Environme ntal effects of currently used termiticides under Australian conditions November 2002 Boyd, A.M., Noller, B., White, P., Gilbert, D., Smith, D., Mortimer, M., Langford, P., Martinkovic, J., Sadler, R., Hodge, M., Moore, M.; Murray, J., Cristaldi, C., Zalucki, M.P., Francis, I., Brown, M., Cruice, R., Connell, D. National Research Centre for Environmental Toxicology ISBN 0-9750259-0-2 EnTox 2002 This work is copyright. Apart from any use permitted under the Copyright Act 1968, no part may be reproduced by any process without prior written permission from the authors. Requests and inquiries concerning reproduction and rights should be addressed to Professor Barry Noller, National Research Centre for Environmental Toxicology, PO Box 594, Archerfield, Brisbane, Queensland, 4108. Photographs are reproduced with the permission of Amalgamated Pest Control. To obtain further copies of this publication contact: Professor Barry Noller National Research Centre for Environmental Toxicology 39 Kessels Road Coopers Plains (PO Box 594, Archerfield) Brisbane, Queensland, 4108. Tel: (+61) (07) 3274 9221 Fax: (07) 3274 9003 Email: [email protected] Disclaimer This document has been prepared in good faith, exercising due care and attention. However, no representation or warranty, expressed or implied, is made as to the relevance, accuracy, completeness or fitness for purpose of this document in respect of any particular users circumstances. Users of this document should satisfy themselves concerning application to and, where necess ary, seek expert advice about their situation. The National Research Centre for Environmental Toxicology (EnTox), Energex Limited, the Department of Public Works, Queensland, the Department of Housing, Queensland, Gold Coast Water, the Queensland Environmental Protection Agency, Queensland Rail, Brisbane City Council, Queensland Health Scientifi c Services, Ergon Energy, The University of Queensland, FMC Chemicals Pty Ltd and Griffith University shall not be liable to any person or entity with respect to any liability, loss or damage caused or alleged to have been caused directly or indirectly by this publication. This document does not necessarily represent the views of the National Research Centre for Environment al Toxicology, Energex Limited, the Department of Public Works, Queensland, the Department of Housing, Queensland, Gold Coast Water, the Queensland Environmental Protection Agency, Queensland Rail, Brisbane City Council, Queensland Health Scientifi c Services, Ergon Energy, The University of Queensland, FMC Chemicals Pty Ltd, or Griffith University Designed by: Chris Clayton Printed by: University of Queensland Printery. List of contributors Ms Ann-M arie Boyd National Research Centre for Environmental Toxicology Dr M ichael Brown FM C Chemicals Pty Ltd and Griffith University Professor Des Connell Griffith University M r Carmelo Cristaldi Ergon Energy M r Roland Cruice Department of Housing, Queensland M r Ian Francis FM C Chemicals Pty Ltd M r Dale Gilbert Department of Public Works, Queensland Dr M ary Hodge Queensland Health Scientific Services M r Peter Langford Queensland Rail M r John M artinkovic Brisbane City Council Professor M ichael M oore Queensland Health Scientific Services Dr M unro M ortimer Environmental Protection Agency M r Jasen M urray Ergon Energy Professor Barry Noller National Research Centre for Environmental Toxicology Dr Ross Sadler Queensland Health Scientific Services M r David Smith Gold Coast Water M r Peter White Energex Limited Professor Myron Zalucki The University of Queensland a b c Termite entry points crossing exposed slab edges (a and b) and entering through weepholes (c). Photos courtesy of Amalgamated Pest Control. Termite caps can stop termites entering structures, to a certain degree. In this case the cap was nailed to the stump top during construction, allowing termites to enter the building through the nailhole after the nail had rusted away. Photos courtesy of Amalgamated Pest Control. Examples of termite damage. Photos courtesy of Amalgamated Pest Control. Contents List of Figures List of Tables Objectives Audience Key words Abbreviations Definition of terms Acknowledgments ii ii iii iii iv iv v vii Executive summary Preamble 1 3 1. Introduction 4 2. Termite ecology 