticide contents were mostly higher in fish muscles from heavily polluted sites. This is worrying because these pesticides may pose health risks for the fish and people of the study area. However, a preliminary risk assessment indicated that the calculated daily intake of detected pesticides by people consuming fish from the Indus River was low and did not present an immediate risk to the fish-consuming people. This study may be used as a benchmark to determine the safety of fish meat in order to develop intervention

  1. 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

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

    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 P=.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.

  3. 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.

  4. Optimization and validation of a methodology for the qualitative determination of polar pesticides in a carbonated soft drink and some cookies for EFS-CG/DEM

    Chemical analysis of polar pesticides has been qualitatively interest in forensic scientific research by toxicological qualities to the attainment of crimes against human life, pets and plants; associating people and objects in the scene and the possible ways in which the events occurred. The Unidad de Toxicos y Varios of the Seccion de Quimica Analitica of the Departamento de Ciencias Forenses has analyzed polar pesticides and other families to concentration levels, is compared to the environmental analysis and quality control of food. The compounds are used in Costa Rica in recent years as acute chemical weapon to commit crimes against human and animal life. The toxic and lethal amounts of polar pesticides in mammals orally have been milligram level. The Seccion de Quimica Analitica has developed a qualitative methodology to analyze polar pesticides as minor components. The need for reliable analytical quality results has made it necessary to approach a review of the methodology of routine. The review has been solved by selecting two matrices characteristics in such cases: a solid food commercially known as maria biscuits and a carbonated cola. Analytes have been selected based on: greater toxicity, broad spectrum of analytes polarity, the octanol-water partition constant, the water solubility among others. The extraction of analytes in matrices has been selected by solid-phase extraction. The instrumental technique used is gas chromatography with mass selective detector. A method of acquisition optimized in its injection is used. The analysis of instrumental signals were obtained in scanning mode all ions formed, known as Scan and by monitoring mode of ions selected ions (MIS), analysis of the data is acquired in Scan mode because concentration levels of work. The methodology for the qualitative determination of pesticide meets the criteria established for the chemical identification of analytes carbofuran, phorate, terbufos, methyl parathion, chlorpyrifos and

  5. 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.”

  6. Influence of pesticides on thyroid gland activity in male rats

    The plasma levels of T3, T4 and TSH were determined following daily administrations of 1/10 LD50 of metacide (organophoshosphorus) or methavine (carbamate or metoxuron (herbicide) pesticides in male albino rats for 45 days. At the end of the experiment, significant increase of body weights were observed in rats treated with metacide or metoxuron while methavine led to significant decreased TSH secretion. Metoxuron caused significant decrease in both T3 and T4 levels in plasma and metacide increased T3 and increased T4 levels in plasma of male rats

  7. Synthesis of Novel Cellulose Carbamates Possessing Terminal Amino Groups and Their Bioactivity.

    Ganske, Kristin; Wiegand, Cornelia; Hipler, Uta-Christina; Heinze, Thomas

    2016-03-01

    Cellulose phenyl carbonates are an excellent platform to synthesize a broad variety of soluble and functional cellulose carbamates. In this study, the synthesis of cellulose carbamates with terminal amino groups, namely ω-aminoethylcellulose- and ω-aminoethyl-p-aminobenzyl-cellulose carbamate, is discussed. The products are well soluble and their structures can be clearly described by NMR spectroscopy. The cellulose carbamates exhibit a bactericide and fungicide activity in vitro. The ω-aminoethylcellulose carbamate possesses a strong activity against Candida albicans and Staphylococcus aureus (IC50 of 0.02 mg mL(-1) and 0.05 mg mL(-1)). The antimicrobial activity and cytotoxicity can be improved by p-amino-benzylamine (ABA) as an additional substituent. The mixed cellulose carbamate exhibits a high biocompatibility (LC50 of 3.18 mg mL(-1)) and forms films on cotton and PES, which exhibit a strong activity against S. aureus and Klebsiella pneumoniae. PMID:26612063

  8. New screening approach for risk assessment of pesticides in ambient air

    Yusà, Vicent; Coscollà, Clara; Millet, Maurice

    2014-10-01

    We present a novel screening approach for inhalation risk assessment of currently used pesticides (CUPs) in ambient air, based on the measurements of pesticide levels in the inhalable fraction of the particulate matter (PM10). Total concentrations in ambient air (gas + particle phases) were estimated using a theoretical model of distribution of semi-volatile organic compounds between the gas and the particulate phase based on the octanol-air partition (Koa) of each pesticide. The proposed approach was used in a pilot study conducted in a rural station in Valencia (Spain) from April through to October 2010. Twenty out of 82 analysed pesticides were detected in average concentrations ranging from 1.63 to 117.01 pg m-3. For adults, children and infants the estimated chronic inhalation risk, expressed as Hazard Quotient (HQ) was pesticides. Likewise, the cumulative exposure for detected organophosphorus, pyrethroids and carbamates pesticides, was estimated using as metrics the Hazard Index (HI), which was less than 1 for the three families of pesticides assessed. The cancer risk estimated for the detected pesticides classified as Likely or Possible carcinogens was less than 1.15E-7 for infants. In our opinion, the screening approach proposed could be used in the monitoring and risk assessment of pesticides in ambient air.

  9. 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.

  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. 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: <0.005, <0.05, <0.5, < 0.4, <0.1, <0.001 and <0.004. The determined contents (mg/kg) of Cu, Cr and As were in the ranges from 16.77 to 80.21, from 7.14 to 15.45 and from 3.31 to 4.43, respectively. Our preliminary results raise concerns about potential adverse effects of herbicides and pesticides on human health, which strengthens the case for a more preventative and protective approach to the uncontrolled presence of herbicides and pesticides in Sarajevo's playground soils. PMID

  12. A meta-analysis synthesizing the effects of pesticides on swim speed and activity of aquatic vertebrates.

    Shuman-Goodier, Molly E; Propper, Catherine R

    2016-09-15

    Pesticide contaminants are ubiquitous in aquatic environments and pose a threat to biodiversity. Pesticides also have diverse mechanisms of action that make it difficult to identify impacts on exposed wildlife. Behavioral measures represent an important link between physiological and ecological processes, and are often used to generalize sub-lethal effects of pesticide exposure. In order to bridge the toxicological and behavioral literature, and identify chemical classes that denote the largest threat, we conducted a meta-analysis summarizing the effects of pesticides on swim speed and activity of aquatic vertebrates. We found that exposure to environmentally relevant concentrations of pesticides reduced the swim speed of exposed amphibians and fish by 35%, and reduced overall activity by 72%. There were also differences in the magnitude of this effect across chemical classes, which likely reflect underlying physiological processes. Pyrethroids, carbamates, and organophosphates all produced a large decrease in swim speed, where as phosphonoglycines and triazines showed no overall effect. Pyrethroids, carbamates, organophosphates, organochlorines, and organotins also produced a large decrease in activity, while phosphonoglycines had no overall effect, and triazines had the opposite effect of increasing activity. Our results indicate that even sub-lethal concentrations of pesticides have a strong effect on critical behaviors of aquatic vertebrates, which can affect fitness and alter species interactions. We expect our synthesis can be used to identify chemical classes producing the largest sub-lethal effects for further research and management. PMID:27261557

  13. 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. PMID:25844860

  14. Applying Pesticides Safely

    Latimer, Joyce G.

