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EPA Method 538: Determination of Selected Organic Contaminants in Drinking Water with Direct Aqueous Injection LC/MS/MS

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EPA Method 538: Determination of Selected Organic Contaminants in Drinking Water with Direct Aqueous Injection LC/MS/MS E. Michael Thurman and Imma Ferrer Center for Environmental Mass Spectrometry University of Colorado Boulder, CO, USA Confidentiality Label 1 March 20, 2012 Abstract EPA Method 538 is a new method from EPA for organophosphate pesticides in drinking water. It uses direct aqueous injection; thus, no sample preparation is needed. We use both UHPLC (Agilent 1290) and MS/MS (Agilent 6460) analysis for rapid analysis and sensitive detection with ng/L limits of detection. A second MRM is added for more reliable identification. Confidentiality Label 2 March 20, 2012 Hypothesis Direct injection of organophosphate pesticides (EPA Method 538) will work by UHPLC (Agilent Model 1290) and LC/MS/MS with Jetstream (Agilent Model 6460) with trace level detection at ng/L concentrations. Confidentiality Label 3 March 20, 2012 1. Introduction-Summary 1.1 EPA Method 538 (published in November 2009 by Shoemaker) deals with Organophosphate pesticides in drinking water (1) and one other contaminant, quinoline. 1.2 The method consists of 10 compounds: acephate, aldicarb, aldicarb sulfoxide, dicrotophos, diisopropylmethylphosphonate (DIMP), fenamiphos sulfone, fenamiphos sulfoxide, methamidophos, oxydemeton methyl, quinoline, and thiofanox with 5 labeled internal standards. 1.3 Direct aqueous injection is used with a large volume sample of 100 microliters; thus, no sample preparation is needed. 1.4 Because solid phase extraction (i.e. concentration of the sample is not carried out) suppression is mimimized in the analysis. 1.5 Part-per-Trillion Detection Limits. Confidentiality Label 4 March 20, 2012 Introduction 1.1: EPA Method 538: Determination of Selected Organic Contaminants in Drinking Water by Direct Aqueous Injection by Jody Shoemaker, EPA Cincinnati, OH [email protected] 513-569-7298 Confidentiality Label 5 March 20, 2012 Introduction: 1.2. Ten Organophosphates and Quinoline Confidentiality Label 6 March 20, 2012 Introduction:1.3. Organophosphate Structures Aldicarb Sulfoxide Acephate Aldicarb O O O O O O N N P NH NH H3C N OCH3 H S S O SCH3 + + + C4H11NO3PS C7H15N2O2S C7H15N2O3S Exact Mass: 184.0192 Exact Mass: 191.0849 Exact Mass: 207.0798 Fenamiphos Sulfone Dicro.tophos Diisopropyl methylphosphonate (DIMP) H3C O N O O H O P O N CH3 H3C O P P O O O O O CH O 3 . S C H NO P+ 8 17 5 C H O P+ Exact Mass: 238.0839 7 18 3 . Exact Mass: 181.0988 O + C13H23NO5PS Exact Mass: 336.1029 Confidentiality Label 7 March 20, 2012 Introduction 1.3. Organophosphate Structures Fenamiphos Sulfoxide Methamidophos Oxydemeton-methyl H3C O O H S O N CH P H C O 3 O S P 3 H N P 2 S O O O O CH3 + O C2H9NO2PS S + Exact Mass: 142.0086 C6H16O4PS2 Exact Mass: 247.0222 + Thiofanox C13H23NO4PS Exact Mass: 320.108 Quinoline N O N S HN O C H N+ 9 8 C H N O S+ Exact Mass: 130.0651 9 19 2 2 Exact Mass: 219.1162 Confidentiality Label 8 March 20, 2012 Introduction 1.4. Five Deuterated Standards Confidentiality Label 9 March 20, 2012 Introduction 1.4. Deuterated Internal Standards Diisopropylmethylphosphonate-d14 (DIMP-d14) Acephate-d6 Methamidophos-d6 O O O O O P O CD3 P P O H3C N OCD3 D C CD H2N CD3 H 3 3 S SCD3 D CD D C D 3 3 + + C2H3D6NO2PS C4H5D6NO3PS + Exact Mass: 148.0463 Exact Mass: 190.0568 C7H4D14O3P Exact Mass: 195.1867 Quinoline-d7 Oxydemeton-methyl-d6 D D N D S O S P CD3 CD O O 3 O D D C H D O PS + 6 10 6 4 2 D D Exact Mass: 253.0599 + C9HD7N Exact Mass: 137.1091 Confidentiality Label 10 March 20, 2012 Introduction 1.5 No solid-phase extraction! 1.Sorption on C-18 or 100-200 mL sample polymer. 2. Washing and cleanup. Condition cartridge Elute with Methanol with Methanol and (5 mL) to remove 50% of the WaterTime and Effortpesticides or 3. Elution and AnalysisRemoved. from Analysispharmaceuticals Cartridges: - C18, polymeric - Oasis HLB, OPT Effluent to waste Confidentiality Label 11 March 20, 2012 Introduction 1.6 Minimizing Compound Suppression •SPE increases background organic matrix by 200 to 500 fold OH •Salts, such as sodium and metal ions, are also concentrated along with the background organic matrix ClFeOOC •These salts suppress the ionization of target analytes. OH HO OH OH O OH O NaOOC O O NaOOC Confidentiality Label 12 March 20, 2012 Introduction 1.6 Direct Aqueous Injection with the 1290 Infinity—UHPLC and 6460 LC/MS/MS Confidentiality Label 13 March 20, 2012 2.0 Experimental Methods: Summary 1. Collect 40 mL sample and preserve with sodium omadine and ammonium acetate. 