40 CFR Ch. I (7–1–18 Edition) § 455.61
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2,4-Dichlorophenoxyacetic Acid
2,4-Dichlorophenoxyacetic acid 2,4-Dichlorophenoxyacetic acid IUPAC (2,4-dichlorophenoxy)acetic acid name 2,4-D Other hedonal names trinoxol Identifiers CAS [94-75-7] number SMILES OC(COC1=CC=C(Cl)C=C1Cl)=O ChemSpider 1441 ID Properties Molecular C H Cl O formula 8 6 2 3 Molar mass 221.04 g mol−1 Appearance white to yellow powder Melting point 140.5 °C (413.5 K) Boiling 160 °C (0.4 mm Hg) point Solubility in 900 mg/L (25 °C) water Related compounds Related 2,4,5-T, Dichlorprop compounds Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) 2,4-Dichlorophenoxyacetic acid (2,4-D) is a common systemic herbicide used in the control of broadleaf weeds. It is the most widely used herbicide in the world, and the third most commonly used in North America.[1] 2,4-D is also an important synthetic auxin, often used in laboratories for plant research and as a supplement in plant cell culture media such as MS medium. History 2,4-D was developed during World War II by a British team at Rothamsted Experimental Station, under the leadership of Judah Hirsch Quastel, aiming to increase crop yields for a nation at war.[citation needed] When it was commercially released in 1946, it became the first successful selective herbicide and allowed for greatly enhanced weed control in wheat, maize (corn), rice, and similar cereal grass crop, because it only kills dicots, leaving behind monocots. Mechanism of herbicide action 2,4-D is a synthetic auxin, which is a class of plant growth regulators. -
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. -
Herbicide Mode of Action Table High Resistance Risk
Herbicide Mode of Action Table High resistance risk Chemical family Active constituent (first registered trade name) GROUP 1 Inhibition of acetyl co-enzyme A carboxylase (ACC’ase inhibitors) clodinafop (Topik®), cyhalofop (Agixa®*, Barnstorm®), diclofop (Cheetah® Gold* Decision®*, Hoegrass®), Aryloxyphenoxy- fenoxaprop (Cheetah®, Gold*, Wildcat®), fluazifop propionates (FOPs) (Fusilade®), haloxyfop (Verdict®), propaquizafop (Shogun®), quizalofop (Targa®) Cyclohexanediones (DIMs) butroxydim (Factor®*), clethodim (Select®), profoxydim (Aura®), sethoxydim (Cheetah® Gold*, Decision®*), tralkoxydim (Achieve®) Phenylpyrazoles (DENs) pinoxaden (Axial®) GROUP 2 Inhibition of acetolactate synthase (ALS inhibitors), acetohydroxyacid synthase (AHAS) Imidazolinones (IMIs) imazamox (Intervix®*, Raptor®), imazapic (Bobcat I-Maxx®*, Flame®, Midas®*, OnDuty®*), imazapyr (Arsenal Xpress®*, Intervix®*, Lightning®*, Midas®* OnDuty®*), imazethapyr (Lightning®*, Spinnaker®) Pyrimidinyl–thio- bispyribac (Nominee®), pyrithiobac (Staple®) benzoates Sulfonylureas (SUs) azimsulfuron (Gulliver®), bensulfuron (Londax®), chlorsulfuron (Glean®), ethoxysulfuron (Hero®), foramsulfuron (Tribute®), halosulfuron (Sempra®), iodosulfuron (Hussar®), mesosulfuron (Atlantis®), metsulfuron (Ally®, Harmony®* M, Stinger®*, Trounce®*, Ultimate Brushweed®* Herbicide), prosulfuron (Casper®*), rimsulfuron (Titus®), sulfometuron (Oust®, Eucmix Pre Plant®*, Trimac Plus®*), sulfosulfuron (Monza®), thifensulfuron (Harmony®* M), triasulfuron (Logran®, Logran® B-Power®*), tribenuron (Express®), -
Acifluorfen Sorption, Degradation, and Mobility in a Mississippi Delta Soil
Acifluorfen Sorption, Degradation, and Mobility in a Mississippi Delta Soil L. A. Gaston* and M. A. Locke ABSTRACT repulsion effects, acifluorfen is sorbed by soil or soil Potential surface water and groundwater contaminants include her- constituents (Pusino et al., 1991; Ruggiero et al., 1992; bicides that are applied postemergence. Although applied to the plant Pusino et al., 1993; Gennari et al., 1994b; NeÁgre et al., canopy, a portion of any application reaches the soil either directly 1995; Locke et al., 1997). Although the extent of sorp- or via subsequent foliar washoff. This study examined sorption, degra- tion in soil is generally proportional to OC content dation, and mobility of the postemergence herbicide acifluorfen (5-[2- (Gennari et al., 1994b; NeÁgre et al., 1995; Locke et al., chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid) in Dundee 1997), sorption likely involves processes other than par- silty clay loam (fine-silty, mixed, thermic, Aeric Ochraqualf) taken titioning between aqueous and organic matter phases. from conventional till (CT) and no-till (NT) field plots. Homogeneous In particular, acifluorfen forms complexes with divalent surface and subsurface samples were used in the sorption and degrada- tion studies; intact soil columns (30 cm long and 10 cm diam.) were and trivalent cations (Pusino et al., 1991; Pusino et al., used in the mobility study. Batch sorption isotherms were nonlinear 1993) that may be sorbed or precipitated. Complex for- (Freundlich model) and sorption paralleled organic C (OC) content. mation and subsequent sorption may partially account All tillage by depth combinations of soil exhibited a time-dependent for increased acifluorfen sorption with decreasing soil approach to sorption equilibrium that was well described by a two- pH or increasing cation exchange capacity (Pusino et site equilibrium±kinetic model. -