    2009-01-01

    Proper use of pesticides is essential for your safety and for that of the environment. Pesticides must be used correctly to be effective. This publication reviews the key factors in the proper use of pesticides.

  15. National Pesticide Information Center

    National Pesticide Information Center npic@ace.orst.edu 1.800.858.7378 Index A B C D E F ... Your Pest Control Your Pest Integrated Pest Management Pesticide Ingredients Active Ingredients Other/Inert Ingredients Pesticide Products ...

  16. 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.

  17. Comparison Between the Efficiency of Advanced Oxidation Process and Coagulation for Removal Organophosphorus and Carbamat Pesticides

    A.R Rahmani

    2011-10-01

    Full Text Available Background and Objectives: Water pollution by pesticides has adverse effects on the environment and human health, as well .In recent years, advanced oxidation processes, have been gone through to a very high degree for pesticides removal. Poly-Aluminum chloride (PAC used for water treatment, can be effective on pesticides removal. The aim of this research was to study the use of UV/O3 and PAC in the removal of pesticides from drinking water.Materials and Methods: In this descriptive- analytical survey, specific concentrations of pesticides (1,5,10,15,20 ppm;namely Diazinon, Chlorpyrifos, Carbaril were prepared through addition to deionized water. Dichloromethane was used for samples' extraction, samples extracted with Liquid- Liquid & Solid-phase extraction , finally entered bath reactor at pH (6,7,9 .The samples then exposed to UV/O3at contact time of (0.5,1,1.5 and 2 hours . In the PAC pilot , the effects of various concentrations of pesticides, and PAC - ranging (12/24 and 36 ppm were investigated for the efficacy of pesticides removal. All samples analyzed by GC/MS/MS and HPLC. Results: It was found that in UV/O3 reactor, with the rise of pH, decrease in pesticides concentration, and rise of contact time, the efficiency of removal increased too. In the PAC pilot, increase in PAC concentration and decrease in pesticides concentration , both increased the efficiency. Besides, both of the methods showed high efficiencies in the removal of both pesticides,i-e. halogenated Organophosphorus (Chlorpyrifos , non- halogenated Organophosphorus (Diazinon at the degree of over (%80 ; In case of carbamate pesticides (e.g. Carbaril efficiency was over (>%90. One-Way Anova & Two -Way Anova were used to analyze the obtained data.Conclusion: According these results these two methods are suggested for the removal of pesticides from aqueous solutions.

  18. Mild and Site-Selective Allylation of Enol Carbamates with Allylic Carbonates under Rhodium Catalysis.

    Sharma, Satyasheel; Han, Sang Hoon; Oh, Yongguk; Mishra, Neeraj Kumar; Han, Sangil; Kwak, Jong Hwan; Lee, Seok-Yong; Jung, Young Hoon; Kim, In Su

    2016-03-18

    The rhodium(III)-catalyzed mild and site-selective C-H allylation of enol carbamates with 4-vinyl-1,3-dioxolan-2-one and allylic carbonates affords allylic alcohols and terminal allylated products, respectively. The assistance of the carbamoyl directing group provides a straightforward preparation of biologically and synthetically important allylated enol carbamates. PMID:26906724

  19. Palladium-Catalyzed Ortho-Arylation of Carbamate-Protected Estrogens.

    Bedford, Robin B; Brenner, Peter B; Durrant, Steven J; Gallagher, Timothy; Méndez-Gálvez, Carolina; Montgomery, Michelle

    2016-05-01

    The palladium-catalyzed ortho-arylation of diethyl carbamate-protected estrone and estriol with aryl iodides gives the 2-arylated analogues. Subsequent removal of the carbamate directing group furnishes 2-arylated estrone, estradiol, or estriol depending on the method used. PMID:27057762

  20. 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.

  1. Facile one-pot synthesis of unsymmetrical ureas, carbamates, and thiocarbamates from Cbz-protected amines.

    Kim, Hee-Kwon; Lee, Anna

    2016-07-26

    A novel one-pot synthesis of unsymmetrical ureas, carbamates and thiocarbamates from Cbz-protected amines has been developed. In the presence of 2-chloropyridine and trifluoromethanesulfonyl anhydride, isocyanates are generated in situ, which facilitate rapid reaction with amines, alcohols, and thiols to afford the corresponding ureas, carbamates and thiocarbamates in high yields. PMID:27406041

  2. 40 CFR 180.212 - S-Ethyl cyclohexylethylthio-carbamate; tolerances for residues.

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false S-Ethyl cyclohexylethylthio-carbamate; tolerances for residues. 180.212 Section 180.212 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Tolerances § 180.212 S-Ethyl cyclohexylethylthio-carbamate; tolerances for residues. (a) General....

  3. 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. PMID:27212069

  4. 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.

  5. 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.

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

    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 (Km = 77.2 mM; Vmax = 38.2 mU/mg protein) and 1-naphthyl acetate (Km = 222 mM, Vmax = 1095 mU/mg protein) substrates, respectively. Acetylcholinesterase activity was concentration-dependently inhibited by chlorpyrifos-oxon, dichlorvos, carbaryl and carbofuran (IC50 = 1.35 x 10-5-3.80 x 10-8 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 10-5-2.98 x 10-8 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

  7. 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.

  8. Inhibition Mechanism of Cholinesterases by Carbamate: A Theoretical Study

    YAO Yuan; LI Ze-sheng

    2008-01-01

    The density functional theory at the B3LYP/6-311G(d,p) level was applied to exploring the inhibition mechanism of cholinesterases by carbamate.The results indicate that the inhibition reactions with or without the catalytic effect of the catalytic triad in cholinesterases underwent a two-step addition-elimination mechanism,which is in good agreement with the proposed mechanism.The solvent has a strong effect on the inhibition reactions and the reaction with the catalytic triad in the solvent phase is close to the real reaction under biological condition.

