Development of a CEN Standardised Method for Liquid Chromatography Coupled to Accurate Mass Spectrometry
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Novel Approach to Fast Determination of 64 Pesticides Using of Ultra-Performance Liquid Chromatography-Tandem Mass Spectrometry
Novel approach to fast determination of 64 pesticides using of ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) Tomas Kovalczuk, Ondrej Lacina, Martin Jech, Jan Poustka, Jana Hajslova To cite this version: Tomas Kovalczuk, Ondrej Lacina, Martin Jech, Jan Poustka, Jana Hajslova. Novel approach to fast determination of 64 pesticides using of ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Food Additives and Contaminants, 2008, 25 (04), pp.444-457. 10.1080/02652030701570156. hal-00577414 HAL Id: hal-00577414 https://hal.archives-ouvertes.fr/hal-00577414 Submitted on 17 Mar 2011 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Food Additives and Contaminants For Peer Review Only Novel approach to fast determination of 64 pesticides using of ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) Journal: Food Additives and Contaminants Manuscript ID: TFAC-2007-065.R1 Manuscript Type: Original Research Paper Date Submitted by the 07-Jul-2007 Author: Complete List of Authors: -
Chemicals Implicated in Colony Collapse Disorder
Chemicals Implicated While research is underway to determine the cause of Colony Collapse Disorder (CCD), pesticides have emerged as one of the prime suspects. Recent bans in Europe attest to the growing concerns surrounding pesticide use and honeybee decline. Neonicotinoids Neonicotinoids are a relatively new class of insecticides that share a common mode of action that affect the central nervous system of insects, resulting in paralysis and death. They include imidacloprid, acetamiprid, clothianidin, dinotefuran, nithiazine, thiacloprid and thiamethoxam. According to the EPA, uncertainties have been identified since their initial registration regarding the potential environmental fate and effects of neonicotinoid pesticides, particularly as they relate to pollinators. Studies conducted in the late 1990s suggest that neonicotinic residues can accumulate in pollen and nectar of treated plants and represent a potential risk to pollinators. There is major concern that neonicotinoid pesticides may play a role in recent pollinator declines. Neonicotinoids can also be persistent in the environment, and when used as seed treatments, translocate to residues in pollen and nectar of treated plants. The potential for these residues to affect bees and other pollinators remain uncertain. Despite these uncertainties, neonicotinoids are beginning to dominate the market place, putting pollinators at risk. The case of the neonicotinoids exemplifies two critical problems with current registration procedures and risk assessment methods for pesticides: the reliance on industry-funded science that contradicts peer-reviewed studies and the insufficiency of current risk assessment procedures to account for sublethal effects of pesticides. • Imidacloprid Used in agriculture as foliar and seed treatments, for indoor and outdoor insect control, home gardening and pet products, imidacloprid is the most popular neonicotinoid, first registered in 1994 under the trade names Merit®, Admire®, Advantage TM. -
Froggatt) (Diptera: Tephritidae
