Utilisation of LC/MSMS (QTRAP) and Polarity Switching for the Quantitative Analysis of Over 300 Pesticides in Crude Quechers
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Routine Multipesticide Analysis Orbitrap
Routine Multi-Pesticide Residue Analysis by Orbitrap MS Technology Osama Abu-Nimreh CMD Sales Support Specialist MECEC , Dubai The world leader in serving science Challenges of Pesticide-Residues Analysis • Sample variability (matrix) • Different compound characteristics • Large number of samples • Hundreds of analytes monitored • Low levels controlled • Baby food (MRL for all pesticides = 0.01 mg/kg) • Fast response required 2 Former Pesticide Multi-Residue Method Setup . Extraction Acetonitrile, Ethyl Mostly replaced acetate, Methanol... by QuEChERS today . Clean-up GPC, SPE, LLE, LC . Determination GC, LC, GC-MS, LC-MS, Thermo Scientific™ QuEChERS™ GC-MS/MS, LC-MS/MS... method 3 Simplified Extraction Procedure Applied 10 g of sample is weighed into Quechers extraction tube + 20 mL of water + 10 mL of ACN shaking 10 min Centrifugation 5 min @ 5000 rpm Injection to LC-HRAM 4 Consumables Used Consumables/Chemicals Part Number Acetonitrile A/0638/17 QuEChERS extraction tube, 50 mL, 250 pack 60105-216 QuEChERS pouches, 50 pack 60105-344 Apparatus/Columns Part Number Horizontal shaker 1069-3391 Horizontal shaker plate 1053-0102 Thermo Scientific™ Barnstead™ EASYpure™II water 3125753 Thermo Scientific™ Heraeus™ Fresco™ 17 micro centrifuge 3208590 Thermo Scientific™ Accucore™ aQ column 100x2.1, 2.6 µm 17326-102130 5 Improving QuEChERS Extraction Tips & Tricks: • Dry food (cereals/dried food, < 25 % water content): • Addition of water to enable adequate partitioning and reducing interaction of pesticides with matrix • Food containing fat/wax (avocado/oil): • After extraction step add a freezing out step and transfer supernatant to clean-up tube • More clean-up might be needed of raw extract (PSA+C18) • Food containing complex matrix (tea/spices) • Additional clean-up with GCB might be necessary (potential loss of planar structure pesticides like thiabendazole) • Acidic food (citrus): • Adjust pH (5-5.5) to increase recovery (e.g. -
Historical Perspectives on Apple Production: Fruit Tree Pest Management, Regulation and New Insecticidal Chemistries
Historical Perspectives on Apple Production: Fruit Tree Pest Management, Regulation and New Insecticidal Chemistries. Peter Jentsch Extension Associate Department of Entomology Cornell University's Hudson Valley Lab 3357 Rt. 9W; PO box 727 Highland, NY 12528 email: [email protected] Phone 845-691-7151 Mobile: 845-417-7465 http://www.nysaes.cornell.edu/ent/faculty/jentsch/ 2 Historical Perspectives on Fruit Production: Fruit Tree Pest Management, Regulation and New Chemistries. by Peter Jentsch I. Historical Use of Pesticides in Apple Production Overview of Apple Production and Pest Management Prior to 1940 Synthetic Pesticide Development and Use II. Influences Changing the Pest Management Profile in Apple Production Chemical Residues in Early Insect Management Historical Chemical Regulation Recent Regulation Developments Changing Pest Management Food Quality Protection Act of 1996 The Science Behind The Methodology Pesticide Revisions – Requirements For New Registrations III. Resistance of Insect Pests to Insecticides Resistance Pest Management Strategies IV. Reduced Risk Chemistries: New Modes of Action and the Insecticide Treadmill Fermentation Microbial Products Bt’s, Abamectins, Spinosads Juvenile Hormone Analogs Formamidines, Juvenile Hormone Analogs And Mimics Insect Growth Regulators Azadirachtin, Thiadiazine Neonicotinyls Major Reduced Risk Materials: Carboxamides, Carboxylic Acid Esters, Granulosis Viruses, Diphenyloxazolines, Insecticidal Soaps, Benzoyl Urea Growth Regulators, Tetronic Acids, Oxadiazenes , Particle Films, Phenoxypyrazoles, Pyridazinones, Spinosads, Tetrazines , Organotins, Quinolines. 3 I Historical Use of Pesticides in Apple Production Overview of Apple Production and Pest Management Prior to 1940 The apple has a rather ominous origin. Its inception is framed in the biblical text regarding the genesis of mankind. The backdrop appears to be the turbulent setting of what many scholars believe to be present day Iraq. -