  9. The Preparation and Application of Methyl Carbamate through Alcoholysis of Urea%氨基甲酸甲酯的尿素醇解法制备及其应用研究进展

    侯国宁

    2012-01-01

    As a kind of important fine chemicals, methyl carbamate was widely applied in many areas of chemical in- dustry, which was the research focus of urea downstream at present. The research progress of methyl carbamate through al- coholysis of urea such as normal temperature and pressure catalytic synthesis, medium temperature and medium pressure catalytic synthesis and high pressure synthesis without catalyst were generalized. At the same time, its applications on or- ganic synthesis, medicine, and pesticides were reviewed to have a thorough understanding on methyl carbamate industry.%氨基甲酸甲酯作为一种重要的精细化学品,在众多领域中有着广泛的应用,当前已成为尿素下游领域竞相开发的重点。概述了常温常压催化合成、中温中压催化合成及无催化剂高压合成尿素醇解法生产氨基甲酸甲酯工艺研究进展,同时展望其在有机合成、医药、农药等领域的应用,以期对氨基甲酸甲酯行业的发展有较为深入的了解。

  10. Solid-Phase Extraction of Pesticides by Using Bioinspired Peptide Receptors

    Valentina Lanzone

    2015-01-01

    Full Text Available A virtual development of hexapeptide receptors bioinspired by the acetylcholinesterase enzyme active site is proposed. A semicombinatorial approach was applied to generate a virtual hexapeptides library with different affinity properties towards organophosphate and carbamate pesticides. The virtual screening process was addressed to obtain peptides able to separate pesticide subclasses in the experimental work. Three hexapeptides, two generated by molecular modeling and one having a scrambled sequence, were used as selective sorbent materials for pesticides in preanalytical solid-phase extraction (SPE method. Selective adsorption and cross-reactivity were tested directly on a mix of four pesticides (carbaryl, chlorpyrifos-ethyl, malathion, and thiabendazole having different structures and physico-chemical properties, at a total concentration of 120 ppb (each pesticide at concentration of 30 ppb. The results were compared to traditional sorbent material such as C-18 and strata-X. Data showed that only one of the hexapeptides virtually designed had significant differences in competitive absorption between aliphatic pesticide malathion, fungicide thiabendazole chosen as negative control, and aromatic pesticides. These results partially supported the simulated strategy.

  11. Evaluation of the protective effect of garlic oil on hepatic injury induced by pesticides

    The present study was directed to evaluate the effect of repeated daily oral administrations of two pesticides; malathion (organophosphorus) and lannate (carbamate) at dose levels of 27.5 and 3.4 mg/kg body weight, respectively. Garlic oil at a dose of 0.2 ml/kg body weight was given by gavage during pesticides treatment (garlic oil + pesticides) to evaluate its role against the harmful effects of the two selected pesticides in male albino rats. The level of serum 14C-isoleucine (4 μCi/100 g body weight) twenty-four hours post administration of malathion or lannate and also garlic oil was studied. Malathion and lannate treatments resulted in significant increase in the activity of alkaline phosphatase, acid phosphatase, gamma glutamyl transferase (GGT), bilirubin, 5-nucleotidase, glucose-6-phosphatase and serum total calcium level. On the other hand, pesticides treatment caused significant decrease in serum inorganic phosphorus. The level of serum 14C-isoleucine twenty-four hours post administration of malathion or lannate and also garlic oil was significantly increased due to pesticides treatment and decreased in case of garlic oil treatment. The protective role of garlic oil was clear to some extent and could ameliorate the activities of some serum enzymes in addition to inorganic phosphorus. The administration of garlic oil to malathion treated animals was more effective in ameliorating the disturbed levels in case of malathion than that occurred with lannate pesticide treatment

  12. Application of ACD/LABS 12 program for determination of conditions for experimental membrane extraction of pesticides

    Đorđević J.

    2010-01-01

    Full Text Available This paper analyzes the conditions for membrane extraction of pesticides using ACD / LABS 12 program. The program contains a large database of more than 2000 compounds and their ionized species, for determining the pKa, further analysis includes 600 new compounds confirmed by Hammett’s equation, which gives more precise values for logD and solubility. The 16 pesticides of different classes (organophosphates, carbamates, carbamidas, neonicotinoids etc. and polarities commonly used in Serbia were examined. The program is used to calculate logD, pKa and solubility at different pH values for the mixture of pesticides. Based on the calculated values, the conditions for the extraction of pesticides in water using two-phase liquid-liquid membrane extraction were optimized.

  13. 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.

  14. 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. PMID:26915268

  15. Evaluation of Four Bio fertilizers for Bioremediation of Pesticide contaminated Soil

    Experiments were conducted to asses the ability of mixed populations of microorganisms which produced as a bio fertilizers by the General Organization of Agriculture Fund, Ministry of Agriculture, Egypt (phosphoren, microbien, cerealin and azospirillum) to degrade five selected pesticides representing different classes including organophosphate, carbamate and chlorinated organic compounds. There were differences in rates of biotransformation, suggesting the selective induction of certain metabolic enzymes. Inoculation of soil incorporated with malathion, fenamiphos, carbaryl, aldicarb and dieldrin, resulted in ca. 80-90% removal of malathion and fenamiphos within 8 days, carbaryl and aldicarb within 11-15 days respectively. Dieldrin removal occurred slowly within 2 months. These data suggest that bioremediate may act as potential candidates for soil inoculation to bioremediate pesticide contaminated soil. The production of Co2 (soil respiration ) was stimulated by some pesticides. In samples with microbien, an about 2 times higher Co2 production was measured

  16. New Water-Soluble Carbamate Ester Derivatives of Resveratrol

    Andrea Mattarei

    2014-10-01

    Full Text Available Low bioavailability severely hinders exploitation of the biomedical potential of resveratrol. Extensive phase-II metabolism and poor water solubility contribute to lowering the concentrations of resveratrol in the bloodstream after oral administration. Prodrugs may provide a solution—protection of the phenolic functions hinders conjugative metabolism and can be exploited to modulate the physicochemical properties of the compound. We report here the synthesis and characterization of carbamate ester derivatives of resveratrol bearing on each nitrogen atom a methyl group and either a methoxy-poly(ethylene glycol-350 (mPEG-350 or a butyl-glucosyl promoiety conferring high water solubility. Ex vivo absorption studies revealed that the butyl-glucosyl conjugate, unlike the mPEG-350 one, is able to permeate the intestinal wall. In vivo pharmacokinetics confirmed absorption after oral administration and showed that no hydrolysis of the carbamate groups takes place. Thus, sugar groups can be attached to resveratrol to obtain soluble derivatives maintaining to some degree the ability to permeate biomembranes, perhaps by facilitated or active transport.

  17. tert-Butyl N-benzyl-N-[4-(4-fluorobenzoylmethyl-2-pyridyl]carbamate

    Pierre Koch

    2008-11-01

    Full Text Available In the crystal structure of the title compound, C25H25FN2O3, the pyridine ring makes dihedral angles of 75.1 (3, 39.4 (3 and 74.6 (3° with the phenyl ring, the carbamate plane and the 4-fluorophenyl ring, respectively. The phenyl ring makes dihedral angles of 77.2 (3 and 23.6 (3° with the carbamate plane and the 4-fluorophenyl ring, respectively. The 4-fluorophenyl ring is perpendicular to the carbamate plane, the dihedral angle between them being 89.5 (3°.