Reduction of Nitroaromatic Pesticides with Zero-Valent Iron
Chemosphere 54 (2004) 255–263 www.elsevier.com/locate/chemosphere Reduction of nitroaromatic pesticides with zero-valent iron Young-Soo Keum, Qing X. Li * Department of Molecular Biosciences and Bioengineering, University of Hawaii, 1955 East-West Road, Ag Sci 218, Honolulu, HI 96822, USA Received 5 February 2003; received in revised form 4 June 2003; accepted 4 August 2003 Abstract Reduction of eleven nitroaromatic pesticides was studied with zero-valent iron powder. Average half-lives ranged from 2.8 to 6.3 h and the parent compounds were completely reduced after 48–96 h. The di-nitro groups of the 2,6- dinitroaniline herbicides were rapidly reduced to the corresponding diamines, with a negligible amount of partially reduced monoamino or nitroso products. Low levels of de-alkylated products were observed after 10 days. The nitro group of the organophosphorus insecticides was reduced dominantly to the monoamines but in a slower rate than the 2,6-dinitroanilines. A trace amount of oxon products was found. Reduction of nitro to amino was also the predominant reaction for the diphenyl ether herbicides. Aromatic de-chlorination and de-alkylation were minor reactions. These amine products were more stable than the parent compounds and 60% or more of the amines were detected after two weeks. Humic acid decreased the reduction rates of pendimethalin, and dichlone (a known quinone redox mediator) counteracted the effect of humic acid on the reactivity. Storage of iron powder under air decreased the reactivity very rapidly due to iron oxidation. Repeated use of iron powder also showed similar results. The reduced activity of air- oxidized iron was recovered by purging with hydrogen, but not nitrogen. -
PUBLIC WATER SUPPLY SAMPLING PLAN for Contaminants with a Vermont Health Advisory – May 2020
PROPOSED PUBLIC WATER SUPPLY SAMPLING PLAN For Contaminants with a Vermont Health Advisory – May 2020 Vermont Department of Environmental Conservation Drinking Water & Groundwater Protection Division A Plan to Sample for Chemicals with a Vermont Health Advisory As required by Act 21 (2019), Section 10(b), the Secretary of the Agency of Natural Resources, on or before January 1, 2020, must publish for public review and comment a plan to collect data for contaminants in drinking water from public community water systems and all non-transient non-community water systems, for which a health advisory has been established, but no Maximum Contaminant Level has been adopted. These health advisories are referred to as Vermont Health Advisories (VHAs) in this document. 1 | P a g e TABLE OF CONTENTS I. Executive Summary …………………………………………………………………………………………..Page 3 II. Background ……………………………………………………………………………………………………… Page 4 III. Determining the VHA contaminants for sampling at public water systems ………..Page 6 IV. Sampling Considerations …..…………………………………………………………………………….. Page 10 V. Proposed Sampling Plan ………………………………………………………………………….………..Page 12 Attachments Table 1 Complete List of Vermont Health Advisories (VHAs) …………………………………………..Page 13 Table 2 Proposed List of VHAs with Potential Concern ……………………………………………………Page 18 2 | P a g e I. Executive Summary The Secretary of the Agency of Natural Resources was tasked with developing a sampling plan for public review, for certain drinking water contaminants that have an established health advisory, also known as the Vermont Health Advisory (VHA) but have no Maximum Contaminant Level (MCL). This Sampling Plan (Plan) is targeted to public community and public non- transient non-community water systems. To provide context for public water system regulation, and standards that apply, a discussion of how VHAs and MCLs are determined is given. -
INDEX to PESTICIDE TYPES and FAMILIES and PART 180 TOLERANCE INFORMATION of PESTICIDE CHEMICALS in FOOD and FEED COMMODITIES