40 CFR Ch. I (7–1–18 Edition) § 455.61
§ 455.61 40 CFR Ch. I (7–1–18 Edition) from: the operation of employee show- § 455.64 Effluent limitations guidelines ers and laundry facilities; the testing representing the degree of effluent of fire protection equipment; the test- reduction attainable by the applica- ing and emergency operation of safety tion of the best available tech- showers and eye washes; or storm nology economically achievable water. (BAT). (d) The provisions of this subpart do Except as provided in 40 CFR 125.30 not apply to wastewater discharges through 125.32, any existing point from the repackaging of microorga- source subject to this subpart must nisms or Group 1 Mixtures, as defined achieve effluent limitations rep- under § 455.10, or non-agricultural pes- resenting the degree of effluent reduc- ticide products. tion attainable by the application of the best available technology economi- § 455.61 Special definitions. cally achievable: There shall be no dis- Process wastewater, for this subpart, charge of process wastewater pollut- means all wastewater except for sani- ants. tary water and those wastewaters ex- § 455.65 New source performance cluded from the applicability of the standards (NSPS). rule in § 455.60. Any new source subject to this sub- § 455.62 Effluent limitations guidelines part which discharges process waste- representing the degree of effluent water pollutants must meet the fol- reduction attainable by the applica- lowing standards: There shall be no dis- tion of the best practicable pollut- charge of process wastewater pollut- ant control technology (BPT). ants. Except as provided in 40 CFR 125.30 through 125.32, any existing point § 455.66 Pretreatment standards for existing sources (PSES). -
4. Chemical and Physical Information
PYRETHRINS AND PYRETHROIDS 131 4. CHEMICAL AND PHYSICAL INFORMATION 4.1 CHEMICAL IDENTITY The naturally-occurring pyrethrins, extracted from chrysanthemum flowers, are esters of chrysanthemic acid (Pyrethrin I, Cinerin I, and Jasmolin I) and esters of pyrethric acid (Pyrethrin II, Cinerin II, and Jasmolin II). In the United States, the pyrethrum extract is standardized as 45–55% w/w total pyrethrins. The typical proportion of Pyrethrins I to II is 0.2:2.8, while the ratio of pyrethrins:cinerins:jasmolins is 71:21:7 (Tomlin 1997). Information regarding the chemical identity of the pyrethrins is presented in Table 4-1. Pyrethroids are synthetic esters derived from the naturally-occurring pyrethrins. One exception to the axiom that all pyrethroids are esters of carboxylic acids is noteworthy. There is a group of oxime ethers that exhibits insecticidal activity similar in nature to the pyrethrins and pyrethroid esters (Davies 1985). Little data exist regarding these compounds, and no commercial products have been produced. Commercially available pyrethroids include allethrin, bifenthrin, bioresmethrin, cyfluthrin, cyhalothrin, cypermethrin, deltamethrin, esfenvalerate (fenvalerate), flucythrinate, flumethrin, fluvalinate, fenpropathrin, permethrin, phenothrin, resmethrin, tefluthrin, tetramethrin, and tralomethrin. Information regarding the chemical identity of pyrethroids is shown in Table 4-2. With the exception of deltamethrin, pyrethroids are a complex mixture of isomers rather than one single pure compound. For pyrethroids possessing the cyclopropane moiety, isomerism about the cyclopropane ring greatly influences the toxicity of these insecticides. The presence of two chiral centers in the ring results in two pairs of diastereomers. The diastereomers and their nonsuperimposable mirror images (enantiomers) are illustrated in Figure 4-1. -