insects Article Efficacy of Chemicals for the Potential Management of the Queensland Fruit Fly Bactrocera tryoni (Froggatt) (Diptera: Tephritidae) Olivia L. Reynolds 1,2,*, Terrence J. Osborne 2 and Idris Barchia 3 1 Graham Centre for Agricultural Innovation (New South Wales Department of Primary Industries and Charles Sturt University), Elizabeth Macarthur Agricultural Institute, Private Bag 4008, Narellan, NSW 2567, Australia 2 New South Wales Department of Primary Industries, Biosecurity and Food Safety, Elizabeth Macarthur Agricultural Institute, Private Bag 4008, Narellan, NSW 2567, Australia; [email protected] 3 New South Wales Department of Primary Industries, Chief Scientist’s Branch, Elizabeth Macarthur Agricultural Institute, Private Bag 4008, Narellan, NSW 2567, Australia; [email protected] * Correspondence: [email protected]; Tel.: +61-246-406-200 Academic Editors: Michael J. Stout, Jeff Davis, Rodrigo Diaz and Julien M. Beuzelin Received: 2 February 2017; Accepted: 2 May 2017; Published: 9 May 2017 Abstract: This study investigated alternative in-field chemical controls against Bactrocera tryoni (Froggatt). Bioassay 1 tested the mortality of adults exposed to fruit and filter paper dipped in insecticide, and the topical application of insecticide to adults/fruit. Bioassay 2 measured the mortality of adults permitted to oviposit on fruit dipped in insecticide and aged 0, 1, 3, or 5 days, plus the production of offspring. Bioassay 3 tested infested fruit sprayed with insecticide. The field bioassay trialed the mortality of adults exposed to one- and five-day insecticide residues on peaches, and subsequent offspring. Abamectin, alpha-cypermethrin, clothianidin, dimethoate (half-label rate), emamectin benzoate, fenthion (half- and full-label rate), and trichlorfon were the most efficacious in bioassay 1, across 18 tested insecticide treatments. -
Immunosuppression in Honeybee Queens by the Neonicotinoids Thiacloprid and Clothianidin
www.nature.com/scientificreports OPEN Immunosuppression in Honeybee Queens by the Neonicotinoids Thiacloprid and Clothianidin Received: 24 November 2016 Annely Brandt1, Katharina Grikscheit2, Reinhold Siede1, Robert Grosse2, Marina Doris Accepted: 19 May 2017 Meixner 1 & Ralph Büchler1 Published: xx xx xxxx Queen health is crucial to colony survival of honeybees, since reproduction and colony growth rely solely on the queen. Queen failure is considered a relevant cause of colony losses, yet few data exist concerning effects of environmental stressors on queens. Here we demonstrate for the first time that exposure to field-realistic concentrations of neonicotinoid pesticides can severely affect the immunocompetence of queens of western honeybees (Apis mellifera L.). In young queens exposed to thiacloprid (200 µg/l or 2000 µg/l) or clothianidin (10 µg/l or 50 µg/l), the total hemocyte number and the proportion of active, differentiated hemocytes was significantly reduced. Moreover, functional aspects of the immune defence namely the wound healing/melanisation response, as well as the antimicrobial activity of the hemolymph were impaired. Our results demonstrate that neonicotinoid insecticides can negatively affect the immunocompetence of queens, possibly leading to an impaired disease resistance capacity. Honeybees are highly eusocial insects that build colonies of several thousand individuals which contain only one fertile female, the queen1. This queen is responsible for all egg laying and brood production within the colony; consequently, her integrity and health is crucial for the colony’s performance and survival, and any impairment can result in adverse effects on colony fitness. In the worst case, if the workers are unable to replace a failing queen, the colony will perish2–4. -
2002 NRP Section 6, Tables 6.1 Through