2. Aliquot 950 µL of sample and add 50 µL of internal standard. 3. Analyze by UHPLC/MS/MS with the Agilent 1290 LC and the Agilent Model 6460 LC/MS/MS. Confidentiality Label 14 March 20, 2012 Experimental Methods 2.1 MRM Transitions for QqQ Method Compound Name Precursor Ion Product Ion Dwell Fragmentor Collision Energy Polarity Acephate 206 165 10 90 5 Positive Acephate 184 143 10 50 0 Positive Aldicarb 213 116 10 90 5 Positive Aldicarb 213 89 10 90 15 Positive Aldicarb-Sulfoxide 229 166 10 70 5 Positive Aldicarb-Sulfoxide 229 109 10 70 10 Positive Dicrotophos 238 193 10 70 0 Positive Dicrotophos 238 112 10 70 5 Positive DIMP 181 139 10 70 0 Positive DIMP 181 97 10 70 5 Positive Fenamiphos-Sulfone 336 308 10 110 10 Positive Fenamiphos-Sulfone 336 266 10 110 15 Positive Fenamiphos-Sulfoxide 320 292 10 110 10 Positive Fenamiphos-Sulfoxide 320 233 10 110 20 Positive Methamidophos 142 125 10 70 10 Positive Methamidophos 142 94 10 70 10 Positive Oxydemeton-methyl 269 191 10 110 5 Positive Oxydemeton-methyl 247 169 10 70 10 Positive Quinoline 130 103 10 110 25 Positive Quinoline 130 77 10 110 35 Positive Thiofanox 241 184 10 90 5 Positive Thiofanox 241 57 10 90 15 Positive Confidentiality Label 15 March 20, 2012 Experimental Methods 2.2 Transitions for Deuterated Standards Compound Transition Frag. CE Acephate-d5 190149 50 0 DIMP –d14 19599 70 5 Methamidophos-d6 14897 70 10 Oxydemeton-methyl-d6 253175 70 10 Quinoline-d7 13781 110 35 Confidentiality Label 16 March 20, 2012 Experimental Methods 2.3 QqQ Experimental Source Parameters Confidentiality Label 17 March 20, 2012 3.0 Results and Discussion 1. EPA Method 538: Organophosphate Pesticides in Drinking Water. 2. Direct Aqueous Injection; Thus, No Sample Preparation Needed. 3. UHPLC/MS/MS Analysis with Minimal Suppression. 4. Part-per-Trillion Detection Limits. Confidentiality Label 18 March 20, 2012 3.1 Multiple Reaction Monitoring Quad Mass Filter (Q1) Quad Mass Filter (Q3) Ions Collision Cell Spectrum with Q1 lets only Collision cell Q3 monitors only background target ion 210 breaks ion 210 characteristic ions (from ESI) pass through apart fragments 158 and 191 from ion 210 210 210 for quant and 222 qual. 158 268 280 158 165 191 210 191 170 210 250 290 190 210 150 170 190 210 160 190 no chemical background Confidentiality Label 19 March 20, 2012 +ESI Product Ion:1 (0.400-0.546 min, 54 Scans) Frag=70.0V [email protected] (229.0 -> **) Aldicarb Sulfoxide_PI Scan Positive 229.d 3.2 Example: x10 4 8 CE=10V 166.0 Fragmentation 6 109.0 Study of Aldicarb 4 2 O O 91.9 0 4 +ESI Product Ion:2 (0.401-0.546 min, 54 Scans) Frag=70.0V [email protected] (229.0 -> **) Aldicarb Sulfoxide_PI Scan Positive 229.d N x10 NH 5 Na CE=15V 109.0 S O 4 3 2 + 166.0 [M+Na] = 229 1 91.9 0 +ESI Product Ion:3 (0.402-0.547 min, 54 Scans) Frag=70.0V [email protected] (229.0 -> **) Aldicarb Sulfoxide_PI Scan Positive 229.d O x10 5 O 1 N CE=5V 166.0 1 NH Na 0 0 0 109.0 m/z = 166 0 0 +ESI Product Ion:4 (0.402-0.548 min, 54 Scans) Frag=70.0V (229.0 -> **) Aldicarb Sulfoxide_PI Scan Positive 229.d x10 5 HO 1 N 1 CE=0V 1 Na 0 166.0 0 m/z = 109 0 0 108.9 0 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 Counts vs. Mass-to-Charge (m/z) Confidentiality Label 20 March 20, 2012 3.3 Extracted Ion Chromatograms of Compounds Column: C18 Eclipse Plus 2.1mm x 50mm, 1.8 um Mobile phase: A=ACN, B=H2O (0.1% Acetic Acid) Flow-rate: 0.4 mL/min Gradient: t=0min. 10% A/90% B t=1.7min. 10% A/90% B t=10 min. 100% B Injection volume: 40uL x10 5 1 1 3 2. 2. 2. Thiofanox 2. methyl DIMP 2 - Aldicarb Sulfoxide Aldicarb 1. 1. 1. 1. Oxydemeton 1 Aldicarb 0. Dicrotophos 0. Sulfone Fenamiphos Quinoline 0. Sulfoxide Fenamiphos Methamidophos Acephate 0. 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 2.8 3 3.2 3.4 3.6 3.8 4 4.2 4.4 4.6 4.8 5 5.2 5.4 5.6 5.8 6 6.2 6.4 6.6 6.8 7 7.2 7.4 7.6 7.8 8 8.2 8.4 8.6 8.8 9 9.2 9.4 9.6 9.8 10 10.2 Counts vs.
