Quantitative Determination of Pyrethroids, Pyrethrins, and Piperonyl Butoxide in Surface Water by High-Resolution Gas Chromatography/High-Resolution Mass Spectrometry
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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. -
Characterization of Residential Pest Control Products Used in Inner City Communities in New York City
Journal of Exposure Science and Environmental Epidemiology (2010), 1–11 r 2010 Nature America, Inc. All rights reserved 1559-0631/10 www.nature.com/jes Characterization of residential pest control products used in inner city communities in New York City MEGAN K. HORTONa, J. BRYAN JACOBSONb, WENDY MCKELVEYb, DARRELL HOLMESa, BETTY FINCHERc, AUDREY QUANTANOc, BEINVENDIDA PAEZ DIAZc, FAYE SHABBAZZc, PEGGY SHEPARDc, ANDREW RUNDLEa AND ROBIN M. WHYATTa aColumbia Center for Children’s Environmental Health, Mailman School of Public Health, Columbia University, New York, New York, USA bNew York City Department of Health and Mental Hygiene, New York, New York, USA cWest Harlem Environmental Action, New York, New York, USA The Columbia Center for Children’s Environmental Health (CCCEH) previously reported widespread residential insecticide use in urban communities in New York City. Research suggests that pyrethroids are replacing organophosphates (OPs) in response to 2000–2001 US EPA pesticide regulations restricting OP use. A systematic assessment of active ingredients used for residential pest control is lacking. We queried a database of pesticide applications reported by licensed applicators between 1999 and 2005 and surveyed pest control products available in 145 stores within 29 zip codes in the CCCEH catchment area including Northern Manhattan and the South Bronx. Pyrethroids, pyrethrins, piperonyl butoxide, and hydramethylnon were the most common insecticide active ingredients reported as used by licensed pesticide applicators within the 29 zip codes of the CCCEH catchment area between 1999 and 2005. Use of certain pyrethroids and some non-spray insecticides such as fipronil and boric acid increased significantly by year (logistic regression, OR41.0, Po0.05), whereas use of OPs, including chlorpyrifos and diazinon decreased significantly by year (logistic regression, ORo1.0, Po0.05). -
Carpenter Ants and Control in Homes Page 1 of 6
Carpenter Ants and Control in Homes Page 1 of 6 Carpenter Ants and Control in Homes Fact Sheet No. 31 Revised May 2000 Dr. Jay B Karren, Extension Entomologist Alan H. Roe, Insect Diagnostician Introduction Carpenter ants are members of the insect order Hymenoptera, which includes bees, wasps, sawflies, and other ants. Carpenter ants can be occasional pests in the home and are noted particularly for the damage they can cause when nesting in wood. In Utah they are more of a nuisance rather than a major structural pest. Carpenter ants, along with a number of other ant species, utilize cavities in wood, particularly stumps and logs in decayed condition, as nesting sites. They are most abundant in forests and can be easily found under loose bark of dead trees, stumps, or fallen logs. Homeowners may bring them into their homes when they transport infested logs from forests to use as firewood. Description Carpenter ants include species that are among the largest ants found in the United States. They are social insects with a complex and well-defined caste system. The worker ants are sterile females and may occur in different sizes (majors and minors). Members of the reproductive caste (fertile males and females) are usually winged prior to mating. All ants develop from eggs deposited by a fertilized female (queen). The eggs hatch into grub-like larvae (immatures) which are fed and cared for by the workers. When fully grown, the larvae spin a cocoon and enter the pupal stage. The pupal stage is a period of transformation from the larva to adult. -
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. -
Pesticides EPA 738-R-06-004 Environmental Protection and Toxic Substances June 2006 Agency (7508C) ______Reregistration Eligibility Decision for Pyrethrins
United States Prevention, Pesticides EPA 738-R-06-004 Environmental Protection And Toxic Substances June 2006 Agency (7508C) _________________________________________________________________ Reregistration Eligibility Decision for Pyrethrins List B Case No. 2580 Reregistration Eligibility Decision (RED) Document for Pyrethrins Approved by: /S/ . Debra Edwards, Ph. D. Director Special Review and Reregistration Division Date: June 7, 2006 . Page 2 of 108 TABLE OF CONTENTS Executive Summary ....................................................................................................................... 7 I. Introduction......................................................................................................................... 11 II. Chemical Overview........................................................................................................... 12 A. Regulatory History...................................................................................................... 12 B. Chemical Identification .............................................................................................. 13 C. Use Profile.................................................................................................................... 16 1. Pyrethrins Use Profile................................................................................................. 16 III. Summary of Pyrethrins Risk Assessments ............................................................... 17 A. Human Health Risk Assessment............................................................................... -