Table 6.1 Scoring Table for Pesticides 2002 FSIS NRP, Domestic Monitoring Plan } +1 0.05] COMPOUND/COMPOUND CLASS * ) (EPA) (EPA) (EPA) (EPA) (EPA) (FSIS) (FSIS) PSI (P) TOX.(T) L-1 HIST. VIOL. BIOCON. (B) {[( (2*R+P+B)/4]*T} REG. CON. (R) * ENDO. DISRUP. LACK INFO. (L) LACK INFO. {[ Benzimidazole Pesticides in FSIS Benzimidazole MRM (5- 131434312.1 hydroxythiabendazole, benomyl (as carbendazim), thiabendazole) Carbamates in FSIS Carbamate MRM (aldicarb, aldicarb sulfoxide, NA44234416.1 aldicarb sulfone, carbaryl, carbofuran, carbofuran 3-hydroxy) Carbamates NOT in FSIS Carbamate MRM (carbaryl 5,6-dihydroxy, chlorpropham, propham, thiobencarb, 4-chlorobenzylmethylsulfone,4- NT 4 1 3 NV 4 4 13.8 chlorobenzylmethylsulfone sulfoxide) CHC's and COP's in FSIS CHC/COP MRM (HCB, alpha-BHC, lindane, heptachlor, dieldrin, aldrin, endrin, ronnel, linuron, oxychlordane, chlorpyrifos, nonachlor, heptachlor epoxide A, heptachlor epoxide B, endosulfan I, endosulfan I sulfate, endosulfan II, trans- chlordane, cis-chlordane, chlorfenvinphos, p,p'-DDE, p, p'-TDE, o,p'- 3444NV4116.0 DDT, p,p'-DDT, carbophenothion, captan, tetrachlorvinphos [stirofos], kepone, mirex, methoxychlor, phosalone, coumaphos-O, coumaphos-S, toxaphene, famphur, PCB 1242, PCB 1248, PCB 1254, PCB 1260, dicofol*, PBBs*, polybrominated diphenyl ethers*, deltamethrin*) (*identification only) COP's and OP's NOT in FSIS CHC/COP MRM (azinphos-methyl, azinphos-methyl oxon, chlorpyrifos, coumaphos, coumaphos oxon, diazinon, diazinon oxon, diazinon met G-27550, dichlorvos, dimethoate, dimethoate -
Chemical Name Federal P Code CAS Registry Number Acutely
Acutely / Extremely Hazardous Waste List Federal P CAS Registry Acutely / Extremely Chemical Name Code Number Hazardous 4,7-Methano-1H-indene, 1,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro- P059 76-44-8 Acutely Hazardous 6,9-Methano-2,4,3-benzodioxathiepin, 6,7,8,9,10,10- hexachloro-1,5,5a,6,9,9a-hexahydro-, 3-oxide P050 115-29-7 Acutely Hazardous Methanimidamide, N,N-dimethyl-N'-[2-methyl-4-[[(methylamino)carbonyl]oxy]phenyl]- P197 17702-57-7 Acutely Hazardous 1-(o-Chlorophenyl)thiourea P026 5344-82-1 Acutely Hazardous 1-(o-Chlorophenyl)thiourea 5344-82-1 Extremely Hazardous 1,1,1-Trichloro-2, -bis(p-methoxyphenyl)ethane Extremely Hazardous 1,1a,2,2,3,3a,4,5,5,5a,5b,6-Dodecachlorooctahydro-1,3,4-metheno-1H-cyclobuta (cd) pentalene, Dechlorane Extremely Hazardous 1,1a,3,3a,4,5,5,5a,5b,6-Decachloro--octahydro-1,2,4-metheno-2H-cyclobuta (cd) pentalen-2- one, chlorecone Extremely Hazardous 1,1-Dimethylhydrazine 57-14-7 Extremely Hazardous 1,2,3,4,10,10-Hexachloro-6,7-epoxy-1,4,4,4a,5,6,7,8,8a-octahydro-1,4-endo-endo-5,8- dimethanonaph-thalene Extremely Hazardous 1,2,3-Propanetriol, trinitrate P081 55-63-0 Acutely Hazardous 1,2,3-Propanetriol, trinitrate 55-63-0 Extremely Hazardous 1,2,4,5,6,7,8,8-Octachloro-4,7-methano-3a,4,7,7a-tetra- hydro- indane Extremely Hazardous 1,2-Benzenediol, 4-[1-hydroxy-2-(methylamino)ethyl]- 51-43-4 Extremely Hazardous 1,2-Benzenediol, 4-[1-hydroxy-2-(methylamino)ethyl]-, P042 51-43-4 Acutely Hazardous 1,2-Dibromo-3-chloropropane 96-12-8 Extremely Hazardous 1,2-Propylenimine P067 75-55-8 Acutely Hazardous 1,2-Propylenimine 75-55-8 Extremely Hazardous 1,3,4,5,6,7,8,8-Octachloro-1,3,3a,4,7,7a-hexahydro-4,7-methanoisobenzofuran Extremely Hazardous 1,3-Dithiolane-2-carboxaldehyde, 2,4-dimethyl-, O- [(methylamino)-carbonyl]oxime 26419-73-8 Extremely Hazardous 1,3-Dithiolane-2-carboxaldehyde, 2,4-dimethyl-, O- [(methylamino)-carbonyl]oxime. -
Assessment of the Endocrine-Disrupting Effects Of
