Astm stp 1595 2016

All materials and products produced from genet-ic engineering as these are not compatible with the general principles of organic production and there- fore are not accepted under this s

Selected technical PaPerS

StP1595

Editors: Craig Pofenberger and Justin Heuser

Pesticide Formulation and

Delivery Systems: 36th Volume, Emerging Trends Building

ISBN: 978-0-8031-7635-5

ISSN: 1545-9004

Copyright © 2016 ASTM INTERNATIONAL, West Conshohocken, PA All rights reserved This material may not be reproduced or copied, in whole or in part, in any printed, mechanical, electronic, flm, or other distribution and storage media, without the written consent of the publisher.

Photocopy Rights

Authorization to photocopy items for internal, personal, or educational classroom use, or the internal, personal, or educational classroom use of specifc clients, is granted by ASTM International provided that the appropriate fee is paid to the Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923, Tel: (978) 646-2600; http://www.copyright.com/

The Society is not responsible, as a body, for the statements and opinions expressed in this publication ASTM International does not endorse any products represented in this publication.

Peer Review Policy

Each paper published in this volume was evaluated by two peer reviewers and at least one editor The authors addressed all of the reviewers’ comments to the satisfaction of both the technical editor(s) and the ASTM International Committee on Publications.

The quality of the papers in this publication refects not only the obvious eforts of the authors and the technical editor(s), but also the work of the peer reviewers In keeping with long-standing publication practices, ASTM International maintains the anonymity of the peer reviewers The ASTM International Committee on Publications acknowledges with appreciation their dedication and contribution of time and efort on behalf of ASTM International.

Citation of Papers

When citing papers from this publication, the appropriate citation includes the paper authors, “paper title,” STP title, STP number, book editor(s), ASTM International, West Conshohocken, PA, year, page range, paper doi, listed in the footnote of the paper A citation is provided on page one of each paper Printed in Bay Shore, NY

November, 2016

THIS COMPILATION OF Selected Technical Papers, STP1595, Pesticide tion and Delivery Systems: 36th Volume, Emerging Trends Building on a Solid Founda-tion, contains peer-reviewed papers that were presented at a symposium held October 27–29, 2015, in Tampa, Florida, USA Te symposium was sponsored by ASTM In-ternational Committee E35 on Pesticides, Antimicrobials, and Alternative Control Agents and Subcommittee E35.22 on Pesticide Formulations and Delivery Systems.

Formula-Symposium Chairpersons and STP Editors:

Craig PofenbergerEvonik CorporationRichmond, VA, USAJustin HeuserEvonik CorporationRichmond, VA, USA

Foreword

StandardsOMRI Listing for Pesticides: What You Need to Know 1 Doug Currier

ASTM Standard Terminology Related to Biorationals Update 15 Lizbeth Rea and Michael C White

Adjuvant TechnologyPolyglycerol Esters as Adjuvants for Enhanced Pesticidal Activity 18 Justin Heuser, Craig Pofenberger, Rene Haensel, and Ewald Sieverding

Lignin-Based Chemicals as Green Dispersants for Liquid Formulation:

Jerry Gargulak, Stig Are Gundersen, Frédérik Bierre, and Pauline Rolland

The Afect of Dew on Herbicide and Adjuvant Efcacy 42 Donald Penner and Jan Michael

Crop Oil Concentrates Comparison: Connecting Chemical Features

Polymeric-Based Compatibility Agents for High Electrolyte Systems 90 Hannah Bofnger, Sharon Ellis, Susan Sun, and Greg Lindner

Contents

Craig Pofenberger, Lars Opfer, Ilia Roisman, and Cameron Tropea

The Efect of Adjuvants at High Spray Pressures for Aerial Applications 133 Bradley K Fritz, W Clint Hofmann, and Ryan S Henry

The Infuence of Nozzle Type, Operating Pressure, and Tank-Mixture Components

on Droplet Characteristics and the EPA’s Drift Reduction Rating 149 Ryan S Henry, Bradley K Fritz, W Clint Hofmann, and Greg R Kruger

Spray Characterization by Optical Image Analysis 162 Sounak Sarkar, Surya Kamin, and Greg R Kruger

Seed CoatingsCorrelation of the Mechanical Properties of Seed Coating Films and

Alan Halecky, Ning Ren, Jie Lu, Jane Q Wang, and Frances E Lockwood

Flowable Seed Treatments: A New Polymeric Dispersing System to

Increase Active Ingredient Content and to Improve Flowable Seed

Rocco Di Modugno, Federico De Pellegrini, Brad Eidem, and Andrea Balestrini

Te 36th Symposium on Pesticide Formulation and Delivery Systems was held in Tampa, Florida, on October 27–29, 2015 It was sponsored by ASTM Committee E35

on Pesticides, Antimicrobials, and Alternative Control Agents and was organized

by Subcomittee E35.22 on Pesticide Formulations and Delivery Systems Te posium was titled, “Emerging Trends Building on a Solid Foundation.” Tirty-three contributed papers ranged in content from current topics such as UAVs, pollinator health, and green chemistries to more traditional ones, such as regulatory issues, spray applications, and formulation and adjuvant research

sym-Tis symposium varied from previous ones in that there were no traditional note speakers Following the conclusion of the 35th Symposium in New Orleans in October 2014, a brainstorming session provided many insightful conference topics Consequently, invited speakers covered a broad range of noteworthy topics:

key-• Precision Ag with Unmanned Aerial Vehicles (presentation by an actual farmer!)

• Irrigation and Water Minimization

• Pollinater Health and RNAi Technology

• Biopesticides

• A How-to on OMRI Listing of Pesticides and Adjuvants

In this publication, the 16 technical papers will be classifed as follows: Standards, Adjuvant Technology, Formulation Development, Spray Applications and Delivery Systems, and Seed Coatings

STANDARDS

Doug Currier presented the basics on how to gain OMRI listings for pesticides and adjuvants, including required documentation Although not presented, Rea and White submitted a paper on standard terminology for Biorationals, as this is under review by the E35.22 subcomittee

ADjuvANTS TeChNoLogy

Heuser et al described the application of polyglycerol esters as benign tank-side vants, and Gargulak et al detailed the application of ligninsulfonates as green disper-sants in fungicidal SC formulations Penner and Michael presented his results on how dew efects various adjuvants upon the application of glyphosate on post-emergent weeds Costa et al evaluated the performance of four crop oil concentrates for drif

adju-Overview

nation and 2) determine efcacy control of a three-component herbicide blend

In a collaboration between four universities, Zollinger et al conducted ized, uniform studies on several weed species known to show glyphosate antagonism with hard water Te intent is to ultimately develop an ASTM standard for water conditioning agents

standard-FoRmuLATIoN DeveLoPmeNT

A new star polymer surfactant was introduced by Kayea et al with benefts including improved emulsion stability and resuspension ability as based on evaluations with multiple formulation types and actives Bofnger et al described how a family of novel amphoteric polymers compatibilizes high electrolyte formulations containing glyphosate, AMS, and fertilizers

Chen et al introduced a high-pressure liquid chromatography (HPLC) method for determination of Lambda-cyhalothrin, which overcomes the limitiations of the CIPAC method of quantifcation by GC wherein the technical is prone to isomerization

SPRAy APPLICATIoNS AND DeLIveRy SySTemS

Papers by Klostermann et al and Fritz et al reported on the mode of action of silicone adjuvants as drif-control adjuvants and how adjuvants afect high-speed aerial appli-cations, respectively Henry et al explained how parameters such as nozzle type, pres-sure, and tank-mix components infuence spray droplet characteristics Optical image analysis was ofered as an alternative to characterize spray droplet size as compared to the traditional laser method by Sarkar et al

SeeD CoATINgS

To address the concerns of dust of of seed coatings, Halecky et al adapted mechanical methods used to predict paint durability in tribological studies with insecticide and fungicide SC formulations Di Modugno et al described a new dispersant approach with a polymeric surfactant which allows for an increased active content in the seed coating and reduced dust of