  18. Leaching and degradation of pesticides in groundwater layers

    To date, most of the published data on pesticides and soil describe the fate of environmental contaminants in the upper soil layers, where low transportation, high adsorption and high microbial degradation occur. In contrast, few data are available for groundwater layers (to a depth of 5 m) with filtration media such as sand or stony layers. Laboratory testing systems were developed that allow examinations to be carried out under conditions that are close to natural. These include original sands and stones from the relevant groundwater filtration areas, original water from the same areas, and measurement of the velocity of water migrations. The temperature and pH were determined and exact analyses of the sand quality and particle size were made prior to the experiments. To produce accurate data on leaching and adsorption, and to identify the degradation products more easily, 14C labelled pesticides were applied. To determine the column characteristics, tritium labelled water was used. The following 12 pesticides were investigated: the carbamate insecticide, carbofuran; chlorinated hydrocarbons, lindane, DDT and DDE; phosphoric acid esters, chlorpyrifos, diazinon, malathion and parathion; phenylurea herbicides, diuron and monolinuron; the triazine herbicide, terbutylazine; and the novel chloronicotinyl insecticide, imidacloprid. Although the recovery data of the individual pesticides were similar in the eluates of the two different sand types, in most cases the elution curves differed significantly. The different degradation rates and procedures for the same pesticide were clearly shown by the significantly different concentration values. Concerning elution and degradation, the behaviour of the chemicals differed, even if they belonged to the same class of bioactive compound. Furthermore, the behaviour of the same chemical differed in different types of sand. Because of the low transportation velocity, and the subsequent long retention times of the pesticides in the

  19. Pesticide transport simulation in a tropical catchment by SWAT

    The application of agrochemicals in Southeast Asia is increasing in rate, variety and toxicity with alarming speed. Understanding the behavior of these different contaminants within the environment require comprehensive monitoring programs as well as accurate simulations with hydrological models. We used the SWAT hydrological model to simulate the fate of three different pesticides, one of each usage type (herbicide, fungicide and insecticide) in a mountainous catchment in Northern Thailand. Three key parameters were identified: the sorption coefficient, the decay coefficient and the coefficient controlling pesticide percolation. We yielded satisfactory results simulating pesticide load dynamics during the calibration period (NSE: 0.92–0.67); the results during the validation period were also acceptable (NSE: 0.61–0.28). The results of this study are an important step in understanding the modeling behavior of these pesticides in SWAT and will help to identify thresholds of worst-case scenarios in order to assess the risk for the environment. - Highlights: • We performed a global LH-sensitivity analysis of all pesticide related parameters. • Key physical parameters are associated to percolation, degradation and sorption. • We simulated the measured loads of three different pesticides. • We performed an uncertainty analysis of all pesticide simulations. • All Pesticides differed considerably in their sensitivity and simulation behavior. - Pesticide load simulations of three pesticides were modeled by SWAT, providing clues on how to handle pesticides in future SWAT studies

  20. Pesticides poisoning

    Pesticides are chemical toxicants which are used to kill by their toxic actions, the pest organisms, known to incur significant economic losses or threaten human life, his health and that of his domesticated animals. These toxicants are seldom species-specific. The presence of these or their metabolites may scientific be vouched not only in the environment they are used, but in the entire ecosystem, in the subsoil, in the underwater reservoirs and in the food chain of all non-target species including man, his friends i.e. predator and parasite organisms which be uses against the pests, and in his cherished domesticated animals. In the present paper a survey is made of different groups of toxic chemicals generally used to manage pests, in the ecosystem, food chain and tissues and body parts of non-target species including man and the ones dear to him. Toxicology and biochemistry of these toxic materials and their important metabolites are also briefly discussed with special reference to ways and means through which these poison the above non-target species. (author)

  1. Pesticide Instrumental Analysis

    This workshop was the evaluation of the pesticides impact on the vegetable matrix with the purpose to determine the analysis by GC / M S. The working material were lettuce matrix, chard and a mix of green leaves and pesticides.

  2. Pesticides and Pregnancy

    Pesticides and Pregnancy In every pregnancy, a woman starts out with a 3-5% chance of having ... risk. This sheet talks about whether exposure to pesticides may increase the risk for birth defects over ...

  3. 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...

  4. The thermal desorption of CO2 from amine carbamate solutions for the 13C isotope enrichment

    Dronca, S.; Varodi, C.; Gligan, M.; Stoia, V.; Baldea, A.; Hodor, I.

    2012-02-01

    The CO2 desorption from amine carbamate in non-aqueous solvents is of major importance for isotopic enrichment of 13C. A series of experiments were carried out in order to set up the conditions for the CO2 desorption. For this purpose, a laboratory- scale plant for 13C isotope separation by chemical exchange between CO2 and amine carbamate was designed and used. The decomposition of the carbamate solution was mostly produced in the desorber and completed in the boiler. Two different-length desorbers were used, at different temperatures and liquid flow rates of the amine-non-aqueous solvent solutions. The residual CO2 was determined by using volumetric and gaschromatographic methods. These results can be used for enrichment of 13C by chemical exchange between CO2 and amine carbamate in nonaqueous solvents.

  5. Ethyl carbamate levels in selected fermented foods and beverages.

    Canas, B J; Havery, D C; Robinson, L R; Sullivan, M P; Joe, F L; Diachenko, G W

    1989-01-01

    Ethyl carbamate (EC), also known as urethane, is an animal carcinogen and a by-product of fermentation. Because EC has been found in distilled spirits and wines, a variety of fermented foods and beverages were analyzed to assess its occurrence in other products. Previously described methods using a gas chromatograph-thermal energy analyzer with a nitrogen converter were modified for each matrix and gave recoveries of greater than 80%, with a limit of detection in the 1-2 micrograms/kg (ppb) range. A total of 152 test samples were analyzed; EC levels ranged from none found to 3 ppb in 15 cheeses, 6 teas, 12 yogurts, and 8 ciders; from none found to 13 ppb in 30 breads and 69 malt beverages; and from none found to 84 ppb in 12 soy sauces. Gas chromatography/mass spectrometry/mass spectrometry was used to confirm EC identity and to quantitate EC in selected food extracts. PMID:2592308

  6. Potent Urea and Carbamate Inhibitors of Soluble Epoxide Hydrolases

    Morisseau, Christophe; Goodrow, Marvin H.; Dowdy, Deanna; Zheng, Jiang; Greene, Jessica F.; Sanborn, James R.; Hammock, Bruce D.

    1999-08-01

    The soluble epoxide hydrolase (sEH) plays a significant role in the biosynthesis of inflammation mediators as well as xenobiotic transformations. Herein, we report the discovery of substituted ureas and carbamates as potent inhibitors of sEH. Some of these selective, competitive tightbinding inhibitors with nanomolar Ki values interacted stoichiometrically with the homogenous recombinant murine and human sEHs. These inhibitors enhance cytotoxicity of trans-stilbene oxide, which is active as the epoxide, but reduce cytotoxicity of leukotoxin, which is activated by epoxide hydrolase to its toxic diol. They also reduce toxicity of leukotoxin in vivo in mice and prevent symptoms suggestive of acute respiratory distress syndrome. These potent inhibitors may be valuable tools for testing hypotheses of involvement of diol and epoxide lipids in chemical mediation in vitro or in vivo systems.