Food and Chemical Toxicology 133 (2019) 110759 Contents lists available at ScienceDirect Food and Chemical Toxicology journal homepage: www.elsevier.com/locate/foodchemtox Assessment of the endocrine-disrupting effects of organophosphorus T pesticide triazophos and its metabolites on endocrine hormones biosynthesis, transport and receptor binding in silico ⁎ Fang-Wei Yanga, Yi-Xuan Lia, Fa-Zheng Rena,b, Jie Luoa,c, Guo-Fang Panga,d, a Beijing Advanced Innovation Center for Food Nutrition and Human Health, College of Food Science and Nutritional Engineering, China Agricultural University, Beijing, 100083, China b Key Laboratory of Functional Dairy, Co-constructed by Ministry of Education and Beijing Government, Beijing Laboratory of Food Quality and Safety, China Agricultural University, Beijing, 100083, China c College of Food Science and Technology, Hunan Agricultural University, Changsha, 410114, China d Chinese Academy of Inspection and Quarantine, Beijing, 100176, China ARTICLE INFO ABSTRACT Keywords: Triazophos (TAP) was a widely used organophosphorus insecticide in developing countries. TAP could produce Triazophos specific metabolites triazophos-oxon (TAPO) and 1-phenyl-3-hydroxy-1,2,4-triazole (PHT) and non-specific Metabolites metabolites diethylthiophosphate (DETP) and diethylphosphate (DEP). The objective of this study involved Endocrine disruption computational approaches to discover potential mechanisms of molecular interaction of TAP and its major Hormones metabolites with endocrine hormone-related proteins using molecular docking in silico. We found that TAP, Molecular docking TAPO and DEP showed high binding affinity with more proteins and enzymes than PHT and DETP. TAPmight interfere with the endocrine function of the adrenal gland, and TAP might also bind strongly with glucocorticoid receptors and thyroid hormone receptors. -
Evidence for the Effects of Neonicotinoids Used in Arable Crop
James et al. Environ Evid (2016) 5:22 DOI 10.1186/s13750-016-0072-9 Environmental Evidence SYSTEMATIC MAP PROTOCOL Open Access Evidence for the effects of neonicotinoids used in arable crop production on non‑target organisms and concentrations of residues in relevant matrices: a systematic map protocol Katy L. James1, Nicola P. Randall1* , Keith F. A. Walters1, Neal R. Haddaway2 and Magnus Land2 Abstract Background: Neonicotinoid insecticides (NNIs) have been routinely used in arable crop protection since their devel- opment in the early 1990s. These insecticides have been subject to the same registration procedures as other groups of pesticides, thus meet the same environmental hazard standards as all crop protection products. However, during the last 10 years the debate regarding their possible detrimental impact on non-target organisms, particularly pollina- tors, has become increasingly contentious and widely debated. Against this background, legislators and politicians in some countries, have been faced with a need to make decisions on the future registration of some or all of this class of insecticides, based on published evidence that in some areas is incomplete or limited in extent. This has created much concern in agricultural communities that consider that the withdrawal of these insecticides is likely to have significant negative economic, socio-economic and environmental consequences. Methods: The proposed systematic map aims to address the following primary question: What is the available evidence for the effects of neonicotinoids used in arable crop production on non-target organisms and concentra- tions of residues in relevant matrices? The primary question will be divided into two sub-questions to gather research literature for (1) the effect of NNIs on non-target organisms (2) the occurrence of concentrations of NNIs in matrices of relevance to non-target organisms (i.e. -