Quantitative Determination of Pyrethroids, Pyrethrins, and Piperonyl Butoxide in Surface Water by High-Resolution Gas Chromatography/High-Resolution Mass Spectrometry
J. Agric. Food Chem. 2006, 54, 6957−6962 6957 Quantitative Determination of Pyrethroids, Pyrethrins, and Piperonyl Butoxide in Surface Water by High-Resolution Gas Chromatography/High-Resolution Mass Spectrometry MILLION BEKELE WOUDNEH* AXYS Analytical Services Ltd., 2045 Mills Road West, Sidney, British Columbia V8L 3S8, Canada DANIEL RAY OROS San Francisco Estuary Institute, 7770 Pardee Lane, 2nd Floor, Oakland, California 94621 A new method for determination of pyrethroids, pyrethrins, and piperonyl butoxide (PBO) by high- resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) was developed for surface water samples. The method is based on sampling 100 L of ambient surface water with a solid phase extraction (SPE) technique that uses both wound glass fiber filters for collecting the particulate-associated chemicals and XAD-2 resin for collecting the dissolved chemicals. The method detection limits of the analytes ranged from 0.58 to 8.16 ng/sample, which is equivalent to a detection limit range of 0.0058-0.082 ng/L for a 100 L water sample collected by the SPE technique. The SPE when coupled with HRGC/HRMS was a suitable match for detecting these chemicals at subnanogram per liter ranges that are toxicologically significant to aquatic organisms. To confirm the utility of this method for environmental applications, pyrethroids and PBO were found at subnanogram per liter concentrations in surface water samples collected from five tributaries (primarily urban creeks) of the San Francisco Bay, California. KEYWORDS: Pyrethroids; pesticides; XAD-2; HRGC/HRMS; San Francisco Bay INTRODUCTION by inhibiting a group of enzymes (mixed-function oxidases) that are involved in pyrethroid detoxification, which as a result The decision of the U.S. -
EWG VERIFIED™ Products Cannot Contain Any of the Ingredients Outlined in This Document
EWG’S UNACCEPTABLE LIST: Baby Diapers EWG VERIFIED™ products cannot contain any of the ingredients outlined in this document. Appendix A. Substances prohibited inEWG VERIFIED diapers based on GHS hazard classifications. A = aquatic toxicity, C = carcinogenicity, D = reproductive toxicity (development), F = reproductive toxicity (fertility), L = reproductive toxicity (lactation [breast-feeding children]), M = mutagenic, Sr = sensitization (respiratory), Ss =sensitization (skin) Chemical name(s) EC Number(s) CAS Number(s) Hazards ((4-phenylbutyl)hydroxyphosphoryl)acetic acid 412-170-7 83623-61-4 Ss (-)(3S,4R)-4-(4-fluorophenyl)-3-(3,4-methylenedioxy-phenoxymethyl)-N-benzylpiperidine hydrochloride 432-360-3 105813-13-6 SsA (+)-(1S,2S,3S,5R)-2,6,6-trimethylbicyclo[3.1.1]heptane-3-spiro-1'-(cyclohex-2'-en-4'-one) 430-460-1 133636-82-5 SsA (+/-)-(R*,R*)-6-fluoro-3,4-dihydro-2-oxiranyl-2H-1-benzopyran; 6-fluoro-2-(2-oxiranyl)chromane 419-620-1 - Ss (±) trans-3,3-dimethyl-5-(2,2,3-trimethyl-cyclopent-3-en-1-yl)-pent-4-en-2-ol 411-580-3 107898-54-4 A (±)-[(R*,R*) and (R*,S*)]-6-fluoro-3,4-dihydro-2-oxiranyl-2H-1-benzopyran 419-600-2 99199-90-3 Ss (±)-4-(3-chlorophenyl)-6-[(4-chlorophenyl)hydroxy(1-methyl-1H-imidazol-5-yl)methyl]-1-methyl-2(1H)-quinolin 430-730-9 - A (±)-4-[2-[[3-(4-hydroxyphenyl)-1-methylpropyl]amino]-1-hydroxyethyl]phenol hydrochloride 415-170-5 90274-24-1 Ss (±)-α-[(2-acetyl-5-methylphenyl)-amino]-2,6-dichlorobenzene-aceto-nitrile 419-290-9 Ss (1,3,4,5,6,7-hexahydro-1,3-di-oxo-2H-isoindol-2-yl)methyl (1R-trans)-2,2-dimethyl-3-(2-methylprop-1- -
