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2009  Chemical Toolbox for AIS Management in Hawaii:   A Review of Substances and Methods  Prepared by Joana F. Tavares-Reager AIS Research Specialist Division of Aquatic Resources Department of Lands and Natural Resources State of Hawai’i A project of the Hawai’i Aquatic Invasive Species LAS, funded by the 2006/2007 NOAA Coral Reef Management Grant Chemical Toolbox for AIS Management in Hawaii: A Review of Substances and Methods Contents  Acknowledgements ........................................................................................... vi  Executive Summary .......................................................................................... vii  Disclaimer ............................................................................................................... x  List of Acronyms and Abbreviations ............................................................ xi  Chapter I: Introduction...................................................................................... 1  Overview of the Aquatic Invasive Species Problem ................................................. 1  AIS in Hawai’i ............................................................................................................... 3  Managing AIS and Choosing Management Strategies ............................................. 4  Chemical Methods’ Advantages and Hazards ......................................................... 10  Pesticide Application and Containment Methods ................................................... 13  Regulatory and Legal Considerations ..................................................................... 17  Chapter II: Piscicides ........................................................................................ 34  USEPA-registered Piscicides ..................................................................... 35  Antimycin A ................................................................................................................ 36  Rotenone .................................................................................................................... 40  Selected Non-registered Piscicides ............................................................ 45  Ammonium compounds and derivatives ................................................................. 45  Chlorination ................................................................................................................ 48  Copper compounds and derivatives ........................................................................ 53  Lime compounds and derivatives ............................................................................ 56  Neem 61  Saponins ..................................................................................................................... 63  Fish Anesthetics (TMS and Clove oil derivatives) .................................................. 66  Comparative Analysis ................................................................................. 69  Chapter III: Aquatic Molluscicides/ Anti­fouling Pesticides ............... 75  USEPA-registered Aquatic Molluscicides ................................................... 76  Copper compounds and derivatives ........................................................................ 76  Niclosamide ................................................................................................................ 80  Selected Non-registered Aquatic Molluscicides/ Anti-fouling Pesticides .... 83  Acetic Acid (Vinegar) ................................................................................................. 83  Ammonium compounds and derivatives ................................................................. 88  Chlorination ................................................................................................................ 89  Iron phosphate ........................................................................................................... 91  ii Lime compounds and derivatives ............................................................................ 92  Neem and papaya extracts ........................................................................................ 94  Potassium permanganate ......................................................................................... 94  Saponins ..................................................................................................................... 95  Comparative Analysis ................................................................................. 99  Chapter  IV:  Aquatic  Herbicides,  Algaecides,  Bactericides  and  Viruscides ......................................................................................................... 103  USEPA-registered Aquatic Herbicides and Algaecides ........................... 104  2,4-D (2,4-dichlorophenoxyacetic acid) ................................................................. 104  Carfentrazone-ethyl ................................................................................................. 108  Copper compounds and derivatives ...................................................................... 110  Diquat 111  Endothall ................................................................................................................... 114  Erioglaucine/ tartrazine (AquashadeTM) ................................................................. 115  Fluridone ................................................................................................................... 117  Glyphosate ............................................................................................................... 120  Imazapyr ................................................................................................................... 125  Penoxsulan ............................................................................................................... 129  Triclopyr salt (TEA) .................................................................................................. 131  USEPA-registered Aquatic Algaecides, Bactericides and Viruscides ...... 134  Algaestats (Hydrogen peroxide) ............................................................................. 134  Selected Non-registered Aquatic Herbicides, Algaecides, Bactericides and Viruscides ................................................................................................. 137  Acetic Acid (Vinegar) ............................................................................................... 137  Acrolein ..................................................................................................................... 138  Ammonium compounds and derivatives ............................................................... 141  Barley Straw ............................................................................................................. 142  Chlorination .............................................................................................................. 143  Diuron 147  Glutaraldehyde ......................................................................................................... 148  Menadione (SeaKleen®) ........................................................................................... 150  Peracetic acid (Peraclean®) ..................................................................................... 