USE and ASSESSMENT of MARKER DYES USED with HERBICIDES
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SERA TR 96-21-07-03b USE and ASSESSMENT OF MARKER DYES USED WITH HERBICIDES Submitted to: Leslie Rubin, COTR Animal and Plant Health Inspection Service (APHIS) Policy and Program Development Environmental Analysis and Documentation United States Department of Agriculture Suite 5A44, Unit 149 4700 River Road Riverdale, MD 20737 Task No. 10 USDA Order Nos. 43-3187-7-0408 USDA Contract No. 53-3187-5-12 Submitted by: Syracuse Environmental Research Associates, Inc. 5100 Highbridge St., 42C Fayetteville, New York 13066-0950 Telephone: (315) 637-9560 Fax: (315) 637-0445 Internet: SERA1@sprynet.com December 21, 1997 USE and ASSESSMENT OF MARKER DYES USED WITH HERBICIDES Prepared by: Michelle Pepling1, Phillip H. Howard1, Patrick R. Durkin2, 1Syracuse Research Corporation 6225 Running Ridge Road North Syracuse, New York 13212-2509 2Syracuse Environmental Research Associates, Inc. 5100 Highbridge St., Building 42C Fayetteville, New York 13066-0950 Submitted to: Leslie Rubin, COTR Animal and Plant Health Inspection Service (APHIS) Policy and Program Development Environmental Analysis and Documentation United States Department of Agriculture Suite 5A44, Unit 149 4700 River Road Riverdale, MD 20737 Task No. 10 USDA Order Nos. 43-3187-7-0408 USDA Contract No. 53-3187-5-12 Submitted by: Syracuse Environmental Research Associates, Inc. 5100 Highbridge St., 42C Fayetteville, New York 13066-0950 Telephone: (315) 637-9560 Fax: (315) 637-0445 Internet: SERA1@sprynet.com December 21, 1997 TABLE OF CONTENTS TABLE OF CONTENTS .....................................................ii ACRONYMS, ABBREVIATIONS, AND SYMBOLS .............................. iii 1. INTRODUCTION .....................................................1 2. CURRENT PRACTICE .................................................2 3. GENERAL CONSIDERATIONS .........................................3 3.1. DEFINITIONS .................................................3 3.2. CLASSES OF DYES .............................................4 3.3. USE OF DYES IN AGRICULTURAL INDUSTRIES ....................5 4. DYES AS MARKERS/INDICATORS ON VEGETATION .....................6 5. ASSESSMENT OF HAZARDOUS COMPONENTS .........................10 5.1. OVERVIEW .....................................................10 5.2. RHODAMINE B .................................................11 5.2.1. Hazard Identification .......................................11 5.2.2. Exposure Assessment .......................................12 5.2.3. Dose-Response Assessment ..................................13 5.2.4. Risk Characterization .......................................14 5.3. GENTIAN VIOLET ...............................................14 5.3.1. Hazard Identification .......................................14 5.3.2. Exposure Assessment .......................................15 5.3.3. Dose-Response Assessment ..................................18 5.3.4. Risk Characterization .......................................18 5.4. OTHER AGENTS ................................................19 6. SUMMARY AND CONCLUSIONS ......................................21 7. REFERENCES ......................................................23 8. GLOSSARY ........................................................28 Appendix 1. Summary of Chemical and Physical Properties of Some Commercial Dyes Used as Vegetation Markers .................31 Appendix 2. Product Labels and Material Safety Data Sheets ......................32 ii ACRONYMS, ABBREVIATIONS, AND SYMBOLS a.e. acid equivalents a.i. active ingredient AEL adverse-effect level ACGIH American Conference of Governmental Industrial Hygienists APHIS Animal and Plant Health Inspection Service ATSDR Agency for Toxic Substances and Disease Registry bw body weight BUN blood urea-nitorgen cm centimeter 2,4-D dichlorophenoxyacetic acid DEA Drug Enforcement Administration EIS environmental impact statement F female FS Forest Service g gram GC gas chromatography HHRA human health risk assessment IARC International Agency for Research on Cancer kg kilogram L liter lb pound LC50 lethal concentration, 50% mortality LD50 lethal dose, 50% mortality LOAEL lowest-observed-adverse-effect level m meter M male mg milligram mg/kg/day milligrams of agent per kilogram of body weight per day mL milliliter MS mass spectrometry MW molecular weight NOAEL no-observed-adverse-effect level NOEL no-observed-effect level ppm parts per million R.E.D. re-registration eligibility document RfD reference dose U.S. EPA U.S. Environmental Protection Agency USDA United States Department of Agriculture > greater than $ greater than or equal to < less than # less than or equal to = equal to • approximately equal to iii 1. INTRODUCTION The U.S. Drug Enforcement Administration (DEA) is finalizing a Supplement to the Environmental Impact Statements (EISs) for the Cannabis Eradication program in the contiguous United States and Hawaii. The supplemental EIS is an update to the DEA's 1985 and 1986 EISs (DEA 1985,1986). Like the 1985 and 1986 EIS, the supplemental EIS is prepared in cooperation with the United States Department of Agriculture (USDA). In previous EISs (DEA 1985 and 1986), the DEA ruled out the use of dyes or markers: Numerous interagency task forces have investigated various types of dyes that could be used to mark potentially contaminated MMmarijuana ... Finding a workable marker has proven to be a difficult task. It is estimated that research first to find an effective marker and then to test its toxicity would cost more than $3 million and would not be completed for more than 3 years. [DEA 1986, p. 2-7] Various dyes are used, however, in current DEA programs (section 2). The dyes are considered necessary in selective or broadcast herbicide applications to allow the applicator to verify that the herbicide formulation was applied to the intended target. Furthermore, dyes discolor the targeted Cannabis plants making them unsuitable for use or marketing. The supplemental EIS supports the use of two dyes: Fluorescent Red Liquid Concentrate and Hi-Light Blue. Another dye, Colorfast Purple, was used in some DEA sponsored programs but is not explicitly considered in the update document. As the quotation above suggests, selecting a dye to use as a herbicide marker is a complex and potentially expensive undertaking. Nonetheless, the DEA decided to explore the use of alternative dyes as an adjunct to the two dyes covered under the supplement to the EIS. The primary purpose of this report is to provide information that may be used to identify commercially available marker dyes for use with herbicides, particularly 2,4-D, glyphosate, and triclopyr, used by DEA in the eradication of marijuana:. Although the primary focus of this review is marker dyes for the eradication of marijuana, information that might apply to marking other types of vegetation is provided. After an exhaustive literature search, it is clear that there is no published information regarding the use of marker dyes with herbicides. Moreover, the manufactures of the dyes and the suppliers of the herbicides do not make recommendations concerning the use of marker dyes. Through personal communication, it became clear that users of the dyes and not the manufacturers or suppliers usually determine the compatibility of a dye with a herbicide. The users also determine the efficacy of the dye for the a particular application. Consequently, this report attempts to summarize most of the essential factors that should be considered when assessing the compatibility and efficacy of different types of dyes over a broad range of applications (section 3). In addition, several specific dyes are used as markers in various applications by the USDA/Forest Service. These dyes may be considered alternatives to the dyes used now by DEA. Specific information regarding these dyes is summarized in section 4. 1 In addition to compatibility and efficacy issues, the potential human health effects of the dyes are of concern to the DEA. As summarized in the supplemental EIS, one of the agents in Fluorescent Red Liquid Concentrate is Rhodamine B, a compound shown to be carcinogenic to experimental mammals. Information about the toxicity of Rhodamine B, taken largely from the update to the EIS, as well as the toxicity of other potentially hazardous agents found in some commercial dyes are summarized in section 5. 2. CURRENT PRACTICE The supplemental EIS indicates that the DEA may use the herbicides, glyphosate, 2,4-D, and triclopyr, in its programs involving the eradication of marijuana. Glyphosate is used in both Hawaii and Oklahoma, and 2,4-D is used in South Dakota. Triclopyr is not used currently in DEA sponsored programs involving the eradication of marijuana, but may be used in future DEA programs. The DEA has used two dyes with commercial formulations of glyphosate. In program in Hawaii, Fluorescent Red Liquid Concentrate is added to a Rodeo/surfactant mixture. In program in Oklahoma, Colorfast Purple has been used with a Roundup Pro/surfactant mixture. Fluorescent Red Liquid Concentrate is a dye formulation that contains Basic Violet 10, also known as Rhodamine B, as well as acetic acid, each at a concentration of 10% (Formulabs 1988). Basic Violet 10 is a xanthine derivative. The physical and chemical properties and structure of Basic Violet 10 are provided in appendix 1. Basic Violet 10, also know as D&C [Drug and Cosmetic] Red No. 19, was once but is no longer approved as a cosmetic colorant in the United States (CTFA 1991). In the Hawaii program, each gallon of the applied mixture contains