Environmental Health Criteria 87 Allethrins
Environmental Health Criteria 87 Allethrins Please note that the layout and pagination of this web version are not identical with the printed version. Allethrins (EHC 87, 1989) INTERNATIONAL PROGRAMME ON CHEMICAL SAFETY ENVIRONMENTAL HEALTH CRITERIA 87 ALLETHRINS - Allethrin - d-Allethrin - Bioallethrin - S-Bioallethrin This report contains the collective views of an international group of experts and does not necessarily represent the decisions or the stated policy of the United Nations Environment Programme, the International Labour Organisation, or the World Health Organization. Published under the joint sponsorship of the United Nations Environment Programme, the International Labour Organisation, and the World Health Organization World Health Orgnization Geneva, 1989 The International Programme on Chemical Safety (IPCS) is a joint venture of the United Nations Environment Programme, the International Labour Organisation, and the World Health Organization. The main objective of the IPCS is to carry out and disseminate evaluations of the effects of chemicals on human health and the quality of the environment. Supporting activities include the development of epidemiological, experimental laboratory, and risk-assessment methods that could produce internationally comparable results, and the development of manpower in the field of toxicology. Other activities carried out by the IPCS include the development of know-how for coping with chemical accidents, coordination of laboratory testing and epidemiological studies, and promotion of research on the mechanisms of the biological action of chemicals. ISBN 92 4 154287 X The World Health Organization welcomes requests for permission to reproduce or translate its publications, in part or in full. Applications and enquiries should be addressed to the Office of Publications, World Health Organization, Geneva, Switzerland, which will be glad to provide the latest information on any changes made to the text, plans for new editions, and reprints and translations Page 1 of 46 Allethrins (EHC 87, 1989) already available. -
Multi-Residue Analysis of 210 Pesticides in Food Samples by Triple Quadrupole UHPLC-MS/MS
Multi-Residue Analysis of 210 Pesticides in Food Samples by Triple Quadrupole UHPLC-MS/MS David R. Baker1, Chris Titman1, Alan J. Barnes1, Neil J. Loftus1, Alexander Mastoroudes2, Simon Hird3 1Shimadzu Corporation, Manchester, UK 2Kings College London, London, UK 3Food and Environment Research Agency, York, UK Abstract Pesticides and their metabolites are of great concern to society as they are harmful to human health, pollute natural resources and disturb the equilibrium of the ecosystem. Consequently, stricter food safety regulations are being enforced around the world, placing pesticide analysis laboratories under increasing pressure to expand the list of targeted pesticides, detect analytes at lower levels and with greater precision, reduce analysis turnaround times, and all the while maintaining or reducing costs. In this study a method was successfully developed for the quantitation of 210 commonly analysed pesticides in food samples using the Nexera UHPLC and LCMS-8040. Initial validation was performed to demonstrate instrument capabilities. Limits of detection (LOD) for 90 % of compounds were less than 0.001 mg kg-1 (1 ppb) and all compounds were less than 0.01 mg kg-1 (10 ppb) for both the quantifying and qualifying transitions using only a 2 µL injection. Repeatability at the 0.01 mg kg-1 reporting level was typically less than 5 %RSD for compounds and correlation coefficients were typically greater than 0.997 in a variety of studied food extracts. Consequently, the LCMS-8040 is ideally suited for routine monitoring of pesticides below the 0.01 mg kg-1 default level set by EU and Japanese legislation. Keywords: Pesticides; Multi-residue analysis; LCMS-8040; Food safety; Fruit; Vegetables 1. -