Eupt-Fv17- Target Pesticide List
EUPT-FV17- TARGET PESTICIDE LIST MRRL Pesticide (mg/Kg) 3-hydroxy-carbofuran 0.01 Acephate 0.01 Acetamiprid 0.01 Acrinathrin 0.01 Aldicarb 0.01 Aldicarb Sulfone 0.01 Aldicarb Sulfoxide 0.01 Azinphos-methyl 0.01 Azoxystrobin 0.01 Benfuracarb 0.01 Benomyl 0.01 Bifenthrin 0.01 Bitertanol 0.01 Boscalid 0.01 Bromopropylate 0.01 Bromuconazole 0.01 Bupirimate 0.01 Buprofezin 0.01 Cadusafos 0.006 Carbaryl 0.01 Carbendazim 0.01 Carbofuran 0.01 Carbosulfan 0.01 Chlorfenapyr 0.01 Chlorfenvinphos 0.01 Chlorobenzilate 0.01 Chlorothalonil 0.01 Chlorpropham (only parent compound) 0.01 Chlorpyrifos 0.01 Chlorpyrifos-methyl 0.01 Clofentezine (only parent compound) 0.01 Clothianidin 0.01 Cyfluthrin (cyfluthrin incl. other mixtures of constituent isomers (sum of isomers)) 0.01 Cypermethrin (cypermethrin incl. other mixtures of constituent isomers (sum of isomers)) 0.01 Cyproconazole 0.01 Cyprodinil 0.01 Deltamethrin 0.01 Demeton-S-methylsulfone 0.006 Desmethyl-pirimicarb 0.01 Diazinon 0.01 Dichlofluanid (only parent compound) 0.01 Dichlorvos 0.01 Dicloran 0.01 Dicofol 0.01 Diethofencarb 0.01 Difenoconazole 0.01 Diflubenzuron 0.01 Dimethoate 0.003 Dimethomorph 0.01 Dimethylaminosulfotoluidide (DMST) 0.01 Diniconazole 0.01 Diphenylamine 0.01 Endosulfan alpha 0.01 Endosulfan beta 0.01 Endosulfan sulfate 0.01 EPN 0.01 Epoxiconazole 0.01 Ethion 0.01 Ethirimol 0.01 Ethoprophos 0.008 Etofenprox 0.01 Fenamidone 0.01 Fenamiphos 0.01 Fenamiphos sulfone 0.01 Fenamiphos sulfoxide 0.01 Fenarimol 0.01 Fenazaquin 0.01 Fenbuconazole 0.01 Fenhexamid 0.01 Fenitrothion 0.01 -
744 Hydrolysis of Chiral Organophosphorus Compounds By
[Frontiers in Bioscience, Landmark, 26, 744-770, Jan 1, 2021] Hydrolysis of chiral organophosphorus compounds by phosphotriesterases and mammalian paraoxonase-1 Antonio Monroy-Noyola1, Damianys Almenares-Lopez2, Eugenio Vilanova Gisbert3 1Laboratorio de Neuroproteccion, Facultad de Farmacia, Universidad Autonoma del Estado de Morelos, Morelos, Mexico, 2Division de Ciencias Basicas e Ingenierias, Universidad Popular de la Chontalpa, H. Cardenas, Tabasco, Mexico, 3Instituto de Bioingenieria, Universidad Miguel Hernandez, Elche, Alicante, Spain TABLE OF CONTENTS 1. Abstract 2. Introduction 2.1. Organophosphorus compounds (OPs) and their toxicity 2.2. Metabolism and treatment of OP intoxication 2.3. Chiral OPs 3. Stereoselective hydrolysis 3.1. Stereoselective hydrolysis determines the toxicity of chiral compounds 3.2. Hydrolysis of nerve agents by PTEs 3.2.1. Hydrolysis of V-type agents 3.3. PON1, a protein restricted in its ability to hydrolyze chiral OPs 3.4. Toxicity and stereoselective hydrolysis of OPs in animal tissues 3.4.1. The calcium-dependent stereoselective activity of OPs associated with PON1 3.4.2. Stereoselective hydrolysis commercial OPs pesticides by alloforms of PON1 Q192R 3.4.3. PON1, an enzyme that stereoselectively hydrolyzes OP nerve agents 3.4.4. PON1 recombinants and stereoselective hydrolysis of OP nerve agents 3.5. The activity of PTEs in birds 4. Conclusions 5. Acknowledgments 6. References 1. ABSTRACT Some organophosphorus compounds interaction of the racemic OPs with these B- (OPs), which are used in the manufacturing of esterases (AChE and NTE) and such interactions insecticides and nerve agents, are racemic mixtures have been studied in vivo, ex vivo and in vitro, using with at least one chiral center with a phosphorus stereoselective hydrolysis by A-esterases or atom. -