  7. Novel aryl carbamate derivatives of metronidazole as potential antiamoebic agents.

    Hayat, Faisal; Wahedi, Hussain Mustatab; Park, Seonghyeok; Tariq, Saba; Azam, Amir; Shin, Dongyun

    2016-01-01

    A series of novel aryl carbamate derivatives of metronidazole (MNZ) were designed, synthesized, and screened for antiamoebic activity. As compared to MNZ, most of the derivatives exhibited moderate to excellent activity against the HM1:IMSS strain of Entamoeba histolytica. Compounds 7, 14, 16, 19, and 21 exhibited the most promising antiamoebic activity with IC50 values of 0.24, 0.08, 0.26, 0.26, and 0.15 μM, respectively, compared to that of MNZ (1.78 μM). Moreover, from the toxicological studies of these compounds on human melanocytes, the melan-a cell line revealed that the potent compounds are nontoxic at concentrations ranging from 2.5 to 50 μM. PMID:26597858

  8. Pesticide exposure - Indian scene

    Use of pesticides in India began in 1948 when DDT was imported for malaria control and BHC for locust control. India started pesticide production with manufacturing plant for DDT and benzene hexachloride (BHC) (HCH) in the year 1952. In 1958, India was producing over 5000 metric tonnes of pesticides. Currently, there are approximately 145 pesticides registered for use, and production has increased to approximately 85,000 metric tonnes. Rampant use of these chemicals has given rise to several short-term and long-term adverse effects of these chemicals. The first report of poisoning due to pesticides in India came from Kerala in 1958 where, over 100 people died after consuming wheat flour contaminated with parathion. Subsequently several cases of pesticide-poisoning including the Bhopal disaster have been reported. Despite the fact that the consumption of pesticides in India is still very low, about 0.5 kg/ha of pesticides against 6.60 and 12.0 kg/ha in Korea and Japan, respectively, there has been a widespread contamination of food commodities with pesticide residues, basically due to non-judicious use of pesticides. In India, 51% of food commodities are contaminated with pesticide residues and out of these, 20% have pesticides residues above the maximum residue level values on a worldwide basis. It has been observed that their long-term, low-dose exposure are increasingly linked to human health effects such as immune-suppression, hormone disruption, diminished intelligence, reproductive abnormalities, and cancer. In this light, problems of pesticide safety, regulation of pesticide use, use of biotechnology, and biopesticides, and use of pesticides obtained from natural plant sources such as neem extracts are some of the future strategies for minimizing human exposure to pesticides

  9. 75 FR 35801 - Notice of Receipt of Several Pesticide Petitions Filed for Residues of Pesticide Chemicals in or...

    2010-06-23

    ... published in the Federal Register of January 27, 2010 (75 FR 4274) (FRL-8807-2). A method validation was..., as published in the Federal Register of January 27, 2010 (75 FR 4274) (FRL-8807-2). A method... AGENCY Notice of Receipt of Several Pesticide Petitions Filed for Residues of Pesticide Chemicals in...

  10. 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.

  11. Kinetic and physicochemical properties of brain acetylcholinesterase from the peacock bass (Cichla ocellaris) and in vitro effect of pesticides and metal ions.

    Silva, Kaline Catiely Campos; Assis, Caio Rodrigo Dias; Oliveira, Vagne Melo; Carvalho, Luiz Bezerra; Bezerra, Ranilson Souza

    2013-01-15

    Brain acetylcholinesterase (AChE; EC 3.1.1.7) from peacock bass (Cichla ocellaris) was characterized and the effect of organophosphorus and carbamate pesticides as well as ions and heavy metals was evaluated. The kinetic parameters K(m) and V(max) were determined as 0.769 mM and 0.189 U/mg of protein respectively. Optimal pH and temperature were found to be 8.0 and 45°C. The enzyme retained approximately half of the activity after incubation at 50°C for 30 min. Total cholinesterase activity on brain of this species can be ascribed to AChE according to selective inhibitors analysis (neostigmine, eserine and BW284c5 reduced its activity whereas no effect was noticed for Iso-OMPA). Seven pesticides (five organophosphates: dichlorvos, diazinon, chlorpyrifos, temephos, tetraethyl pyrophosphate - TEPP and two carbamates: carbaryl and carbofuran) showed inhibitory effects on C. ocellaris AChE. However, the strongest effect was observed with carbofuran (IC(50)=0.21 μM and K(i)=2.57 × 10(-3) μM). The following ions (1 mM) showed to inhibit its activity (decrescent order): Hg(2+)>As(3+)>Cu(2+)>Zn(2+). EDTA(2-) did not affect enzyme activity. The present study provides assay conditions and data to suggest this enzyme as in vitro biomarker of organophosphorus and carbamate pesticides in routine environmental screening programs. PMID:23220411

  12. Carbamate Toxicity and Protective effect of vit. A and vit. E on some biochemicalaspects of male albino rats

    Samir, A.M. Zaahkouk* ; Eman, G.E. Helal

    2000-12-01

    Full Text Available The effect of daily oral administration of carbamate (1/10 L.D50 on rats for 30 successive days were studied. The male rats were divided into five groups (control, control + oil, carbamate, carbamate + vit. A and carbamate + vit. E. Each group (except control and control + oil was daily administrated carbamate (0.012 mg/kg B.wt.. Two groups of carbamate ­ intoxicated animals provided with vit. A (700 mg/kg.B.wt or vit. E (10 mg/kg.B.wt. Poisoning symptoms were recorded, e.g. unbalanse, diarrhea, have poor health and posterior limbs rigidity. Haematological parameters showed a significant decrease in red blood corpuscles (R.B.Cs, white blood corpuscles (W.B.Cs count, Haemoglobin concentration and haematocrit value in groups treated with carbamate, and an improvement in these values was observed in groups treated with the anti-oxidants (vit. A and vit. E. Total lipids cholesterol, total proteins, albumin, glucose, LDH, AST, ALT, adrenaline and noradrenaline were measured in serum. Total proteins, total lipids, of tissues (liver, heart, muscle and kidney were investigated. The present study declare that, carbamate induced a significant elevetion in serum LDH, glucose. total lipids,cholesterol, AST, ALT, adrenaline and noradrenaline. On the other hand, causes a significant reduction in total proteins and albumin. The total lipids and total proteins of the tissue were recorded highly significant decrease in the group treated with carbamate only. From another point of view, antioxidant ameliorated the effect of carbamate on tissues. So, it is clear that administration of vit. E or vit. A. reduced the effect of carbamate on biochemical alteration to various extent. The antioxidant property of vitamin A and vitamin E seem to be responsible for the observed protection against carbamate intoxication.