US Environmental Protection Agency Office of Pesticide Programs INDEX to PESTICIDE TYPES and FAMILIES and PART 180 TOLERANCE INFORMATION of PESTICIDE CHEMICALS in FOOD and FEED COMMODITIES Note: Pesticide tolerance information is updated in the Code of Federal Regulations on a weekly basis. EPA plans to update these indexes biannually. These indexes are current as of the date indicated in the pdf file. For the latest information on pesticide tolerances, please check the electronic Code of Federal Regulations (eCFR) at http://www.access.gpo.gov/nara/cfr/waisidx_07/40cfrv23_07.html 1 40 CFR Type Family Common name CAS Number PC code 180.163 Acaricide bridged diphenyl Dicofol (1,1-Bis(chlorophenyl)-2,2,2-trichloroethanol) 115-32-2 10501 180.198 Acaricide phosphonate Trichlorfon 52-68-6 57901 180.259 Acaricide sulfite ester Propargite 2312-35-8 97601 180.446 Acaricide tetrazine Clofentezine 74115-24-5 125501 180.448 Acaricide thiazolidine Hexythiazox 78587-05-0 128849 180.517 Acaricide phenylpyrazole Fipronil 120068-37-3 129121 180.566 Acaricide pyrazole Fenpyroximate 134098-61-6 129131 180.572 Acaricide carbazate Bifenazate 149877-41-8 586 180.593 Acaricide unclassified Etoxazole 153233-91-1 107091 180.599 Acaricide unclassified Acequinocyl 57960-19-7 6329 180.341 Acaricide, fungicide dinitrophenol Dinocap (2, 4-Dinitro-6-octylphenyl crotonate and 2,6-dinitro-4- 39300-45-3 36001 octylphenyl crotonate} 180.111 Acaricide, insecticide organophosphorus Malathion 121-75-5 57701 180.182 Acaricide, insecticide cyclodiene Endosulfan 115-29-7 79401 -
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. -
Appendix a Analysis of Products with Two Or More Active Ingredients
APPENDIX A ANALYSIS OF PRODUCTS WITH TWO OR MORE ACTIVE INGREDIENTS The Agency does not routinely include, in its risk assessments, an evaluation of mixtures of active ingredients, either those mixtures of multiple active ingredients in product formulations or those in the applicator’s tank. In the case of the product formulations of active ingredients (that is, a registered product containing more than one active ingredient), each active ingredient is subject to an individual risk assessment for regulatory decision regarding the active ingredient on a particular use site. If effects data are available for a formulated product containing more than one active ingredient, they may be used qualitatively or quantitatively1 2. There are no product LD50 values, with associated 95% Confidence Intervals (CIs) available for glyphosate. As discussed in USEPA (2000) a quantitative component-based evaluation of mixture toxicity requires data of appropriate quality for each component of a mixture. In this mixture evaluation an LD50 with associated 95% CI is needed for the formulated product. The same quality of data is also required for each component of the mixture. Given that the formulated products for glyphosate do not have LD50 data available it is not possible to undertake a quantitative or qualitative analysis for potential interactive effects. However, because the active ingredients are not expected to have similar mechanisms of action, metabolites, or toxicokinetic behavior, it is reasonable to conclude that an assumption of dose-addition would be inappropriate. Consequently, an assessment based on the toxicity of glyphosate is the only reasonable approach that employs the available data to address the potential acute risks of the formulated products. -
Dicamba Emissions Under Field Conditions As Affected by Surface
Weed Technology Dicamba emissions under field conditions as www.cambridge.org/wet affected by surface condition Thomas C. Mueller1 and Lawrence E. Steckel2 1 2 Research Article Professor, Department of Plant Sciences, University of Tennessee, Knoxville, TN, USA and Professor, Department of Plant Sciences, University of Tennessee, Knoxville, TN, USA Cite this article: Mueller TC and Steckel LE (2021) Dicamba emissions under field Abstract conditions as affected by surface condition. Weed Technol. 35: 188–195. doi: 10.1017/ The evolution and widespread distribution of glyphosate-resistant broadleaf weed species cata- wet.2020.106 lyzed the introduction of dicamba-resistant crops that allow this herbicide to be applied POST to soybean and cotton. Applications of dicamba that are most cited for off-target movement Received: 15 June 2020 have occurred in June and July in many states when weeds are often in high densities and Revised: 13 July 2020 Accepted: 11 September 2020 at least 10 cm or taller at the time of application. For registration purposes, most field studies First published online: 17 September 2020 examining pesticide emissions are conducted using bare ground or very small plants. Research was conducted in Knoxville, TN, in the summer of 2017, 2018, and 2019 to examine the effect of Associate Editor: application surface (tilled soil, dead plants, green plants) on dicamba emissions under field con- Kevin Bradley, University of Missouri ditions. Dicamba emissions after application were affected by the treated surface in all years, Nomenclature: with the order from least to most emissions being dead plants < tilled soil < green plant Dicamba; cotton; Gossypium hirsutum l.; material.