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Chemical Research in Toxicology Jun 2022Oxime-type carbamate pesticides having an oxime moiety such as aldicarb, butocarboxim, methomyl, oxamyl, and thiofanox are widely used and have been detected in many...
Oxime-type carbamate pesticides having an oxime moiety such as aldicarb, butocarboxim, methomyl, oxamyl, and thiofanox are widely used and have been detected in many fatal cases of accidental exposure or suicide. In forensic toxicology, the accurate determination of blood pesticide concentration is obligatory to prove death by oxime-type carbamate pesticide poisoning. However, the fatal pesticide concentration in blood at autopsy differs from that at the time of death. In this study, we found that oxime-type carbamate pesticides were decomposed by Hb in a temperature-dependent fashion. The mechanism underlying methomyl, aldicarb, oxamyl, and thiofanox decomposition involves the formation of adducts with the amino acids in Hb. With regard to butocarboxim, its decomposition involves the oxidation of the free form and the formation of adducts with the amino acids in Hb. The mass spectra obtained by liquid chromatography quadrupole time-of-flight mass spectrometry revealed that carbamylated amino acid adducts such as W-adduct and V-adduct were formed in Hb solution incubated with methomyl, aldicarb, oxamyl, and thiofanox, whereas alkylated amino acid adducts such as W-adduct were formed in Hb solution incubated with butocarboxim. These results indicate that aldicarb, butocarboxim, methomyl, oxamyl, and thiofanox are post-mortem changed by Hb.
Topics: Aldicarb; Amino Acids; Autopsy; Carbamates; Cholinesterase Inhibitors; Hemoglobins; Humans; Methomyl; Oximes; Pesticides
PubMed: 35559618
DOI: 10.1021/acs.chemrestox.2c00092 -
Photochemical & Photobiological... May 2016A liquid chromatography method with post-column photoinduced chemiluminescence (PICL) detection is proposed for the simultaneous determination of eight carbamate...
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.
Topics: Carbamates; Chromatography, High Pressure Liquid; Equipment Design; Groundwater; Limit of Detection; Luminescence; Luminescent Measurements; Pesticides; Solid Phase Extraction; Water Pollutants, Chemical
PubMed: 27079156
DOI: 10.1039/c6pp00056h -
Archives of Environmental Contamination... Jul 1996Recent organic fertilizer treatments (cow manure, pig slurry, composts, or green manure) simultaneously increase insecticide adsorption onto soil and the insecticide...
Recent organic fertilizer treatments (cow manure, pig slurry, composts, or green manure) simultaneously increase insecticide adsorption onto soil and the insecticide soil persistence, indicating a mechanism of slow release of insecticide into soil by the organic matter. This occurred in sugar beet crops with aldicarb, thiofanox and imidacloprid; also, in leek, cauliflower and brussels sprouts crops with chlorpyrifos and chlorfenvinphos. In contrast, organic fertilizer treatments applied once or repeatedly in the past, have no significant influence on adsorption or persistence of insecticides; the same is observed for the old soil organic matter, when its soil concentrations change in limited ranges
Topics: Adsorption; Biodegradation, Environmental; Fertilizers; Half-Life; Insecticides; Soil Microbiology; Soil Pollutants
PubMed: 8687996
DOI: 10.1007/BF00203913 -
International Journal of Epidemiology Apr 2019Pesticide exposures are suspected to be implicated in the excess of central nervous system (CNS) tumours observed in farmers, but evidence concerning individual...
BACKGROUND
Pesticide exposures are suspected to be implicated in the excess of central nervous system (CNS) tumours observed in farmers, but evidence concerning individual pesticides remains limited. Carbamate insecticides, used on a wide range of crops, have shown evidence of carcinogenicity in some experimental studies. In the cohort AGRICAN (AGRIculture & CANcer), we assessed the associations between potential exposures to carbamate insecticides and the incidence of CNS tumours, overall and by histological subtype.
METHODS
AGRICAN enrolled 181 842 participants involved in agriculture. Incident CNS tumours were identified by linkage with cancer registries from enrolment (2005-07) until 2013. Carbamate exposure was assessed by combining information on lifetime periods of pesticide use on crop or livestock and the French crop-exposure matrix PESTIMAT, individually for each of the 19 carbamate insecticides registered in France since 1950. Associations were estimated using proportional hazards models with age as the underlying time scale, adjusting for gender, educational level and smoking.
RESULTS
During a 6.9-year average follow-up, 381 incident cases of CNS tumours occurred, including 164 gliomas and 134 meningiomas. Analyses showed increased risks of CNS tumours with overall exposure to carbamate insecticides and linear trends with duration of use of each carbamate. Considering tumour subtypes, hazard ratios for gliomas ranged from 1.18 for thiofanox to 4.60 for formetanate, and for meningiomas from 1.51 for carbaryl to 3.67 for thiofanox.
CONCLUSIONS
Findings reinforce carcinogenicity evidence for already suspected active ingredients and draw attention to additional active ingredients, notably used on fruit trees, vineyards, potatoes and beets.
Topics: Adult; Aged; Agricultural Workers' Diseases; Agriculture; Central Nervous System Neoplasms; Farmers; Female; France; Humans; Male; Middle Aged; Occupational Exposure; Pesticides; Proportional Hazards Models; Prospective Studies
PubMed: 30476073
DOI: 10.1093/ije/dyy246 -
Journal of Agricultural and Food... 1975
Topics: Carbamates; Gossypium; Insecticides; Oximes; Pesticide Residues; Seeds
PubMed: 1194563
DOI: 10.1021/jf60202a003 -
Journal of Chromatography Dec 1976
Topics: Carbamates; Chromatography, Thin Layer; Gels; Insecticides; Methods; Oximes; Silicon Dioxide
PubMed: 187610
DOI: 10.1016/s0021-9673(00)87810-3 -
Journal of Agricultural and Food... 1975
Topics: Carbamates; Gossypium; Insecticides; Oximes; Pesticide Residues; Plants; Seeds; Soil Pollutants; Vegetables; Water Pollutants; Water Pollutants, Chemical
PubMed: 1159201
DOI: 10.1021/jf60201a015 -
Journal of Agricultural and Food... 1980
Topics: Animals; Biotransformation; Carbamates; Female; Insecticides; Male; Rats
PubMed: 7451737
DOI: 10.1021/jf60232a007 -
Journal of Agricultural and Food... 1980
Topics: Animals; Biotransformation; Carbamates; Cholinesterase Inhibitors; Female; Insecticides; Male; Rats
PubMed: 7451763
DOI: 10.1021/jf60232a029 -
Journal of Agricultural and Food... 1976
Topics: Carbamates; Cooking; Drug Stability; Hot Temperature; Insecticides; Oximes; Pesticide Residues; Time Factors; Vegetables
PubMed: 965582
DOI: 10.1021/jf60207a037