Organophosphate Insecticides
CHAPTER 4 HIGHLIGHTS Organophosphate Insecticides Acts through phosphorylation of the acetylcholinesterase enzyme Since the removal of organochlorine insecticides from use, organophosphate at nerve endings insecticides have become the most widely used insecticides available today. More Absorbed by inhalation, than forty of them are currently registered for use and all run the risk of acute ingestion, and skin and subacute toxicity. Organophosphates are used in agriculture, in the home, penetration in gardens, and in veterinary practice. All apparently share a common mecha- Muscarinic, nicotinic & CNS nism of cholinesterase inhibition and can cause similar symptoms. Because they effects share this mechanism, exposure to the same organophosphate by multiple routes or to multiple organophosphates by multiple routes can lead to serious additive Signs and Symptoms: toxicity. It is important to understand, however, that there is a wide range of Headache, hypersecretion, toxicity in these agents and wide variation in cutaneous absorption, making muscle twitching, nausea, specific identification and management quite important. diarrhea Respiratory depression, seizures, loss of consciousness Toxicology Miosis is often a helpful Organophosphates poison insects and mammals primarily by phosphory- diagnostic sign lation of the acetylcholinesterase enzyme (AChE) at nerve endings. The result is a loss of available AChE so that the effector organ becomes overstimulated by Treatment: the excess acetylcholine (ACh, the impulse-transmitting substance) in the nerve Clear airway, improve tissue ending. The enzyme is critical to normal control of nerve impulse transmission oxygenation from nerve fibers to smooth and skeletal muscle cells, glandular cells, and Administer atropine sulfate autonomic ganglia, as well as within the central nervous system (CNS). -
The More I Learned About the Use of Pesticides, the More
PESTICIDE P.3 ACTION WELCOME NETWORK “The more I learned about 1 2 EUROPE P.7 WHO WE ARE & WHAT WE DO 2 0 the use of pesticides, the POLITICAL 3 1 9 UPDATES ON EU P.11 ANNUAL PESTICIDE POLICY REVIEW more appalled I became... OUR HISTORY 4 & ACTION ON P.14 5 THE SUD What I discovered was that P.16 AGRICULTURE PESTICIDE RISK6 ASSESSMENT everything which meant most P.18 REFORM ENDOCRINE 7 DISRUPTING to me as a naturalist was P.20 CHEMICALS 8 SAVE BEES being threatened, and that P.23 & FARMERS! EU NETWORK 9 OF PESTICIDE- FREE TOWNS P.25 nothing I could do would COURT CASES10 & CONFLICT P.28 OF INTEREST be more important.” OTHER RELEVANT11 WORK AREAS & INSIDE Rachel Carson, 1962 Biologist & Author of Silent Spring RESULTS IN 2019 PAN EUROPE12 eflecting on our work as was evident upon the accession of in 2019, it has been an the new European Commission and WELCOME incredible and challenging publication of its flagship Green Deal. year. The key issues we have been working at PAN As PAN, we have been on the frontline Europe have come under of civil society action, working on EU Message from the President Rthe spotlight at national, EU and even pesticide-related policies. We have strived world level. Mounting scientific evidence to achieve a higher level of protection Francois Veillerette1 keeps revealing the severe effects of from pesticides and at the same time PAN Europe President pesticides on human health and the we showed that working with nature & Director of Générations Futures environment, with insect “Armageddon” is the way forward.