  13. Toxic effects of pesticide mixtures at a molecular level: Their relevance to human health

    Highlights: ► Toxic effects of pesticide mixtures can be independent, dose addition or interaction. ► Metabolic interactions involve inhibition or induction of detoxifying enzymes. ► Organophosphates can potentiate pyrethroid, carbaryl and triazine toxicity. ► Synergism occurs when two active pesticides elicit greater than additive toxicity. ► Endocrine disruptors have the potential for additivity rather than synergism. - Abstract: Pesticides almost always occur in mixtures with other ones. The toxicological effects of low-dose pesticide mixtures on the human health are largely unknown, although there are growing concerns about their safety. The combined toxicological effects of two or more components of a pesticide mixture can take one of three forms: independent, dose addition or interaction. Not all mixtures of pesticides with similar chemical structures produce additive effects; thus, if they act on multiple sites their mixtures may produce different toxic effects. The additive approach also fails when evaluating mixtures that involve a secondary chemical that changes the toxicokinetics of the pesticide as a result of its increased activation or decreased detoxification, which is followed by an enhanced or reduced toxicity, respectively. This review addresses a number of toxicological interactions of pesticide mixtures at a molecular level. Examples of such interactions include the postulated mechanisms for the potentiation of pyrethroid, carbaryl and triazine herbicides toxicity by organophosphates; how the toxicity of some organophosphates can be potentiated by other organophosphates or by previous exposure to organochlorines; the synergism between pyrethroid and carbamate compounds and the antagonism between triazine herbicides and prochloraz. Particular interactions are also addressed, such as those of pesticides acting as endocrine disruptors, the cumulative toxicity of organophosphates and organochlorines resulting in estrogenic effects and the

  14. 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

  15. Pesticides and children

    Prevention and control of damage to health, crops, and property by insects, fungi, and noxious weeds are the major goals of pesticide applications. As with use of any biologically active agent, pesticides have unwanted side-effects. In this review, we will examine the thesis that adverse pesticide effects are more likely to occur in children who are at special developmental and behavioral risk. Children's exposures to pesticides in the rural and urban settings and differences in their exposure patterns are discussed. The relative frequency of pesticide poisoning in children is examined. In this connection, most reported acute pesticide poisonings occur in children younger than age 5. The possible epidemiological relationships between parental pesticide use or exposure and the risk of adverse reproductive outcomes and childhood cancer are discussed. The level of consensus among these studies is examined. Current concerns regarding neurobehavioral toxicity and endocrine disruption in juxtaposition to the relative paucity of toxicant mechanism-based studies of children are explored

  16. 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. PMID:23567114

  17. Quality Control Of Selected Pesticides With GC

    The practical quality control of selected pesticides with GC is treated. Detailed descriptions are given on materials and methods used, including sample preparation and GC operating conditions. The systematic validation of multi methods is described, comprising performance characteristics in routine analysis, like selectivity, specificity etc. This is illustrated by chromatograms, calibration curves and tables derived from real laboratory data. (author)

  18. Pesticides: chemicals for survival

    Pesticides are chemicals used to control pests such as insects, weeds, plant diseases, nematodes, and rodents. The increased use of pesticides since 1945 has greatly aided the increase in crop production, protected livestock from diseases such as trypanosomiasis, protected man from diseases such as malaria and filarisis, decreased losses of stored grain, and has generally improved man's welfare. Despite the enormous benefits derived from pesticides these chemicals are not problem-free. Many pesticides are toxic to living organisms and interfere with specific biochemical systems. To measure the very small quantities of a pesticide radiolabelled chemicals are frequently essential, particularly to measure changes in the chemical structure of the pesticide, movement of the pesticide in soil, plants, or animals, amounts of pesticide going through various steps in food processing, etc. The use of radiolabelled pesticides is shortly shown for metabolism of the pesticide in crop species, metabolism in ruminant, in chickens and eggs, in soil, and possibly leaching and sorption in soil, hydrolysis, bio-concentration, microbial and photodegradation, and toxicity studies

  19. Pesticide exposure in children.

    2012-12-01

    This statement presents the position of the American Academy of Pediatrics on pesticides. Pesticides are a collective term for chemicals intended to kill unwanted insects, plants, molds, and rodents. Children encounter pesticides daily and have unique susceptibilities to their potential toxicity. Acute poisoning risks are clear, and understanding of chronic health implications from both acute and chronic exposure are emerging. Epidemiologic evidence demonstrates associations between early life exposure to pesticides and pediatric cancers, decreased cognitive function, and behavioral problems. Related animal toxicology studies provide supportive biological plausibility for these findings. Recognizing and reducing problematic exposures will require attention to current inadequacies in medical training, public health tracking, and regulatory action on pesticides. Ongoing research describing toxicologic vulnerabilities and exposure factors across the life span are needed to inform regulatory needs and appropriate interventions. Policies that promote integrated pest management, comprehensive pesticide labeling, and marketing practices that incorporate child health considerations will enhance safe use. PMID:23184103

  20. Pesticides (Environmental Health Student Portal)

    ... Pesticides Climate Change Climate Change Home What is Climate Change ... Pesticides The Basics Pesticides are substances we use to control or kill pests. Pests can be weeds, insects, rodents, or bacteria — anything we don’t want ...

  1. Copper(II) catalysis in cyanide conversion into ethyl carbamate in spirits and relevant reactions.

    Aresta, M; Boscolo, M; Franco, D W

    2001-06-01

    The role of copper(II) species in the oxidation of inorganic cyanide to cyanate and in the conversion of cyanate or urea into ethyl carbamate was investigated. The oxidation process has been shown to be independent from the dissolved oxygen. Elemental analysis and infrared spectroscopy have shown the formation of a mixed copper carbonate/hydroxide in the process of oxidation of cyanide to cyanate in water/ethanol. The complexation to Cu(II) of cyanate formed upon cyanide oxidation makes the former more susceptible to nucleophilic attack from ethanol, with conversion into ethyl carbamate. Comparatively, urea has a minor role with respect to cyanide in the formation of ethyl carbamate. Therefore, the urea present in some samples of Brazilian sugar cane spirit (cachaça) has been shown to have almost no influence on the ethyl carbamate content of cachaças, which comes essentially from cyanide. Fe(II,III) affords results similar to those found with Cu(II). Some suggestions are presented to avoid ethyl carbamate formation in spirits during distillation. PMID:11409971