Pyrethroid Insecticides: Use, Environmental Fate, and Ecotoxicology
11 Pyrethroid Insecticides: Use, Environmental Fate, and Ecotoxicology Katherine Palmquist, Johanna Salatas and Anne Fairbrother Exponent United States 1. Introduction There was little public concern over potential nontarget effects of pesticides until the 1962 publication of Rachel Carson’s Silent Spring (Delaplane, 2000; Moore et al., 2009). Organochlorine insecticides (such as DDT) had been used intensively and were credited for many of the problems highlighted by Carson. Because of their accumulation in the environment and reproductive toxicity in people, their use was eventually phased out in most industrialized countries in the late 1970s and early 1980s (Moore et al., 2009). Organophosphate (OPs) and carbamate pesticides (based on the same chemistry and mode of action as nerve gas used by the military) took the place of the organochlorine products and have been widely used since the late 1970s. For the past three decades, OP pesticides have been the insecticides most commonly used by professional pest-control bodies and homeowners (Feo et al., 2010). However, in the late 1980s, OPs in California came under scrutiny when they began to show up in groundwater samples. In addition, because of their potentially toxic effects on people, The U.S. Environmental Protection Agency (EPA) considered a ban on both OP and carbamate insecticides as part of the Food Quality Protection Act (FQPA) of 1996. The FQPA mandated that the EPA reassess all pesticide tolerance levels considering aggregate exposures, cumulative effects from pesticides sharing common mechanisms of toxicity, and special protection for infants and children (Metcalfe et al. 2002). During the early 2000s, the EPA began phasing out residential uses of the two primary OPs, diazinon, and chlorpyrifos (CDPR 2008). -
Parameters for Pyrethroid Insecticide QSAR and PBPK/PD Models for Human Risk Assessment
Parameters for Pyrethroid Insecticide QSAR and PBPK/PD Models for Human Risk Assessment (March 13, 2012) James B. Knaak*, Curtis C. Dary, Xiaofei Zhang, Robert W. Gerlach, R. Tornero-Velez, Daniel T. Chang, Rocky Goldsmith and Jerry N. Blancato J.B. Knaak* (Corresponding author: [email protected]) Department of Pharmacology and Toxicology, School of Medicine and Biomedical Sciences, SUNY at Buffalo, 3435 Main Street, Buffalo, NY 14214, USA. C.C. Dary U.S. Environmental Protection Agency, Human Exposure and Atmospheric Sciences Division, 944 East Harmon Avenue, Las Vegas, NV 89193-3478, USA. R.W. Gerlach ڄ X. Zhang General Dynamics Information Technology, 181 North Arroyo Grande Boulevard, Suite 105A, Henderson, NV 89074-1624, USA. ;R. Goldsmith, Mail Code E205-01 ڄ D. Chang ڄ R. Tornero-Velez J.N. Blancato, Mail Code B143-04 U.S. Environmental Protection Agency, National Exposure Research Laboratory, 109 T.W. Alexander Drive, Research Triangle Park, NC 27709, USA. 1 2 Contents 1 Introduction ..............................................................................................................................x 2 Nature of Pyrethrin and Pyrethroid Insecticides ......................................................................x 2.1 Discovery .......................................................................................................................x 2.2 Isomers and Technical Products ....................................................................................x 2.3 Stereochemistry..............................................................................................................x -