Te editors wish to acknowledge the sincere eforts undertaken by those who sented at the conference, those who followed with a contributed paper, and those who reviewed the papers Session chairs were selected to highlight the dynamic of a new generation of researchers taking the reins of Subcomittee E35.22 on Pesticide Formula-tions and Delivery Systems Evonik Corporation actively supported the endeavors and time demands imposed on the symposium chairman and editors

Doug Currier1

OMRI Listing for Pesticides:

What You Need to Know

Citation

Currier, D., “OMRI Listing for Pesticides: What You Need to Know,” Pesticide Formulation and Delivery Systems: 36th Volume, Emerging Trends Building on a Solid Foundation, ASTM STP1595, C Poffenberger and J Heuser, Eds., ASTM International, West Conshohocken, PA,

2016, pp 1–14, http://dx.doi.org/10.1520/STP159520150090 2

ABSTRACT

The regulations that govern the production of certified organic produce in theUnited States are complex and cover all points of production from start (e.g.,seed, input materials, origins of livestock) to finish (e.g., product handling,labeling, delivery) These regulations help ensure that organic produce ismeeting a standard that everyone must follow The Organic Materials ReviewInstitute (OMRI) helps clarify this complex regulatory environment by focusing

on one piece of certified organic production: input materials Created by organiccertifiers in 1997 to conduct this type of work, OMRI has built a reputation overthe last 18 years as the leader in material review This paper examines andexplains the specific reviewcriteria OMRI uses when evaluating the compliance

of pesticide products for use in organic production under the U.S Department

of Agriculture’s National Organic Program

Keywords

pesticides, National Organic Program, Canada Organic Regime, U.S Department

of Agriculture (USDA), Canadian Food Inspection Agency (CFIA), Organic

Materials Review Institute (OMRI), organic farming

Manuscript received October 26, 2015; accepted for publication May 10, 2016.

1 The Organic Materials ReviewInstitute, P O Box 11558, Eugene, OR 97440-3758

2 ASTM 36th Symposium on Pesticide Formulation and Delivery Systems: Emerging Trends Building on a Solid Foundation on October 27–29, 2015 in Tampa, Florida.

Copyright V 2016 by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959.

PESTICIDE FORMULATION AND DELIVERY SYSTEMS: 36TH VOLUME 1

STP 1595, 2016 / available online at www astm org / doi: 10 1520/STP159520150090

The Organic Materials Review Institute (OMRI) is a 501V C

(3) not-for-profitorganization located in Eugene, Oregon OMRI is International Organization forStandardization (ISO) 17065-accredited by the U.S Department of Agriculture’s(USDA) Quality Assessment Division (QAD) for input material review and listingunder the National Organic Program (NOP) and Canada Organic Regime (COR)standards The term “input material” is wide-ranging but, in general, is defined

as any substance added to the soil, sprayed on a crop, fed to an animal, applieddirectly to an animal, or added directly to a processed food OMRI reviews inputmaterials in three ways: (1) through application- and fee-based technical reviews

of brand-name products, (2) through the completion of USDA NOP technicalreports for use in standards revision, and (3) in the form of public comments to theUSDA’s National Organic Standards Board (NOSB)

By far, OMRI’s main organizational goal is completing reviews of brand-nameproducts Their decisions on the allowance of products are communicated to thepublic through the OMRI Products ListV C

(OPL), which includes all the productscurrently allowed or allowed with restrictions OMRI also communicates decisions

on products through their subscriber updates, which include new products added

to the list and all of the recent products that were assigned a status of prohibited orthat were removed from the OPL for any other reason

OMRI Application Materials

For companies applying for OMRI listing, navigating the review process is a crucialcomponent to the work OMRI does Successfully working within OMRI’s policiesand standards ensures that reviews are fairly and thoroughly conducted This paperfocuses on OMRI’s application processes specific to products applying in the pesticideclasses crop pest, weed, and disease control (CP), livestock external parasiticidesand pesticides (LP), and processing pest controls (PP) This paper also addressesapplication processes specific to inert ingredients applying in OMRI’s crop manage-ment tools and production aids (CT) class The specific compliance criteria that apply

to the review of input materials in these two classes are the list of allowed synthetics

in §205.601 and §205.603 of the NOP Rules (USDA) and on the Permitted ces List (PSL), Table 4.3, in the COR regulations (CFIA) There also is a component

Substan-to OMRI review that examines the broader, interagency regulaSubstan-tory compliance of aproduct Specifically, products that must be registered with the EnvironmentalProtection Agency (EPA) or the Pest Management Regulatory Agency (PMRA) arerequired to submit proof of registration For products that are required to carry regis-tration and are also organic compliant, OMRI lists these products with a caution.This caution communicates to the public that the product is compliant for use inorganic production but cannot be used in the United States or Canada

The majority of the work OMRI conducts involves the review of brand-nameproducts with respect to the NOP and COR standards This process begins when a

company applies for a technical review of their product through the submission of

a product application This product application includes forms that are designed toask questions of an applicant that will help OMRI staff develop a picture of a prod-uct in order to make a recommendation on its allowance in organic production Forexample, one of the main questions for a company to answer when preparing anapplication is which class and category they would like the product reviewed under.This information is important because it gives an indication of which set ofstandards OMRI staff will use in the course of the review It also is important in thelisting process because OMRI lists products in the OPL in a specific class andcategory

An OMRI application kit includes all of the materials a company needs tocomplete the initial (administrative) portion of the OMRI review One component ofthe application kit is the Product Information form (see Fig 1) This form is forreporting the company name, brand name, and product name as well as under whichorganic standard and OMRI class and category the product should be reviewed Theproduct information form is a generic document completed by all companies regard-less of the class and category under which they are applying

The OMRI Pesticide Report (Fig 2) specifically is used when companies areapplying for the review of a product in the crop pest, weed, and disease control(CP), livestock external parasiticides and pesticides (LP), or processing pest controls(PP) class The form includes many questions that will assist with technical review

Technical Review

In this section, how OMRI conducts the technical reviews of pesticides will beoutlined Two points of technical review, with reference to the organic regulations,will be highlighted: (1) preventative management practices and (2) the list ofallowed synthetic materials (NOP) and the list of permitted substances (COR)

Confidentiality

OMRI takes confidentiality seriously because the credibility of its decisions relies oncompanies submitting a great deal of information for review OMRI is ISO 17065accredited, meaning that it is audited annually to ensure that the policies andstandards required to complete independent and transparent reviews are in placeand are being followed

Organic Regulations

Specific parts of the organic regulations allow for, or prohibit, the use of pesticideproducts in organic farming Those specific compliance standards are found in multi-ple places in the NOP and COR organic regulations (SeeTable 1andTable 2for moredetails on the applicable regulations.) What OMRI does during a technical reviewinvolves the consideration of all parts of the regulations when recommending theallowance of a material and ultimately a final product

OMRI’s policies and standards are based on NOP and COR standards; fore, changes to those standards may affect how OMRI conducts reviews Withchanges to U.S and Canadian organic standards pending, OMRI is attentive tohow standards updates affect its work Once updates to national organic standardsare finalized, the OPL is examined and any products affected are re-reviewed

TABLE 1 Allowed materials for use in pesticide products under NOP.

As algicide, disinfectants, and sanitizer, including irrigation system

cleaning systems:

§205.601(a) Alcohols including (i) ethanol and (ii) isopropanol §205.601(a)(1), §205.603(a)(1) Chlorine materials: For preharvest use, residual chlorine levels in the

water in direct crop contact or as water from cleaning irrigation

systems applied to soil must not exceed the maximum residual

disinfectant limit under the Safe Drinking Water Act, except that

chlo-rine products may be used in edible sprout production according to

EPA label directions (i) Calcium hypochlorite, (ii) chlorine dioxide,

(iii) sodium hypochlorite.