RR Program's RCL Spreadsheet Update
RR Program’s RCL Spreadsheet Update March 2017 RR Program RCL Spreadsheet Update DNR-RR-052e The Wisconsin DNR Remediation and Redevelopment Program (RR) has updated the numerical soil standards in the August 2015 DNR-RR- 052b RR spreadsheet of residual contaminant levels (RCLs). The RCLs were determined using the U.S. EPA RSL web- calculator by accepting EPA exposure defaults, with the exception of using Chicago, IL, for the climatic zone. This documentThe U.S. provides EPA updateda summary its Regionalof changes Screening to the direct-contact Level (RSL) RCLs website (DC-RCLs) in June that2015. are To now reflect in the that March 2017 spreadsheet.update, the The Wisconsin last page ofDNR this updated document the has numerical the EPA exposuresoil standards, parameter or residual values usedcontaminant in the RCL levels calculations. (RCLs), in the Remediation and Redevelopment program’s spreadsheet of RCLs. This document The providesU.S. EPA a RSL summary web-calculator of the updates has been incorporated recently updated in the Julyso that 2015 the spreadsheet.most up-to-date There toxicity were values no changes for chemi - cals madewere certainlyto the groundwater used in the RCLs,RCL calculations. but there are However, many changes it is important in the industrial to note that and the non-industrial web-calculator direct is only a subpartcontact of the (DC) full RCLsEPA RSL worksheets. webpage, Tables and that 1 andthe other 2 of thissubparts document that will summarize have important the DC-RCL explanatory changes text, generic tablesfrom and the references previous have spreadsheet yet to be (Januaryupdated. -
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- -
Pesticide Incident Reporting and Tracking Review Panel
Agency Data 2004 PIRT 2005 Annual Report Pesticide Incident Reporting and Tracking Review Panel December 2005 PIRT Review Panel Representatives We wish to acknowledge and thank our panel representatives for their contributions: Chair Maryanne Guichard, Washington State Department of Health Coordinator Lucy Harter, Washington State Department of Health Members Ann Wick, Washington State Department of Agriculture Maria Victoria Peeler, Washington State Department of Ecology Vacant, Washington State Department of Fish and Wildlife Dorothy Tibbetts, Washington State Department of Health Gabrielle Toutonghi, Washington State Department of Labor and Industries Karen Ripley, Washington State Department of Natural Resources Alice Larson, PhD, General Public Steve Gilbert, PhD, DABT, Practicing Toxicologist Matthew Keifer, MD, MPH, University of Washington William Robertson, MD, Washington Poison Center Allan Felsot, PhD, Washington State University Pesticide Incident Reporting and Tracking Review Panel Annual Report A report to the legislature as required by Chapter 380, Laws of 1989, and RCW 70.104. December 2005 DOH 333-175 December 2005 To obtain copies or for additional information, see www.doh.wa.gov/pesticidecontact. This annual report is available online at www.doh.wa.gov/DataandStatisticalReports/EnvironmentalHealth/Pesticides.aspx. Report suspected pesticide-related illness to the Washington State Department of Health at 1-877-485-7316 or the Washington Poison Center at 1-800-222-1222. For people with disabilities, this document is available -
Ingleby Prohibited Pesticides May 2018
1[5] INGLEBY PROHIBITED PESTICIDES MAY 2018 Active ingredient Type Acaricides Cyhexatin Acaricide Parathion-ethyl Acaricide/Insecticide Tetradifon Acaricide Tebufenpyrad Acaricide Fumigants 1,2-Dibromoethane Fumigant 1,2-dichloroethane Fumigant Fungicides 2-Aminobutane (aka sec-butylamine) Fungicide Allyl alcohol Fungicide Benomyl Fungicide Binapacryl Fungicide Bitertanol Fungicide Blasticidin-S Fungicide Cadmium Fungicide Captafol Fungicide Chloranil Fungicide Chloromethoxypropyl-mercuric-acetate (CPMA) Fungicide Chlozolinate Fungicide Di(phenylmercury)dodecenylsuccinate (PMDS) Fungicide Diammonium ethylenebis Fungicide DNOC Fungicide / Herbicide /Insecticide Edifenphos Fungicide Fenarimol Fungicide Fentin acetate Fungicide Flusilazole Fungicide Hexachlorobenzene (HCB) Fungicide Hexaconazole Fungicide Iminoctadine Fungicide Leptophos Fungicide Maneb Fungicide Mercuric oxide Fungicide Mercurous chloride (calomel) Fungicide Mercury compounds Fungicide Nickel bis Fungicide Nuarimol Fungicide Oxadixyl Fungicide Penconazole Fungicide Ingleby Farms & Forests May 2018 Prohibited Active Ingredients 2[5] INGLEBY PROHIBITED PESTICIDES MAY 2018 Active ingredient Type Fungicides (continued) Phenylmercury acetate Fungicide/Herbicide Phenylmercuric oleate [PMO] Fungicide Prochloraz Fungicide Procymidone Fungicide Propineb Fungicide Pyrazophos Fungicide Pyrifenox Fungicide Tecnazene Fungicide Tricyclazole Fungicide Tridemorph Fungicide Vinclozolin Fungicide Zineb Fungicide Herbicides 2,4,5-T Herbicide Acifluorfen Herbicide Alachlor Herbicide Arsenic -
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.