  2. Lignin is linked to ethyl-carbamate formation in ume (Prunus mume) liqueur.

    Hashiguchi, Tomokazu; Izu, Hanae; Sudo, Shigetoshi

    2012-01-01

    Ethyl carbamate concentrations in oak barrel-aged ume (Prunus mume) liqueurs were measured, and possible explanations for elevated levels were examined. The average concentration was 0.30 mg/L, significantly higher than in ume liqueurs not aged in oak (0.08 mg/L). Oak powder extracts were prepared from both untoasted and toasted oak powder by extraction with aqueous ethanol, and these were used to make ume liqueurs. Relative to a no-oak control, the ethyl carbamate concentrations were 3.8 and 11 times higher in the ume liqueur made with the untoasted and toasted oak powder extracts respectively. The extracts were loaded onto a C18 column, washed with water, and eluted with methanol. The (13)C-NMR spectra for the main constituents of the methanol elution fractions were consistent with those for lignin or fragments thereof. The methanol fractions were added to ume liqueur which was stored for 3 months. Relative to a control, the ethyl carbamate concentrations in the 3-month old liqueurs were found to be 1.2 and 4.6 higher for the untoasted oak-powder and the toasted oak-powder respectively. Ethyl carbamate was formed when lignin was added to a 40% aqueous ethanol solution that contained potassium cyanide. These observations suggest that lignin or fragments thereof promote the formation of ethyl carbamate. PMID:22232267

  3. Pesticides and childhood cancers.

    Daniels, J L; Olshan, A.F.; Savitz, D A

    1997-01-01

    To evaluate the possible association between pesticides and the risk of childhood cancers, epidemiologic studies published between 1970 and 1996 were critically reviewed. Thirty-one studies investigated whether occupational or residential exposure to pesticides by either parents or children was related to increased risk of childhood cancer. In general, the reported relative risk estimates were modest. Risk estimates appeared to be stronger when pesticide exposure was measured in more detail. ...

  4. Pesticides and childhood cancer.

    Zahm, S H; Ward, M H

    1998-01-01

    Children are exposed to potentially carcinogenic pesticides from use in homes, schools, other buildings, lawns and gardens, through food and contaminated drinking water, from agricultural application drift, overspray, or off-gassing, and from carry-home exposure of parents occupationally exposed to pesticides. Parental exposure during the child's gestation or even preconception may also be important. Malignancies linked to pesticides in case reports or case-control studies include leukemia, n...

  5. 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...

  6. 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.

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

    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

  8. 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.

  9. 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 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...

  10. 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. PMID:23500396

  11. 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.

  12. New synthesis of carbamate, thiocarbamate and urea type herbicides: preparation of 14C-labelled diuron and EPTC

    N,N-dialkyl-carbamic acid-trimethylsilyl-esters were synthesized starting with 14CO2. The new synthesis route is simple and provides good radiochemical yield. Silyl-carbaminates directly or through carbamoyl-halogenides may be used for preparation of labelled herbicides: carbamates, thiocarbamates and ureas. (author)

  13. 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.

  14. 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.

  15. The carcinogenic potential of ethyl carbamate (urethane): risk assessment at human dietary exposure levels

    Schlatter, J; Werner K Lutz

    2012-01-01

    Ethyl carbamate is found in fermented foods: bread contains 3-15 ng/g, stone-fruit brandies 200-20,000 ngfg, and about one-third of table-wine samples analysed contained more than 10 ng/g. In animals, ethyl carbamate is degraded to C02, H20 and NH3, with intermediate formation ofethanol. This degradation has been shown tobe inhibited (postponed) in the mouse by ethanol concentrations in the blood of about 0.15% and higher. A quantitatively minor pathway involves a two-step oxidation of the et...

  16. Gas chromatographic-mass spectrometric determination of ethyl carbamate in alcoholic beverages.

    Lau, B P; Weber, D; Page, B D

    1987-07-31

    A sensitive and specific method based on gas chromatography-mass spectrometry for the quantitative determination of ethyl carbamate in table wines, fortified wines (such as ports and sherries), distilled spirits, brandies and liqueurs has been developed. Three characteristic ions from ethyl carbamate [m/z 89 (molecular ion), 74 and 62] were monitored in the selected-ion monitoring (SIM) mode. The lowest detection limit (based on the response on the m/z 62 ion) was estimated to be 0.5 ng/g (ppb). Additional confirmation techniques, including high-resolution SIM, and methane or isobutane chemical ionization are described. PMID:3654867

  17. Screening Pesticides for Neuropathogenicity

    Doherty, John D.

    2006-01-01

    Pesticides are routinely screened in studies that follow specific guidelines for possible neuropathogenicity in laboratory animals. These tests will detect chemicals that are by themselves strong inducers of neuropathogenesis if the tested strain is susceptible relative to the time of administration and methodology of assessment. Organophosphate induced delayed neuropathy (OPIDN) is the only known human neurodegenerative disease associated with pesticides and the existing...

  18. 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....

  19. Pesticider 2 i overfladevand

    Nyeland, B.; Kvamm, B. L.

    DMU har den 29. september 1999 afholdt en metodeafprøvning: Pesticider 2 i overfladevand. Der var tilmeldt 17 danske og udenlandske laboratorier i metodeafprøvningen. Prøvningen omfattede 32 pesticider i overfladevand fra en sjællandsk sø. Koncentrationsniveauet for hver komponent var på 0,025 - 0...

  20. 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.

  1. PESTICIDES: BENEFITS AND HAZARDS

    Ivan Maksymiv

    2015-05-01

    Full Text Available Pesticides are an integral part of modern life used to prevent growth of unwanted living  organisms. Despite the fact that scientific statements coming from many toxicological works provide indication on the low risk of the pesticides and their residues, the community especially last years is deeply concerned about massive application of pesticides in diverse fields. Therefore evaluation of hazard risks particularly in long term perspective is very important. In the fact there are at least two clearly different approaches for evaluation of pesticide using: the first one is defined as an objective or probabilistic risk assessment, while the second one is the potential economic and agriculture benefits. Therefore, in this review the author has considered scientifically based assessment of positive and negative effects of pesticide application and discusses possible approaches to find balance between them.

  2. 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 products comply with the labelled content. The tolerance of deviation from the labelled content of active ingredient is set by the Danish Statutory Order on pesticides. In addition to the examination of the content of active ingredients, all collected samples are examined for the content of octylphenol...... ethoxylates (OPEO) and nonylphenol ethoxylates (NPEO). The industry and the Danish authorities have agreed on removing these compounds from all Danish-sold pesticide formulations produced after June 2000. Four different groups of products covered by the pesticide regulation were included in the 2006...

  3. 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...