§205.601(a)(2), §205.603(7)

Copper sulfate: For use as an algicide in aquatic rice systems; limited

to one application per field during any 24-month period Application

rates are limited to those that do not increase baseline soil test values

for copper over a timeframe agreed upon by the producer and

accred-ited certifying agent.

§205.601(3)

Hydrogen peroxide §205.601(4), §205.603(13)

Ozone gas: For use in irrigation system cleaners only §205.601(5)

Peracetic acid: For use in disinfecting equipment, seed, and asexually

propagated planting material Also permitted in hydrogen peroxide

formulations as allowed in §205.601(a) at a concentration of no more

than 6 % as indicated on the pesticide product label.

§205.601(6), §205.603(18)

Soap-based algicide/demossers §205.601(7)

Sodium carbonate peroxyhydrate (CAS#-15630-89-4): Federal law

restricts the use of this substance in food crop production to approved

food uses identified on the product label.

§205.601(8)

Phosphoric acid: Allowed as an equipment cleaner, provided that no

direct contact with organically managed livestock or land occurs.

§205.603(20)

As herbicides, weed barriers, as applicable: §205.601(b)

Herbicides, soap-based: For use in farmstead maintenance (roadways,

ditches, right of ways, building perimeters) and ornamental crops.

§205.601(b)(1) Mulches including (i) newspaper or other recycled paper, without

glossy or colored inks, (ii) plastic mulch and covers (petroleum-based

other than polyvinyl chloride [PVC]), (iii) biodegradable biobased

mulch film as defined in §205.2 Must be produced without organisms

or feedstock derived from excluded methods.

§205.601(b)(2)

As animal repellents—soaps, ammonium—for use as a large animal

repellant only, no contact with soil or edible portion of crop.

§205.601(d)

As insecticides (including acaricides or mite control) §205.601(e)

Ammonium carbonate: For use as bait in insect traps only; no direct

contact with crop or soil.

§205.601(e)(1) Aqueous potassium silicate (CAS #-1312-76-1)—The silica, used in the

manufacture of potassium silicate, must be sourced from naturally

TABLE 1 (Continued)

Copper sulfate: For use as tadpole shrimp control in aquatic rice

production; limited to one application per field during any 24-month

period Application rates are limited to levels that do not increase

baseline soil test values for copper over a timeframe agreed upon by

the producer and accredited certifying agent.

§205.601(e)(4),

Elemental sulfur §205.601(e)(5) Lime sulfur, including calcium polysulfide §205.601(e)(6) Oils, horticultural—Narrow range oils as dormant, suffocating, and

summer oils.

§205.601(e)(7) Soaps, insecticidal §205.601(e)(8) Sticky traps/barriers §205.601(e)(9) Sucrose octanoate esters (CAS #s—42922-74-7; 58064-47-4)—In

accordance with approved labeling.

§205.601(e)(10), §205.603(b)(8) Formic acid (CAS# 64-18-6): For use as a pesticide solely within

honeybee hives.

§205.603(b)(2)

As insect management Pheromones §205.601(f)

As rodenticides Vitamin D 3 §205.601(g)

As slug or snail bait Ferric phosphate (CAS # 10045-86-0) §205.601(h)

As plant disease control §205.601(i) Aqueous potassium silicate (CAS #-1312-76-1)—The silica, used in the

manufacture of potassium silicate, must be sourced from naturally

occurring sand.

205.601(i)(1)

Coppers, fixed—Copper hydroxide, copper oxide, copper oxychloride,

includes products exempted from EPA tolerance, provided that

copper-based materials must be used in a manner that minimizes

accumulation in the soil and shall not be used as herbicides.

§205.601(i)(2)

Copper sulfate—Substance must be used in a manner that minimizes

accumulation of copper in the soil.

§205.601(i)(3) Hydrated lime §205.601(i)(4), §205.603(b)(5) Hydrogen peroxide §205.601(i)(5) Lime sulfur §205.601(i)(6) Oils, horticultural, narrow range oils as dormant, suffocating, and

summer oils.

§205.601(i)(7) Peracetic acid: For use to control fire blight bacteria Also permitted in

hydrogen peroxide formulations as allowed in §205.601(i) at

concentra-tion of no more than 6 % as indicated on the pesticide product label.

As synthetic inert ingredients as classified by the EPA, for use with

nonsynthetic substances or synthetic substances listed in this section

and used as an active pesticide ingredient in accordance with any

limitations on the use of such substances.

§205.601(m)

TABLE 1 (Continued)

EPA List 4—Inerts of minimal concern §205.601(m)(1), §205.603(e)(1) EPA List 3—Inerts of unknown toxicity: For use in passive pheromone

§205.2–Pesticide Any substance which alone, in

chemical combination, or in any formulation with

one or more substances is defined as a pesticide

in section 2(u) of the Federal Insecticide,

Fungi-cide, and Rodenticide Act (7 U.S.C 136(u) et seq).

§3.1–Pesticide Any substance or mixture of substances intended to prevent, destroy, repel, or mitigate any pests or plants.

§205.105–To be sold or labeled as “100 percent

organic,” “organic,” or “made with organic

(speci-fied ingredients or food group(s)),” the product

must be produced and handled without the use of:

§1.4.1–When producing or handling organic products, it is forbidden to use any of the following substances or techniques:

(Excerpt of items impacting pesticide products)

(Excerpt of items impacting pesticide products) (a) Synthetic substances and ingredients, except

as provided in §205.601 or §205.603;

(b) Nonsynthetic substances prohibited in

§205.602 or §205.604;

a All materials and products produced from

genet-ic engineering as these are not compatible with the general principles of organic production and there- fore are not accepted under this standard, except for vaccines only that have been grown on geneti- cally engineered substrates but are not themselves

a product of genetic engineering, as specified in CAN/CGSB-32.311, Organic Production Systems—

Permitted Substances Lists.

b Synthetic pesticides (e.g., defoliants and cants, fungicides, insecticides, and rodenticides), wood preservatives (e.g., arsenate) or other pesti- cides, except as specified in CAN/CGSB-32.311, Organic Production Systems — Permitted Substances Lists

desic-e Synthetic growth regulators

h Ionizing radiation and forms of irradiation on products destined for food or their inputs, as defined in this standard, except as specified in CAN/CGSB-32.311, Organic Production Systems — Permitted Substances Lists

TABLE 2 (Continued)

j Substances that are not included in CAN/ CGSB-32.311, Organic Production Systems — Permitted Substances Lists, except as provided by this standard

l Intentionallymanufactured nanotechnology products, or nanoprocesses involving intentional manipulation of matter at the nano scale to achieve new properties or functions that are different than properties and functions of the materials at the macro scale, except naturallyoccurring nano-sized particles, or those produced incidentallythrough normal processes such as grinding flour, or nano- sized particles used in a waythat guarantees no transference to product.

§205.206–(a) The producer must use

manage-ment practices to prevent crop pests, weeds, and

diseases including but not limited to:

CAN/CGSB-32.310-2006

§6.10–Pest Management–Pest management shall involve in descending order of preference (1) Crop rotation and soil and crop nutrient man-

agement practices, as provided for in §§205.203

and 205.205;

(2) Sanitation measures to remove disease vectors,

weed seeds, and habitat for pest organisms; and

(3) Cultural practices that enhance crop health,

including selection of plant species and varieties

with regard to suitabilityto site-specific conditions

and resistance to prevalent pests, weeds, and

dis-eases.

(b) Pest problems maybe controlled through

me-chanical or physical methods including but not

(1) Augmentation or introduction of predators or

parasites of the pest species;

(2) Development of habitat for natural enemies of

pests;

(3) Nonsynthetic controls such as lures, traps, and

repellents.