153  Metsulfuron-methyl .................................................................................................. 155  Lime compounds and derivatives .......................................................................... 157  Phosphorus inactivation products ......................................................................... 158  Comparative analysis ............................................................................... 159  Chapter V: Other products that have been tested for AIS control . 166  Atrazine ..................................................................................................................... 166  Tavares-Reager, J.F. (2009) iii Chemical Toolbox for AIS Management in Hawaii: A Review of Substances and Methods Azinphos-methyl ...................................................................................................... 166  Benzene compounds ............................................................................................... 167  Carbaryl- organocarbamate pesticides.................................................................. 167  Carbon dioxide ......................................................................................................... 169  Chlordane ................................................................................................................. 169  Chlorothalonil ........................................................................................................... 170  Chlorpyrifos .............................................................................................................. 171  Croton seed powder ................................................................................................ 172  Dalapon ..................................................................................................................... 173  DDT (Dichloro-diphenyl-trichloroethane) .............................................................. 173  Dichlobenil ................................................................................................................ 174  Dieldrin/ Aldrin ......................................................................................................... 175  Endosulfan ............................................................................................................... 175  Endrin 176  Fluazifop-P-Butyl ..................................................................................................... 177  Ichthyothereol .......................................................................................................... 177  Malathion .................................................................................................................. 177  Metaldehyde ............................................................................................................. 178  Poychlorpinene ........................................................................................................ 179  Formaldehyde/ formalin .......................................................................................... 179  Glufosinate-ammonium ........................................................................................... 180  Hydrochloric acid ..................................................................................................... 180  Lindane ..................................................................................................................... 181  Pentachlorophenol (PCP) ........................................................................................ 181  Thanite ...................................................................................................................... 182  Sodium cyanide ....................................................................................................... 182  Sodium sulfite .......................................................................................................... 183  Sodium hydroxide .................................................................................................... 184  Tobacco waste (Nicotine) ........................................................................................ 184  Toxaphene ................................................................................................................ 184  Simazine ................................................................................................................... 187  Chapter VII: Conclusions and Recommendations ............................... 188  Appendix 1: Overview of Non­Chemical AIS Control Methods ........ 197  References ........................................................................................................ 208  Glossary ............................................................................................................. 229  Conversion Tables .......................................................................................... 238  Common Names Index .................................................................................. 240  Taxa Index ........................................................................................................ 242  iv Suggested citation: Tavares-Reager, J.F. (2009) Chemical Toolbox for AIS Management in Hawaii: A Review of Substances and Methods (Internal Report) State of Hawaii’s Department of Lands and Natural Resources, Division of Aquatic Resources/ NOAA’s Coral Reef Conservation Program. 245 p. Tavares-Reager, J.F. (2009) v Chemical Toolbox for AIS Management in Hawaii: A Review of Substances and Methods Acknowledgements  This report was prepared for the State of Hawaii’s Department of Lands and Natural Resources, Division of Aquatic Resources (DLNR, DAR) with funding from the National Oceanic and Atmospheric Agency (NOAA) Coral Reef Conservation Program. I would like to thank the support received from all members of the Aquatic Invasive Species Advisory Group: Earl Campbell and Jeff Herod (USFWS); Eric Conklin (TNC); Domingo Cravalho and Vernon Nakamoto (DOA); Lu Eldredge (Bishop Museum), John Ford and Heidi Heirsh (SWCA); Scott Godwin (Papahanaumokuakea MNM); Bruce Mundy (NOAA/ PCS); Matt Parry (NOAA/ PIRO); Allison Sherwood and Celia Smith (UH/ Botany Dept.); Thierry Work (USGS); Brian Hauk, Jason Leonard, and Tony Montgomery (DLNR/ DAR). Many thanks also go to other fellow DAR/ DLNR personnel who have participated in various stages of this project: Dan Polhemus, Bob Nishimoto, Sara Pelleteri, Petra MacGowan, Katherine Cullison, and Alton Miyasaka. Finally, I am sincerely grateful to researchers and managers with whom I exchanged ideas and information regarding the use of chemicals for the control of AIS: Derek Shield (Aquenal Ltd., Australia); Dave Aldridge (University of Cambridge/ Zoology Dept.), John Russell and Malcolm Pearce (Queensland Primary Industries and Fisheries), Alan Webb (James Cook University), Amber Rossi (California Dept. of Fish and Game); Jim Brooks, Gary Schetrompf and Chris Horsch (USFWS). vi Executive Summary   In response to the prominent negative impacts that aquatic invasive species (AIS) have inflicted on Hawaii’s natural resources, federal and state government officials joined forces with representatives from academia, non-governmental organizations, and various industries and developed the AIS Management