Method 1660: the Determination of Pyrethrins and Pyrethroids in Municipal and Industrial Wastewater
Office of Water www.epa.gov August 1993 Method 1660: The Determination of Pyrethrins and Pyrethroids in Municipal and Industrial Wastewater Method 1660 The Determination of Pyrethrins and Pyrethroids in Municipal and Industrial Wastewater Method 1660 The Determination of Pyrethrins and Pyrethroids in Municipal and Industrial Wastewater 1. SCOPE AND APPLICATION 1.1 This method covers the determination of pyrethrins and pyrethroids in wastewater by extraction and high-performance liquid chromatography (HPLC) with an ultra-violet detector (UV). The compounds in Table 1 may be determined by this method. 1.2 This method is designed to meet the monitoring requirements of the U.S. Environmental Protection Agency under the Clean Water Act at 40 CFR Part 455. Any modification of this method beyond those expressly permitted shall be considered a major modification subject to application and approval of alternative test procedures under 40 CFR 136.4 and 136.5. 1.3 When this method is applied to analysis of unfamiliar samples, compound identity must be supported by at least one additional qualitative technique. This method lists a second UV wavelength that can be used to confirm measurements made with the primary wavelength. 1.4 This method is specific to the determination of two pyrethrins and seven pyrethroids, but should be applicable to other pyrethroids as well. The quality control requirements in this method give the steps necessary to determine this applicability. 1.5 The detection limit of this method is usually dependent on the level of interferences rather than instrumental limitations. The limits in Table 2 typify the minimum quantity that can be detected with no interferences present. -
Pyrethrum Secondary Metabolism: Biosynthesis, Localization and Ecology of Defence Compounds
Pyrethrum Secondary Metabolism: Biosynthesis, Localization and Ecology of Defence Compounds Aldana Ramirez Thesis committee Promotors Prof. dr.ir. H.J. Bouwmeester Professor of Plant Physiology Wageningen University Prof. dr. M. Dicke Professor of Entomology Wageningen University Thesis co-supervisor Dr.ir. M. A. Jongsma Senior scientist, Plant Research International Wageningen University and Research Center Other members Prof.dr.ir. N.P.R. Anten, Wageningen University Prof. A. Tissier, Leibniz Institute of Plant Biochemistry, Halle, Germany Dr. K. Posthuma, Enza Zaden, Research & Development B.V., Enkhuizen Dr. M.C.R. Franssen, Wageningen University This research was conducted under the auspices of the Graduate School of Experimental Plant Sciences Pyrethrum Secondary Metabolism: Biosynthesis, Localization and Ecology of Defence Compounds Aldana Ramirez Thesis submittted in fulfillment of the requirements for the degree of doctor at Wageningen University by the authority of the Rector Magnificus Prof. dr. M.J. Kropff, in the presence of the Thesis Committee appointed by the Academic Board to be defended in public on Friday 3 May 2013 at 1.30 p.m. in the Aula. Aldana Ramirez Pyrethrum Secondary Metabolism: Biosynthesis, Localization and Ecology of Defence Compounds, 190 pages Thesis, Wageningen University, Wageningen, NL (2013) With references, with summaries in Dutch and English ISBN 978-94-6173-517-1 “Consistency is the last refuge of the unimaginative” Oscar Wilde Contents Chapter 1 General introduction. 9 Chapter 2 Bidirectional secretions from glandular trichomes 27 of pyrethrum enable immunization of seedlings. Chapter 3 A single cytochrome P450 enzyme catalyses the 63 formation of chrysanthemic acid from chrysanthemol in pyrethrin biosynthesis. Chapter 4 Cloning and characterization of a trichome-specific 101 13-lipoxygenase expressed during pyrethrin biosynthesis in pyrethrum (Tanacetum cinerariifolium).