(c) Weed problems maybe controlled through:

(1) Mulching with fullybiodegradable materials;

(2) Mowing;

(3) Livestock grazing;

(4) Hand weeding and mechanical cultivation;

(5) Flame, heat, or electrical means; or

(6) Plastic or other synthetic mulches: Provided,

That, theyare removed from the field at the end

of the growing or harvest season.

TABLE 2 (Continued)

(d) Disease problems may be controlled through:

(1) Management practices which suppress the

spread of disease organisms; or

(2) Application of nonsynthetic biological,

botani-cal, or mineral inputs.

(e) When the practices provided for in paragraphs

(a) through (d) of this section are insufficient to

prevent or control crop pests, weeds, and

dis-eases, a biological or botanical substance or a

substance included on the National List of

syn-thetic substances allowed for use in organic crop

production may be applied to prevent, suppress,

or control pests, weeds, or diseases: Provided,

That, the conditions for using the substance are

documented in the organic system plan

§205.271 Facility pest management practice

standard

§8.4 Pest Management (a) The producer or handler of an organic facility

must use management practices to prevent pests,

including but not limited to:

8.4.1 Good manufacturing practices shall be adopted to prevent pests.Pest management prac- tices shall first involve the removal of pest habitat and food; second, the prevention of access and environmental management (light, temperature and atmosphere) to prevent pest intrusion and reproduction; and third, mechanical and physical methods (traps), lures and repellents listed in CAN/CGSB-32.311, Organic Production Systems — Permitted Substances Lists.

8.4.2 If the practices given in par 8.4.1 are ineffective, the operator may use pest control substances listed

in CAN/CGSB-32.311, Organic Production Systems — Permitted Substances Lists.The operator shall record the use and disposition of all such substances.

8.4.3 If the practices given in par 8.4.1 and 8.4.2 are ineffective, the operator may use pest control sub- stances not listed in CAN/CGSB-32.311, Organic Pro- duction Systems — Permitted Substances Lists.In situations in which pest control substances not listed in CAN/CGSB-32.311, Organic Production Sys- tems — Permitted Substances Lists, are used indoors, the operator shall ensure that no organic products or packaging materials for those products are present.Documentation shall be maintained showing the movement of organic products in order

to avoid contact with these substances and to cord the use and disposition of all such substances.

re-(1) Removal of pest habitat, food sources, and

breeding areas;

(2) Prevention of access to handling facilities; and

(3) Management of environmental factors, such as

temperature, light, humidity, atmosphere, and air

circulation, to prevent pest reproduction.

(b) Pests may be controlled through:

(1) Mechanical or physical controls including but

not limited to traps, light, or sound; or

(2) Lures and repellents using nonsynthetic or

synthetic substances consistent with the National

List.

(c) If the practices provided for in paragraphs (a)

and (b) of this section are not effective to prevent

or control pests, a nonsynthetic or synthetic

substance consistent with the National List may

be applied.

(d) If the practices provided for in paragraphs (a),

(b), and (c) of this section are not effective to

pre-vent or control facility pests, a synthetic

sub-stance not on the National List may be applied:

Provided, That, the handler and certifying agent

agree on the substance, method of application,

and measures to be taken to prevent contact of

the organically produced products or ingredients

with the substance used.

TABLE 2 (Continued)

(e) The handler of an organic handling operation

who applies a nonsynthetic or synthetic substance

to prevent or control pests must update the

oper-ation’s organic handling plan to reflect the use of

such substances and methods of application The

updated organic plan must include a list of all

measures taken to prevent contact of the

organi-cally produced products or ingredients with the

substance used.

(f) Notwithstanding the practices provided for in

paragraphs (a), (b), (c), and (d) of this section, a

handler may otherwise use substances to prevent

or control pests as required by Federal, State, or

local laws and regulations: Provided, That,

mea-sures are taken to prevent contact of the

organi-cally produced products or ingredients with the

substance used.

8.4.4 Organic products shall be exposed only to pesticides or pest control substances listed in CAN/CGSB-32.311, Organic Production Systems — Permitted Substances Lists, during any stage of production, transit, storage, or border crossing Section 6–Permitted Substances Lists for Processing

*§6.7–Pest Control Substances

*Various allowed materials are included in this ble Examples include:

ta-(1) Boric acid–May be used for structural pest trol (e.g., ants) No direct contact with organic food

con-or crops is allowed.

(2) Neem oil

§205.601–Synthetic substances allowed for use in

organic crop production.

CAN/CGSB–32.311-2006

§205.602–Nonsynthetic substances prohibited for

use in organic crop production.

Section 4–Permitted Substances Lists for Crop Production

*PSL Table 4.3–Crop Production Aids and Materials

—Unless otherwise specified, the crop production aids and materials listed below shall not contain substances prohibited by par 1.4.1 of CAN/CGSB

?32.310, Organic Production Systems — General Principles and Management Standards, or not per- mitted by this standard.

*Various active and inert (formulants) substances are identified as allowed here Examples include: (1) Gibberellic acid–”Acceptable if made from a fermentation process Fermentation process shall not use organisms from genetic engineering See also Growth regulators for plants.”

(2) Botanical pesticides–”Botanical pesticides shall

be used in conjunction with a biorational pest agement program but shall not be the primary method of pest control in the farm plan The least toxic botanicals shall be used in the least ecologi- cally disruptive way possible All label restrictions and directions shall be followed including restric- tions concerning crops, livestock, target pests, safety precautions, pre-harvest intervals, and worker re-entry.”

man-Moreover, any updates to the national organic standards are used in the review ofnewly applying products.

Preventative Practices—NOP and COR

Preventative management practices are important components of organic ture and are specifically written into organic regulations as generally being requiredbefore using a pesticide Specifically, §205.206(a) and (b) in the USDA’s NOP rulesstates that producers must use preventative practices, such as crop rotation andvarietal choice It is only after these preventative practices fail that, “A biological orbotanical substance included on the National List of synthetic substances allowedfor use in organic crop production may be applied to prevent, suppress, or controlpests, weeds, and diseases: Provided that the conditions for using the substance aredocumented in the organic system plan.”

agricul-The way OMRI communicates these preventative management practicerequirements to the public is through assigning a general restriction to productslisted in pesticide categories This restriction is as follows: “May be used as a pesti-cide if the requirements of 205.206(e) are met, which requires the use of preventa-tive, mechanical, physical, and other pest, weed, and disease managementpractices.” OMRI publishes this restriction on the product certificate issued to acompany and in the OPL if the product is searched by category However, not allpesticide products listed by OMRI are restricted Some products may be allowed be-cause they are considered preventative management practices Examples of thesetypes of products include nonsynthetic biological controls that are not regulated asbiopesticides (e.g., sterile insects or nematodes), nonsynthetic mulches (e.g., straw),and rodent traps that do not include synthetic materials allowed at §205.601

Standards for Pesticides—NOP and COR

§205.603–Synthetic substances allowed for use in

organic livestock production

CAN/CGSB–32.311-2006

§205.604–Nonsynthetic substances prohibited

for use in organic livestock production

Section 5–Permitted Substances Lists for Livestock Production

PSL Table 5.3-Health Care Products and Production Aids

a USDA Agricultural Marketing Service, 2015.

b Canadian General Standards Board, 2011.

general allowance of nonsynthetic materials identified in §205.602 and §205.604 inthe National List of Allowed and Prohibited Substances Arsenic, lead salts, sodiumflualuminate (mined), strychnine, and tobacco dust (nicotine sulfate) are all non-synthetic materials that are prohibited for use in organic production OMRI con-firms the nonsynthetic status of a material by conducting an in-depth review of itsmanufacturing process A company applying for OMRI listing is responsible forsubmitting enough information regarding the manufacturing process of the activeingredient in order for OMRI to determine its synthetic/nonsynthetic status.Just as there is a general allowance for nonsynthetic active ingredients, there is

a general prohibition on synthetic actives and inert ingredients under the NOPstandard There are also exceptions to the general prohibition of synthetic materials

in organic production that are identified in §205.601 and §205.603 of the NationalList of Allowed and Prohibited Materials The synthetic materials identified in thesetwo sections are allowed in organic production as long as an organic operation firstuses preventative practices as outlined in §205.206, §205.238, and §205.271 Thelists of allowed synthetics in §205.601 and §205.603 include the active ingredientsfound in products that are regularly used and relied upon in organic production.Examples of allowed synthetic active ingredients include elemental sulfur, fixedcopper products such as copper oxide, and lime sulfur