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    STATE OF WASHINGTON DEPARTMENT OF AGRICULTURE P.O. Box 42560 • Olympia, Washington 98504-2560 • (360) 902-1800 WASHINGTON STATE FENAMIPHOS USE SUMMARY • The products containing fenamiphos registered for use in Washington State are restricted use pesticides (RUP) and may be purchased and applied by only a certified applicator. • Fenamiphos is used to control a number of nematode pests. Nematodes can live as parasites on the outside or the inside of a plant. They may be free living or associated with cyst and root-knot formations in plants. • Fenamiphos is used on a wide variety of plants nationally including fruit, some vegetables, turf and grains. The compound is absorbed by the roots and translocated throughout the plant. • Fenamiphos blocks the enzyme acetylcholinesterase in the target pest. It also has secondary activity against other invertebrates such as sucking insects and spider mites. • Fenamiphos is available in emulsifiable concentrate, granular or emulsion formulations. It may also be found in formulations with other pesticides such as carbofuran and disulfoton. • Fenamiphos is classified toxicity class I - highly toxic. Products containing fenamiphos bear the signal word, “Danger.” Fenamiphos belongs to the organophosphate chemical class. • Fenamiphos is labeled for use on several crops in Washington State. (See table, “Product Names and Labeled Crops” provided below.) With the exception of red raspberries, it is not commonly used. WASS* EST. % EST. EST. LBS. 2001 EST. EST. LBS. # OF ACRES ACRES A.I. CROP ACRES A.I./ACRE APPS TREATED TREATED APPLIED PLANTED Red raspberries 9,500 10 3.0 1 950 2850 * Washington Agricultural Statistics Service Washington State Department of Agriculture/Endangered Species Program Page 1 of 4 http://agr.wa.gov/PestFert/EnvResources/EndangSpecies.htm November 2003 MAJOR USES (listed alphabetically): The major use listing supplies the most commonly used formulations of the active ingredient.
  • 744 Hydrolysis of Chiral Organophosphorus Compounds By

    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.
  • Chlorpyrifos: Time to Ban the Controversial Pesticide

    Chlorpyrifos: Time to Ban the Controversial Pesticide

    CHLORPYRIFOS: TIME TO BAN THE CONTROVERSIAL PESTICIDE FACULTY OF LAW VICTORIA UNIVERSITY OF WELLINGTON 2020 1 Abstract Chlorpyrifos is an organophosphate pesticide used worldwide. It is used extensively in agricultural sectors, eradicating pests through neurotoxicity. Chlorpyrifos is proven to be harmful to human health, particularly the developmental health of young children, as well as detrimental to non-target organisms such as bees, birds, fish and earthworms. New Zealand’s Environmental Protection Agency reassessed chlorpyrifos in 2012, concluding that it was too beneficial to New Zealand’s agricultural sector to phase out, proposing instead a new regulatory scheme. The reassessment was widely criticised as being deficient in evidence, external analysis and environmental concern. Similarly, the new regulations that emerged from the reassessment are non-specific, poorly policed and avoidant of user responsibility. Recent studies have proven the failure of the regulatory scheme in protecting the environment, with chlorpyrifos continuing to be found in high concentration in streams, hives and soil. This indicates the need for a complete ban of chlorpyrifos in New Zealand. California, Hawaii and New York have recently proposed a ban on chlorpyrifos in what hopefully indicates the beginning of a global movement. 2 I Introduction to Chlorpyrifos A Introduction For thousands of years, farming and agricultural practices, both within New Zealand and internationally, have relied on the extensive use of pesticides and insecticides as an aggressive form of pest control1. Public awareness of the detrimental effects attached to such widespread and often indiscriminate use of these high-toxicity chemicals, rose drastically in the mid 20th century with the publication of Rachel Carson’s Silent Spring2.