  4. Investigations of primary and secondary amine carbamate stability by 1H NMR spectroscopy for post combustion capture of carbon dioxide

    Highlights: ► Carbamate stability constants of series of amines have been measured at (288 to 318) K. ► Standard molar enthalpies and entropies have been determined by van’t Hoff analyses. ► A ΔHmo-ΔSmo plot for carbamate formation gives a linear relationship. ► This relationship provides a guide for the selection of amines for PCC applications. ► Stereochemical effects and intramolecular H-bonding affect carbamate formation. - Abstract: Carbamate formation is one of the major chemical reactions that can occur in solution in the capture of CO2 by amine-based solvents, and carbamate formation makes a significant enthalpy contribution to the absorption-desorption of CO2 that occurs in the absorber/stripper columns of the PCC process. Consequently, the formation of carbamates of selected series of primary and secondary amines over the temperature range (288 to 318) K has been investigated by equilibrium 1H NMR studies, and the stability constants (K9) for the equilibrium: RNH2+HCO3-⇄K9RNHCOO-+H2O are reported. van’t Hoff analyses have resulted in standard molar enthalpies, ΔHmo, and entropies, ΔSmo, of carbamate formation. A ΔHmo-ΔSmo plot generates a linear correlation for carbamate formation (providing a mean standard molar free energy, ΔGmo, for carbamate formation of about −7 kJ · mol−1), and this relationship helps provide a guide to the selection of an amine(s) solvent for CO2 capture, in terms of enthalpy considerations. A linear ΔHmo-ΔSmo plot also occurs for carbamate protonation. The formation of the carbamates has been correlated with systematic changes in composition and structure, and steric effects have been identified by comparing molecular geometries obtained using density functional B3LYP/6-311++G(d,p) calculations. Trends in steric effects have been identified in the series of compounds monoethanolamine (MEA), 1-amino-2-propanol, 2-amino-1-propanol (AP) and 2-amino-2-methyl-1-propanol (AMP). In the case of 2

  5. Effect Of Fenugreek Seed Powder In Toxicity Induced By MALAPHOS And METHAVINE Pesticides In Male Rats

    Pesticides administration to rats led to an enhancement in oxidative stress and generation of free radicals. These free radicals may be involved in the toxicity of some pesticides. Therefore, the present study was undertaken to assess the effect of pre-treatment of rats with fenugreek seed powder at the dose level of 250 mg/kg b.wt in inhibiting the oxidative damage induced by administration malaphos (organophosphorus) at the dose level of 343.75 mg/kg b.wt and methavine (carbamate) at the dose level of 4 mg/kg b.wt for 6 weeks. Also the present study was carried out to evaluate the strength of fenugreek seed powder and the influence of both pesticides, malaphos and methovine on serum glucose, insuline, total bilirubin, total protein, albumin and gamma glutamyl transferase (γGT), calcium (Ca), inorganic phosphorus and iron (Fe) contents. The metabolism of14C-glucose injected 24 hours post-treatments with the two pesticides and fenugreek seed powder were studied. The results obtained demonstrated that the deleterious damage due to malaphos and methavine administration was manifested by the significant elevation in serum glucose, gamma glutamyl transferase (γ -GT), calcium (Ca), and iron content. Also, there was significant decrease in insulin level, total bilirubin, total protein, albumin and inorganic phosphorus. On the other hand, the data recorded a reduction in the tracing of metabolizable of14C- glucose which was more pronounced in urine of rats administrated malaphos compared to those received methavine pesticide. It could be concluded that administration of fenugreek seed powder (FSP) to rats during the treatment with malaphos or methavine pesticide attenuated to a great extent the damaging effects of both pesticides on the here in assayed parameters. According, by fenugreek administration at the used dose may have an indirect physiological effect on the metabolism of14C- glucose.

  6. 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.

  7. Pesticide residues in fruit samples: comparison of different QuEChERS methods using liquid chromatography-tandem mass spectrometry.

    Christia, C; Bizani, E; Christophoridis, C; Fytianos, K

    2015-09-01

    Acetate- and citrate-buffered quick, easy, cheap, effective, rugged, safe (QuEChERS) pretreatment methods were evaluated for the determination of various pesticides in peaches, grapes, apples, bananas, pears, and strawberries from various regions of Greece, using LC-MS/MS. The purposes of this study were (i) to evaluate which type of QuEChERS method was the most appropriate and effective for each matrix; (ii) to apply the selected QuEChERS method for each matrix, in order to detect and quantify pesticide residues in various fruit samples using UPLC-MS/MS; (iii) to examine the concentration distribution of pesticide classes among fruit originating from various areas; and (iv) to assess pesticide concentration distribution between peel and flesh of fruit in order to evaluate the penetration of pesticide residues in the fruit flesh. Acetate-buffered QuEChERS was found to be the most suitable technique for most of the fruit matrices. According to the recovery values at two different concentration levels, peaches should preferably be treated by the citrate-buffered type, whereas grapes, bananas, apples, pears, and strawberries are best treated by the acetate-buffered version, although the differences in efficiency were small. The addition of graphitized carbon black significantly decreases the recovery of specific pesticides in all matrices except for strawberries. The majority of values do not exceed the official maximum residue levels set by the European Commission. Organophosphates proved to be the most commonly detected category along with triazines-triazoles-conazoles group and by carbamates. Apples and pears seem to be the most contaminated fruit matrices among those tested. Distribution of pesticide classes shows variations between different regions, suggesting different pesticide application practices. In the case of peaches and pears, there is an equal distribution of detected pesticides between peel and flesh, indicating penetration of contaminants into the

  8. 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

  9. Presence of organophosphorus pesticide oxygen analogs in air samples

    Armstrong, Jenna L.; Fenske, Richard A; Yost, Michael G.; Galvin, Kit; Tchong-French, Maria; Yu, Jianbo

    2013-01-01

    A number of recent toxicity studies have highlighted the increased potency of oxygen analogs (oxons) of several organophosphorus (OP) pesticides. These findings were a major concern after environmental oxons were identified in environmental samples from air and surfaces following agricultural spray applications in California and Washington State. This paper reports on the validity of oxygen analog measurements in air samples for the OP pesticide, chlorpyrifos. Controlled environmental and lab...

  10. Computational study of structural properties of lithium cation complexes with carbamate-modified disiloxanes.

    Jeschke, Steffen; Wiemhöfer, Hans-Dieter; Mück-Lichtenfeld, Christian

    2014-07-21

    Lithium cation solvation structures [Li(S)(n=1-4)](+) with ligands of cyclic or noncyclic carbamate-modified disiloxanes are optimized at B3LYP level of theory and compared to their corresponding simplified carbamates and to the organic carbonates ethylene carbonate (EC) and dimethyl carbonate (DMC). The electrostatic potentials (ESP) of these investigated carbonyl-containing solvents are mapped on the electron density surface. The maximum ESP is located at the C=O-oxygen, whereas the disiloxane functionality represents an unpolar residue. Natural Bond Orbitals (NBO) analysis reveals strong n(N) →π(C[double bond, length as m-dash]O) donor-acceptor interactions in carbamates which outrun dipolar properties. As a result, higher total binding energies (ΔE(B)) for solvation of Li(+) in carbamates (-148 kcal mol(-1)) are found than for carbonates (-137 kcal mol(-1)). Furthermore, the disiloxane moiety with its Si-O bond is stabilized by n(O) →σ*(Si-C) hyperconjugation that provides additional electron density to a nearby SiCH3 methyl group thus supporting an additional SiCH2-H...Li(+) coordination. The formation of all investigated solvation structures is exothermic. Owing to steric hindrance of noncyclic carbonyl-containing ligands and the bulky disiloxane functionality, the solvation structure [Li(S)3](+) is the preferred structure according to Gibbs free energy ΔG(B) results. PMID:24914737