INERT INGREDIENTS—NOP

The same review criteria for active ingredients also apply to inert ingredients used

in pesticide formulations: materials must be nonsynthetic and allowed or be allowedsynthetic materials Again, materials that claim compliance by being nonsyntheticwill need to submit a manufacturing process details to OMRI for review If the inertingredient is synthetic, it must be allowed under §205.601(m) and §205.603(e).Those rule citations reference EPA Lists 3 and 4 inert ingredients The NOPhas clarified that these refer to the EPA’s 2004 list of inert ingredients in GuidanceDocument 5008 [1] This means that synthetic inert ingredients may be used in pes-ticide formulations with active ingredients if they appear on the 2004 EPA list of in-ert ingredients as a List 4A or 4B material (List 3 inert ingredients are allowed only

in passive pheromone dispensers.)

Currently, the NOP is in the process of reassessing the reference to this EPAlist as a basis for organic compliance In 2010, the EPA notified the NOP that the

2004 list of inert ingredients is no longer being maintained and that any reference

to it should cease In response, the NOP has worked since then to determine how tohandle inert ingredients in pesticides This work has culminated in the NOSB pro-posing that inert ingredients that appear on the EPA’s list of inert ingredientsallowed in products exempt from registration under Federal Insecticide, Fungicide,and Rodenticide Act 25(b) and those inert ingredients that are included on the SaferChemical Ingredients List should be allowed in pesticide products used in organicproduction [2]

ACTIVE INGREDIENTS—COR

A review of pesticides with respect to COR standards mirrors many of the reviewstandards established for NOP: both active and inert ingredients must be allowed.However, although the NOP approach offers a blanket allowance for nonsyntheticmaterials (with exceptions) and allowance only for synthetic materials as identified

in §205.601 and §205.603, the COR regulation approach offers a closed list ofallowed materials Active ingredients in a pesticide used in organic production inCanada must appear in PSL Table 4.3 [3] OMRI will review the manufacturingprocess for any material included in Table 4.3, and whose annotation allows for use

as an active ingredient, to ensure that the material is only formulated with ted substances For example, PSL Table 4.3 identifies gibberellic acid as an allowedactive ingredient if manufactured from fermentation processes Therefore, a compa-

permit-ny applying for OMRI listing will be required to submit manufacturing processdetails confirming the methods used to manufacture gibberellic acid The annota-tion for gibberellic acid in Table 4.3 also requires that organisms used for fermenta-tion must not be genetically modified Again, OMRI requires genetic engineeringdeclarations from applicants that allow review staff to identify and evaluate whengenetically modified organisms are used to manufacture a material

The COR standards also identify materials that are allowed in processingfacilities PSL Table 6.7 outlines which substances are allowed for use in processingfacilities This approach to organic standards differs from the NOP standard.Specifically, the NOP standard references §205.601 and §205.603 as allowed whenpreventative, cultural practices fail

INERT INGREDIENTS—COR

Inert ingredients (COR language uses “formulants”) utilized in pesticides with anactive ingredient are allowed in PSL Table 4.3 That substance entry states thatformulants must either be nonsynthetic or included in List 3 (for use only in passivepheromone dispensers) or in List 4 on the PMRA’s 2010 List of Formulants [4]

To confirm the compliance of formulants used in pesticides, OMRI references thisPMRA list If the inert ingredient is not included, an applicant must submitmanufacturing process details to OMRI for review to confirm its nonsyntheticstatus

Adjuvants for Pesticide Use

OMRI reviews adjuvant products in the category adjuvants for pesticide use in theclass crop tools and production aids Products listed in this category and classinclude sticker/spreaders and wetting agents The same review criteria as outlinedearlier (see inert ingredients—NOP and COR) is used to review the compliance ofthese products that apply for OMRI listing In addition to these review criteria,OMRI will ensure that the labels of these adjuvant products do not claim an active

ingredient An example of alternate language that is acceptable in lieu of “activeingredient” is “principle functioning agent.”

Conclusion

The regulations that address which materials are allowed and which materials areprohibited in organic production are complex OMRI helps to clarify these complexregulations by providing in-depth product reviews based on NOP and COR organicstandards OMRI review of pesticides includes confirmation of organic complianceand also confirmation of the regulatory status that allows a pesticide to be sold inthe United States or Canada Pesticide products that are required to be registeredwith the EPA or PMRA must show proof of registration with their OMRI applica-tion Those products that are required to be registered and are not will be issued acaution if their organic compliance is confirmed

OMRI standards are based on either NOP or COR organic standards Materialsare regularly evaluated by the NOSB and COR for addition to the list of allowed mate-rials Any company can petition to have a material evaluated for organic compatibility.For more information regarding the petition process contact the NOP or COR

References

[1] USDA National Organic Program, “Guidance Reassessed Inert Ingredients,” Guidance Document, Wash ington, DC, 2011, https://www.ams.usda.gov/sites/default/files/media/ 5008.pdf (accessed October 4, 2016).

Change 2004 EPA List 4 Inerts on §205.601(m) and §205.603(e),” NOSB mendations Fall 2015, October 29, 2015, https://www.ams.usda.gov/sites/default/ files/media/CS%20LS%20EPA%20List%204InertsAnnotation_final%20rec.pdf (accessed October 4, 2016).

Recom-[3] Committee on Organic Agriculture, “Organic Production Systems–Permitted Substances Lists,” CAN/CGSB-32.311-2015, Canadian General Standards Board, Gatineau, 2015 [4] Pest Management Regulatory Agency, “PMRA List of Formulants,” HealthCanada, Ottawa, August 31, 2010.

Lizbeth Rea1and Michael C White2

ASTM Standard Terminology

Related to Biorationals Update

Citation

Rea, L and White, M C., “ASTM Standard Terminology Related to Biorationals Update,” Pesticide Formulation and Delivery Systems: 36th Volume, Emerging Trends Building on a Solid Foundation, ASTM STP1595, C Poffenberger and J Heuser, Eds., ASTM International, West Conshohocken, PA, 2016, pp 15–17, http://dx.doi.org/10.1520/STP159520150092 3

ABSTRACT

The ASTME35.22 Standard for Terminology Related to Biorationals Task Group(Biorationals Task Group) was formed in 2010 as a result of changes inconsumer preference about how food is produced and the related increaseddevelopment and marketing of nontraditional pest control and nutritionalproducts The goal of the task group is to develop standard definitions tominimize the use of confusing and inconsistent terminology for these types ofproducts The standard came to life in 2013 with the definition of “biorational,”which is an umbrella term for these pest control and nutritional products.The first biorational term approved was the U.S Environmental ProtectionAgency’s definition of “biopesticide,” which was published in 2015 Subsequently,several other terms relating to biorationals (e.g., “biopesticides” and specificbiopesticides such as “biochemical,” “microbial,” and “plant-incorporatedprotectant” biopesticides) have been approved

Keywords

biorationals, terminology, biopesticides

Manuscript received November 4, 2015; accepted for publication February 1, 2016.

1 SipcamAgro USA, Inc., 2525 Meridian Pkwy., Suite 350, Durham, NC 27713

2 Council of Producers & Distributors of Agrotechnology, 1730 Rhode Island Ave., NW, Suite 812, Washington,

DC 20036

3 ASTM 36th Symposium on Pesticide Formulation and Delivery Systems: Emerging Trends Building on a Solid Foundation on October 27–29, 2015 in Tampa, Florida.