Plan for the State of Hawaii. Some of the specific AIS management goals established in this plan published in 2003 were 1) “the implementation of a system for rapid response to contain newly detected AIS”, 2) “the integration of knowledge from efforts to both long-term containment and eradication”, and 3) “the production of a review of management efforts and effective measures to be used when developing strategies and plans to address specific AIS in Hawaii”. This Chemical Toolbox is a step toward fulfilling these goals. It consists of a broad literature review of chemical methods to control and eradicate AIS complemented by comparative analyses and recommendations suited for current and potential AIS problems in Hawaii. This report is organized into six chapters. Chapter I introduces readers to the AIS problem and provides an overview of management and policy strategies for the control and eradication of AIS, in addition to a summary of pertinent legal and regulatory matters. The following three chapters (Chapters II- IV) deal with chemical substances classified according to major target AIS groups: Fish; Mollusks and other fouling animals; Aquatic plants, algae, bacteria, and viruses. Efforts to control and eradicate AIS that do not belong to any of these broad groups but that are relevant to this review (e.g. invasive crustaceans, echinoderms, fungi) are also reported and can be located by searching for their scientific or common name in this report’s Species and Common Names Indexes. Within Chapters II- IV, chemical methods with potential use in control and eradication actions are grouped into USEPA-registered active ingredients and non- registered active ingredients. Each product is reviewed for its chemical nature and suitability to control and eradicate different groups of AIS in individual chemical profiles, within each respective target group chapter. Tavares-Reager, J.F. (2009) vii Chemical Toolbox for AIS Management in Hawaii: A Review of Substances and Methods Chemical profiles identify active ingredients’ origin, toxic effects to target organisms and to non-target species, metabolic processes, pathways, and persistence in the environment, as well as common presentation and uses. This information is organized in the following subsections: Mode of action, Selectivity, Toxicology, Environmental fate and decomposition, Formulations and application methods, and Uses against unwanted AIS. Some profiles do not contain all of these subsections. That is the case of active ingredients that can be used to control more than one target group and, therefore, have more than one profile in different chapters. In these instances, information presented in preceding profiles is not repeated and instead, the reader is directed to the section which contains that information. At the end of each chapter, active ingredients are evaluated in a comparative analysis section, with the objective of identifying which chemical methods are most appropriate to control or eradicate AIS in environments and circumstances of interest. In this analysis, I also considered data limitations, advantages, and potential side effects of active ingredients and I indicated which components are worth further investigation and perhaps the development of specific research and experiments. In chapter V, I briefly present chemical methods that have been tested and evaluated for the control of AIS but that have been shown to be of little or no suitability for this purpose, either because they are not efficient or because they may cause unacceptable levels of undesirable effects. Lastly, in Chapter VI, I offer an overall summary, conclusions and a list of technical and policy recommendations. There, I identify rotenone, antimycin A, acetic acid, and chlorine as promising chemical methods for some AIS management actions. Other active ingredients that merit further testing and consideration are imazapyr, hydrated lime, menadione (SeaKleen) and peracetic acid (Peraclean). I conclude the main portion of this report with a list of actions and experiments that I propose as the next step toward the establishment of an effective framework for rapid response and management of new and established AIS in Hawaii. I also identify legal and regulatory impediments that must be resolved in order to implement these actions and experiments. While the scope of this toolbox is limited to chemical methods to control and eradicate AIS, in appendix 1, I offer a concise assessment of non-chemical methods viii that are available to be used instead or in combination with chemical methods to combat aquatic invasions. Most information presented here comes from peer reviewed papers, official government documents (e.g. USEPA Reregistration Eligibility Decisions and associated Risk Assessments and Toxicological Studies), or from reports prepared by other parties per governmental requests (e.g. studies developed by consulting agencies in lieu of governmental agencies). There are some references to electronic databases, and in these cases I cited both the date on which the information was posted (whenever available) and the most recent date on which I accessed the website. In some instances, I contacted pesticide experts, manufacturers, scientists, and managers directly and all information acquired in this way is cited in the text as personal communication. I sincerely hope this toolbox can assist Hawaii’s natural resource managers in the challenging mission of controlling, and whenever possible eradicating aquatic invasive species that threaten ecological balance in this remarkable archipelago. Tavares-Reager, J.F. (2009) ix Chemical Toolbox for AIS Management in Hawaii: A Review of Substances and Methods Disclaimer  This report is not an endorsement of pesticide use. Chemical products, whether synthetic or organic, should be regarded as hazardous substances and as potential contaminants to the environment. Consequently, their use should be limited to instances of demonstrated need in which potential benefits outweigh potential losses and practical alternatives do not exist. Management plans and chemical applications should be developed and carried out by competent and trained professionals furnished with preliminary studies, and post-application monitoring programs. This document has been developed to serve as a bibliographic reference tool kit for management support and has no legal or regulatory application. Policy reviews and technical analyses presented in this report represent the views of the author at the time this report was completed and shall not be quoted, referred to, or alluded to as being an official position by any government officials or institutions. While striving to develop the most truthful and constructive bibliographic reference tool kit, the author accepts no legal responsibility for the topicality, correctness, completeness or quality of the information provided. Liability claims against the author regarding material or immaterial damage arising from the use or non-use of the information provided, will therefore be rejected. Mention of trade names or commercial products does not constitute endorsement or recommendation for use. x

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Derek Shield (Aquenal Ltd., Australia); Dave Aldridge (University of Cambridge/ Zoology. Dept.), John Russell and Malcolm Pearce (Queensland Primary
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