Copyright V 2016 by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959.

PESTICIDE FORMULATION AND DELIVERY SYSTEMS: 36TH VOLUME 15

STP 1595, 2016 / available online at www astm org / doi: 10 1520/STP159520150092

produc-Similar conditions existed in the early 1990s with the tank-mix adjuvant industry.Marketing claims and terms had been used interchangeably for many years, causingmarket confusion and potential regulatory action To address this situation, a groupwithin the Chemical Producers & Distributors Association (since renamed the Coun-cil of Producers & Distributors of Agrotechnology, or CPDA) worked throughASTM in the early 1990s to develop standardized terminology for the tank-mix adju-vant industry Ultimately, the ASTM Committee E-35 on Pesticides and AlternativeControl Systems, through its Subcommittee E-35.22 (Formulation and Application),created a Tank-Mix Adjuvant Task Force that developed two documents dealing withstandard terminology for tank-mix adjuvants (ASTM E1519, Standard TerminologyRelating to Agricultural Tank Mix Adjuvants) and Pesticides (ASTME-609, StandardTerminology Relating to Pesticides) [1,2] With the approval of these standards, the in-dustry was able to move forward with defined and useful terminology.

industry began to use these standardized definitions in technical presentations and inmarketing products Since 1993, CPDA’s Adjuvants & Inerts Committee (AIC) has ledefforts to develop standards for adjuvants in the United States The AIC has also incor-porated (by reference) ASTM test methods and definitions into CPDA’s program forcertifying the compliance ofadjuvant products with specified product quality and stew-ardship related standards [3] The goal of this program is to ensure that good qualityadjuvants meeting a minimum set ofindustry standards are available on the market

Biorationals Task Group

The Biorationals Task Group was created in September 2010 to develop standarddefinitions for the biorational product industry On March 1, 2011, the BiorationalsTask Group met to identify terms and to develop the scope for a standard ofbiorational terminology and definitions for an initial group of biorational terms.These terms included biorational, biopesticide, biosurfactant, biostimulant, bioyieldenhancer, bioplant health promoter, and biosoil conditioner, and the scope anddefinitions of these terms were discussed and voted on during an April 2011 meet-ing of the E35.22 subcommittee The term “biorational” was selected as an umbrella

term and defined in terms of the core characteristics that all biorational-type ucts must have (e.g., a biological or natural origin) Thus, a biosurfactant orbiostimulant would have to meet the definition of a biorational plus the definingcharacteristics established for a biosurfactant or biostimulant.

prod-However, these early discussions also clarified that the Biorationals Task Groupneeded to include broader representation and input from the manufacturers anddistributors of these products Therefore, the Biopesticide Industry Alliance and thenewly formed Biostimulants Coalition were contacted and encouraged to partici-pate and share their expertise and experience in manufacturing and marketingbiorational products As a result of the participation of these organizations, a newscope for the biorationals terminology standard was developed, and definitions forthe umbrella term “biorational” and the term “biostimulant” were developed andballoted for the 2011 fall meeting The scope and term for biorationals waspublished in 2013 under ASTME2880-14, Standard Terminology Related to Biora-tionals [4], which provides a framework for development of additional definitions

of biorational products Subsequently, the EPA’s definition for “biopesticide,”

“biochemical,” “biosurfactant,” and “plant-incorporated protectant” was approvedfor publication The Biorationals Task Group continues to work on other termssuch as “microbial,” while the Biostimulants Coalition continues to work with theEPA and the states on a definition for “biostimulant.” Other terms are currently be-ing considered for defining and balloting

Conclusion

The Biorationals Task Group continues to develop standardized definitions throughASTM that the biorationals industry can adopt to ensure the consistency and credi-bility of their products in the marketplace, such as the tank-mix adjuvants industrydid for its products

[4] ASTM E2880 -14, Standard Terminology Related to Biorationals , ASTM International, West Conshohocken, PA, 2014, www.astm.org

Justin Heuser,1Craig Poffenberger,1Rene Haensel,2and

Ewald Sieverding2

Polyglycerol Esters as Adjuvants

for Enhanced Pesticidal Activity

Citation

Heuser, J., Poffenberger, C., Haensel, R., and Sieverding, E., “Polyglycerol Esters as Adjuvants for Enhanced Pesticidal Activity,” Pesticide Formulation and Delivery Systems: 36th Volume, Emerging Trends Building on a Solid Foundation, ASTM STP1595, C Poffenberger and

J Heuser, Eds., ASTM International, West Conshohocken, PA, 2016, pp 18–29, http:// dx.doi.org/10.1520/STP159520150093 3

ABSTRACT

Regulatory agencies, applicators, and the public are becoming more awarethat pesticide inert ingredients are not entirely “inert.” There is an increasingdemand for efficacious adjuvants derived from renewable resources and havingmore benign toxicological profiles Biodegradable polyglycerol esters (PGEs),constructed from vegetable-based fatty acids and glycerin, have long beenincorporated into personal care and food products as emulsifiers Because thesematerials are approved in such sensitive markets, Evonik has undertaken thedevelopment of a series of formulated polyglycerol adjuvant blends for use inthe agrochemical segment Previously, we presented data confirming that theseblends improved penetration for foliar uptake using confocal laser scanningmicroscopy This presentation will review the field-trial performance of twopolyglycerol blends, one hydrophilic and one lipophilic in character Specifically,the efficacy of these materials as tank-side adjuvants combined with herbicides,fungicides, and insecticides will be compared against traditional nonionicadditives Wind tunnel data will also be presented to demonstrate the influence

on formation of driftable fines during spray applications PGEs are “tunable”across a wide range of hydrophilic-lipophilic balance values This flexibility makes

Manuscript received November 5, 2015; accepted for publication May 6, 2016.

1 Evonik Corp., Nutrition and Care, 7801 Whitepine Rd., Richmond, VA 23237

2 Evonik Nutrition and Care GmbH, Goldschmidtstraße 100, 45127, Essen, Germany

3 ASTM 36th Symposium on Pesticide Formulation and Delivery Systems: Emerging Trends Building on a Solid Foundation on October 27–29, 2015 in Tampa, Florida.

Copyright V 2016 by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959.

STP 1595, 2016 / available online at www astm org / doi: 10 1520/STP159520150093

them useful as emulsifiers for oils, solvents, and liquid pesticides in agriculturalformulations.

PGEs can be synthesized and blended with additional components to tate enhanced performance for both hydrophilic and lipophilic pesticide activeingredients (see Fig 1) Based on the degree of glycerin polymerization and fattyacid selection, these molecules can be tailored for a given application andhydrophilic-lipophilic balance value PGE materials, unlike many adjuvant ingre-dients that cannot be formulated into a pesticide product due to stability con-cerns, offer a wide pH range and often function as co-emulsifiers or dispersingpromoters

facili-This paper contains data collected in support of two products developed by

SP 131 (PGE-1) and BREAK-THRU SP 133 (PGE-2).Both products are blends incorporating PGE technology Results from laboratoryand field experiments indicate enhanced efficacy of pesticides with the addition ofthese materials

subsequent PGE; RCOOH ¼ C 9 – C 21 fatty acid (saturated/unsaturated,

branched).

Methods and Materials

inha-Confocal Scanning Laser Microscopy

Penetration data were presented previously by Rene Haensel [1] and obtained fromPlant Protection Chemistry’s laboratory in New Zealand led by Robyn Gaskin.Confocal scanning laser microscopy (CSLM) was utilized to observe fluorescent dyepenetration into bean leaves as has been detailed previously by this group [2] Con-ditions and test materials are provided as follows:

• Plant: Bean (Vicia faba)—used approximately 4 weeks after sowing

• Dyes: Oregon GreenV R

(OG) 488 in aqueous acetone (3 þ 2) solution at0.5 mg/mL; Rhodamine B (RB) in double-distilled water at 0.5 mg/mL.Note that to ensure stomata were closed, all plants were kept in the dark for 4 hprior to treatment No sign of stomatal penetration was observed on application ofany treatment After treatment, the plants were returned to controlled environmentcabinets and remained in the dark to reduce photodegradation of the dyes untilCLSM examination (2–16 h after treatment [HAT]) All leaf surfaces treated with

OG and RB were washed thoroughly with 25 % aqueous ethanol (3 þ 1) solution toremove any residual (unabsorbed) dye immediately prior to examination

WIND TUNNEL SPRAY DRIFT

Trials were conducted at the University of Nebraska-Lincoln (UN-L) in NorthPlatte and followed ASTME2798-11, Standard Test Method for Characterization ofPerformance of Pesticide Spray Drift Reduction Adjuvants for Ground Application,guidelines [3] This site houses a sophisticated chamber to both simulate low-speed

Acute oral toxicity, up and down 425

Acute dermal irritation 404

Acute dermal toxicity 402

Acute eye irritation 405

wind flow and capture droplet size distributions of spray solutions [4] Testingdetails are as follows:

• Application sprays: water; TouchdownV R

HiTech at 2.34 L/ha

• Adjuvants: nonionic surfactant (NIS) at 0.30 %; PGE-2at 0.125 % (v/v)

• Spray nozzle and pressure: TeeJetV R

Three field trials were conducted to observe the adjuvant effect in enhancing

effica-cy of an insecticide, fungicide, and herbicide All data from the trials were subject toanalysis of variance using Agricultural Research Manager software

The first trial was the control of silverleaf whitefly (Bemisia tabaci) nymphs intomatoes (Solanum lycopersicum) using VenomV R

(dinotefuran) The tomato var Tygress was transplanted on March 26, 2014, at Vero Beach, Florida, on plasticbeds (32in wide and 6 in tall) The trial was a randomized complete block designwith four replicates Plots were 6 ft wide and 20 ft long and consisted of a single rowwith 1.5-ft plant spacing within the row Within each replicate, the treated plotswere separated by a buffer (untreated) row Maintenance of the trial was conductedusing local commercial practices that included daily drip irrigation with a typicalfertigation program There were two applications with a water volume of 600 L/ha(63.9 GPA) applied at 2.75 bar (40 psi) with TXVS8 nozzles The applicationsoccurred on May 18, 2014, and May 27, 2014 Whitefly nymphs (second and thirdinstar nymphs) were counted on leaf samples taken at 8 days after application(DAA), 8 DAB, and 15 DAB Seven leaves were sampled from each plot; these wereplaced into paper bags and counted in the laboratory on the same day In the labo-ratory, the ten uppermost leaflets were removed, starting from the terminal leaflet(ten leaflets per plot) Nymphs (second and third instars) on these leaflets werecounted under a dissecting microscope

culti-The second trial was the control of leafspot (Cercospora sojina) in soybeans(Glycine max) using PriaxorV R

(fluxapyroxad plus pyraclostrobin) Soybeans wereplanted on May 25, 2014, in Cheneyville, Louisiana The trial was a randomizedcomplete block design with four replicates Plots were approximately 13 ft by 50 ftlong Maintenance of the trial was conducted using local commercial practices.There were two applications with water volumes of 100 L/ha applied at 1.172bar(17 psi) with Twin TeeJet 11003 nozzles Applications occurred on July 16, 2014,and July 31, 2014, when the plants were at the R1 (beginning bloom) and R3(beginning pod) growth stages, respectively At maturity, the soybeans were har-vested, and the yield was assessed for each plot (calculated as tons per hectare)

The third trial was the control of the weed hairy fleabane (Conyza bonariensis)

in almonds (Prunus dulcis) using GramoxoneV R

(paraquat dichloride) The trial wasconducted in an established almond orchard near Sanger, California The trial

was a randomized complete block design with five replications Plots were 20 ft by

14 ft, with 20 ft between rows and 16 ft between trees in each row Asingle tion occurred on June 10, 2015, with a water volume of 100 L/ha applied at 100 to

applica-115 psi with TeeJet D3 DC56 nozzles at a height of 2 ft Assessment of biomass trol was rated on a percentage scale, with 0 % control assigned to untreated plotsand other plots rated relative to the control plot Percent loss of biomass is a meth-

con-od of assessing canopy density and green biomass (weed density) by assigning a

0 % rating for the loss of green biomass to the untreated plots; the stunting, ing, chlorosis, and drying of weeds in treated plots is then a reflection of the percentloss of green biomass The data were collected with remote sensing equipment(RapidSCAN) to measure canopy greenness (normalized difference red end) anddensity (normalized difference vegetative index) Arating of 100 % was assigned toplots with no weed pressure Ratings were taken at 3, 7, and 14 DAA

shrivel-Results and Discussion

TOXICOLOGICAL DATA

Results from toxicological testing were favorable in supporting PGE products asbenign materials The data shown in Table 2indicate low oral and dermal toxicityconcerns Although mild or moderate irritation was observed for both dermal andeye contact, this would be anticipated for most surfactant materials Because of thelow vapor pressures, inhalation waivers were prepared and accepted for registration

in Washington In addition, skin sensitization data from an analogous PGE wereused to satisfy this test requirement

CONFOCAL SCANNING LASER MICROSCOPY PENETRATION DATA

Penetration data were collected using CSLM after treating bean leaves with dye utions with and without PGE products Because stomata were intentionally closed

sol-by storing the plants in darkness prior to treatment, the penetration enhancement

OECD

402 Acute dermal toxicity Wistar strain rat >5,000 mg/kg >5,000 mg/kg

403 Acute inhalation N/A (waivers)Vapor pressure ¼

0.0036 Pa

Vapor pressure ^ 0.01 Pa

404 Acute dermal irritation Rabbit Moderate irritant Mild irritant

405 Acute eye irritation Rabbit Mild irritant Mild irritant

406 Skin sensitization Guinea pig Not sensitizing

(analogous PGE)

Not sensitizing (analogous PGE)

425 Acute oral toxicity Female wistar

strain rat

>5,000 mg/kg >5,000 mg/kg

is specifically through the cuticle and epidermal cell vacuoles [2] Fig 2provides aseries of images at 63 times magnification taken 2 h after the RhodamineV R

B dyesolutions were placed onto the leaves This dye was meant to represent a lipophilicspecies even though it is readily soluble in water The left image is dye solutiononly; the middle image is dye solution with PGE-2; and the last image is dye solu-tion with PGE-1 Initially, the images were collected at 24 HAT, but no fluorescencewas detected This was attributed to significant translocation of fluid within theplant such that the application location no longer contained an observable amount

of dye Therefore, subsequent testing was performed at 2 HAT, which resulted inthese images

A second series of images, shown inFig 3, was collected at 16 HAT and againwas under 63 times magnification Here, Oregon GreenV R

was used to simulate a

B dye fluorescence images demonstrating enhanced penetration into wheat leaves when PGE is included.

dye fluorescence images demonstrating enhanced penetration into wheat leaves when PGE is included.

hydrophilic active ingredient This time duration was selected based on fluorescencedetection—earlier time points showed faint signals only.

The penetration enhancement was obvious with either dye used However,based on the time required for observed fluorescence, the dye with more the lipo-philic character had a significantly greater uptake response with adjuvant present

SPRAY DROPLET DISTRIBUTION

Driftable fines during application are those water droplets below 105 lm based onASTM E2798-11 For the purposes of this testing, values below either 105 or

150 lm were analyzed to more fully characterize the sprays Based on this tion, data were collected from the UN-L wind tunnel when PGE-2 was includedwith water alone and with a commonly used herbicide (containing no other surfac-tant).Fig 4provides a comparison in droplet distributions when water was sprayedboth with and without PGE-2

informa-There was an approximately 50 % reduction in driftable fines at <150 lm andslightly greater than 50 % reduction at <105 lm with the adjuvant present at0.125 % Both the distributions below 105 and 150 lm were lowered indicating thePGE effectively increased the spray droplet size distributions To simulate an actualfield application, this test was then repeated using TouchdownV R

HiTech, a cial glyphosate herbicide (containing no surfactant) Spray droplets observed withthis pesticide incorporated numerically were somewhat larger in profile, but theamount of driftable liquid remained substantial Drift from this material would causedamage to off-target fields because it is a broad-spectrum weed control pesticide

The results of spray application without and with PGE are shown inFig 5 In tion, a commonly used NIS was included at the label rate for general comparison.

addi-Both additives effectively reduced driftable fines in this test Although not tistically significant, the reduction by the PGE was numerically better These com-bined data support the claim of certain PGE materials also functioning as agents toincrease overall spray droplet particle size Because only one PGE blend was tested,however, additional data would be required to expand the claim across this generalchemistry class

sta-PEST CONTROL AND YIELD DATA

Field trials were contracted to obtain data across three pesticide applications to lectively demonstrate adjuvant enhancement by PGE materials The first was aninsecticide trial containing both PGE-1 and PGE-2 products Whitefly nymphcounts were used as a basis for efficacy determination after applications of VenomV Rinsecticide (dinotefuran) Two applications were made (A and B) with evaluations

col-at 8 days after each and then again col-at 15 days after B Both a full rcol-ate and a third rate of insecticide were applied along with two levels of adjuvant at thereduced rate The purpose of this setup was to demonstrate enhanced efficacy,which is not always realized when full rates are used Results of the trial are pre-sented inFig 6andFig 7

one-Focusing on the 15 days after the second application graph bars, it is evidentthat both PGE materials enhanced nymph control of the reduced rate insecticide

HiTech with and without NIS or PGE adjuvants.

There was statistical equivalence between the full rate data and those reduced ratescontaining adjuvant.

The second trial consisted of PriaxorV R

(pyraclostrobin) fungicide to controlleafspot in soybeans Instead of visual damage assessment,as would be typically

reported, the data presented in Fig 8 and Fig 9 are yield values from the testplots Values were extrapolated in order to plot data in terms of metric tons perhectare.

There was a numerical yield increase with 0.125 % PGE-1 included in the cide application However, this effect was seemingly lost with the higher dose ofadjuvant In addition, the full rate of fungicide resulted in fewer metric tons of soy-bean yield versus the halfrate (numerically) A number ofexplanations could behypothesized for these latter effects, often making field trial data difficult to inter-pret Whether the weather conditions had a significant influence or the field soilhad nutrient gradients were unknown factors Regardless, the adjuvant effect wasdiscernible from this trial Inclusion of PGE-2 had a predictable dose response, andthe trends presented in that graph align to expected outcomes.

pesti-The final trial tested only PGE-2 as an additive to enhance weed control aroundalmond trees using GramoxoneV R

(paraquat) at 1.46 L/ha A visual assessment ofbiomass reduction was performed at 3, 7, and 14 DAT Data from the trial are pro-vided inFig 10

An interesting phenomenon was observed when comparing adjuvant ment at 3 DAT versus 14 DAT Although the performance appeared to lag early on

in the trial, overall the PGE inclusion resulted in numerical weed control ment It is difficult to offer an explanation for the delay in efficacy enhancement be-cause the expectation was to observe faster initial effects

enhance-Conclusions

Spray mixtures containing PGEs increased the efficacy of pesticide formulations as

is evident from both laboratory and field testing Foliar uptake enhancement wasalso gleaned from the CLSM data As an added benefit, the driftable fines from

application sprays were reduced, which would aid in preventing off-target tion either in populated areas or adjacent fields The benign nature of PGE materi-als appeals to the movement toward safer chemistries in the crop production world.Although only two varieties have been presented here, there exists a significantopportunity to tailor-make future molecules and broaden pesticide applicationefficacy.

deposi-References

[1] Haensel, R., Riedl, C., and Poffenberger, C., “Polyglycerolester as Sticker-Penetrant Adjuvants,” Proceedings of the Crops and Chemicals Europe Conference & Exhibition, Berlin, Germany, February 10–11, 2015.

[2] Liu, Z and Gaskins, R., “Visualisation of the Uptake of Two Model Xenobiotics into Bean Leaves by Confocal Laser Scanning Microscopy: Diffusion Pathways and Implication in Phloem Translocation,” Pest Manag Sci , Vol 60, No 5, 2004, pp 434–439.

[3] ASTM E2798 -11, Standard Test Method for Characterization of Performance of Pesticide Spray Drift Reduction Adjuvants for Ground Application , ASTM International, West Conshohocken, PA, 2011, www.astm.org

[4] Fritz, B., Hoffmann, W C., Kruger, G., Henry, R., Hewitt, A., and Czaczyk, Z., “Comparison

of Drop Size Data from Ground and Aerial Application Nozzles at Three Testing ratories,” Atomization and Sprays , Vol 24, No 2, 2014, pp 181–192.

Jerry Gargulak,1Stig Are Gundersen,2Fre´de´rik Bierre,2

and Pauline Rolland2

Lignin-Based Chemicals as Green

Dispersants for Liquid

Formulation: Better Protection

Against Crystal Growth

Citation

Gargulak, J., Gundersen, S A., Bierre, Fre´de´rik, and Rolland, P., “Lignin-Based Chemicals as Green Dispersants for Liquid Formulation: Better Protection Against Crystal Growth,” Pesticide Formulation and Delivery Systems: 36th Volume, Emerging Trends Building on a Solid Foundation, ASTM STP1595, C Poffenberger and J Heuser, Eds., ASTM International, West Conshohocken, PA, 2016, pp 30–41, http://dx.doi.org/10.1520/STP159520150085 3 ABSTRACT

The development of liquid formulations such as suspension concentrates isincreasing in the crop-protection industry However, Ostwald ripening, also calledcrystal growth, can irreversibly occur in the aqueous suspension even at lowsolubility levels of the active material and can cause severe changes in theformulation during storage Lignosulfonates are natural water-soluble polymersbased on wood biorefinery that can be used as crystal growth inhibitors insuspension concentrates In addition, lignosulfonates are highly efficientdispersants because they rapidly adsorb onto the newly created surfaces duringmilling of the active material, preventing its re-agglomeration The purpose ofthe present study was to characterize the stability of fungicide-based suspensionconcentrates using different kinds of dispersants A special-grade lignin-basedproduct from Borregaard LignoTech, Greensperse S7, was tested and comparedwithkraft lignin, sulfonated naphthalene formaldehyde condensate, acryliccopolymer, and a standard sodium lignosulfonate The active material was milleddown to 1 lm in order to encourage the destabilization of the formulation during

Manuscript received October 21, 2015; accepted for publication May 31, 2016.

1 LignoTech USA, 100 Grand Ave., Rothschild, WI 54474

2 Borregaard AS, P.O Box 162, 1701 Sarpsborg, Norway

3 ASTM 36thSymposium on Pesticide Formulation and Delivery Systems: Emerging Trends Building on a Solid Foundation on October 27–29, 2015 in Tampa, Florida.

Copyright V 2016 by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959.

STP 1595, 2016 / available online at www astm org / doi: 10 1520/STP159520150085

“accelerated” storage (i.e., 2 weeks at 54?C) Based on evaluation of formulationstability after accelerated storage, we demonstrated that lignosulfonatesrepresent very interesting alternatives to synthetic dispersants and kraft lignins

in suspension concentrates Our results show that, after accelerated storage,formulations dispersed by Greensperse S7 are stable in terms of particle size andviscosity, reducing the eventuality of crystal growth This can be explained by thepresence of an electrical double layer at the particle/solution interface, leading

to electrostatic repulsive forces, combined withsteric repulsion of the adsorbedmacromolecule

Introduction

The development of liquid formulations such as suspension concentrates is ing in the crop-protection industry However, Ostwald ripening, also called crystal