5 3. Historical termite management in Australia 7 4. Current chemical termite management in Australia 4.1 The organophosphate termiticides 4.2 The natural pyrethrin and synthetic pyrethroid termiticides 4.3 The chloronicotinyls 4.4 The phenyl pyrazoles 4.5 Growth inhibitors 4.6 Other chemicals 7 10 11 14 16 17 17 5. Migration and behaviour of currently used termiticides in soils 18 6. The efficacy and persistence of currently used termiticides in soils 19 7. S olvents 19 8. Toxicology and risks to human health from termiticide usage 20 9. Potential effects of termiticides on non-target species 23 10. Incidents involving termiticides in southeast Queensland 25 11. Potential new chemical treatments 26 12. Biological control 26 13. Alternative treatments and management tools 27 14. Future directions Recommended further reading References cited Index 31 34 37 44 i List of Figures Figure 1. Key changes in termite management practices in Australia 8 Figure 2. Generalised fate of termiticides after application to soil 9 List of Tables Table 1. Summary of the physicochemical properties of chlorpyrifos 10 Table 2. Summary of the physicochemical properties of permethrin 11 Table 3. Summary of the physicochemical properties of bifenthrin 12 Table 4. Summary of the physicochemical properties of alpha-cypermethrin 13 Table 5. Summary of the physicochemical properties of deltamethrin 14 Table 6. Summary of the physicochemical properties of imidacloprid 15 Table 7. Summary of the physicochemical properties of fipronil 16 ii Objectives This document presents a review of historical, current and future uses of termiticides in Australia. It broadly examines the migration and fate of currently used termiticides in soils. The focus is on identifying risks to the environment and human health and identifying knowledge gaps, research priorities and industry concerns. Where detailed information or reviews are available elsewhere, either electronically or in print, users are directed to those. Audience This document is primarily intended for use by environmental health agencies reviewing risk assessments, by people preparing risk assessments for environmental health agencies and by those regulatory agencies reviewing risk assessments. It is also intended to be of assistance to a broader audience seeking information about termiticides in Australia. iii Key words termite, termiticide, organochlorine, organophosphate, chlorpyrifos, permethrin, cypermethrin, bifenthrin, imidacloprid, fipronil Abbre viations AchE – Acetylcholinesterase ADI – Acceptable Daily Intake AEPM A – Australian Environmental Pest M anagers Association ARD – Acute Reference Dose AS – Australian Standards ATPase/ATPASE - Adenosine Triphosphatase BCA – Building Code of Australia BERU – Built Environment Research Unit, Queensland Department of Housing EC - Emulsifiable concentrate/s EPA – Environmental Protection Association (USA) EPA (Aust.) – Environmental Protection Association (Australia) FSANZ – Food Standards Australia and New Zealand GUS – Groundwater Ubiquity Score GUS = log10(half-life) x (4 – log(Koc )) Hg - M ercury IARC – International Agency for Research on Cancer kg – kilograms Koc – Soil sorption constant Kow – Water octanol partition coefficient L – litre LC50 – the concentration (in water, food or air) that results in 50% mortality LD50 – the dose that results in 50% mortality mg/kg – milligrams per kilogram mg/L – milligrams per litre M SDS - M aterial Safety Data Sheets NHM RC – National Health and M edical Research Council (Australia) NOEC – No Observed Effect Concentration NOEL – No Observed Effect Level NRA – National Registration Authority for Agricultural and Veterinary Chemicals (Australia) ppm – parts per million TCP - 3,5,6-trichloro-2-pyridinol TGA – Therapeutic Goods Act (Australia) iv Definition of terms Terms and parameters are used to describe the physical, chemical and toxicological properties of a pesticide. Described below are some of the terms used in this report to summarise the characteristics of the termiticides listed. Persistence describes the tendency of a chemical to survive in the environment without transformation or loss. Persistence in soils is usually described by the half-life (the time taken for the chemical to degrade to half of the original concentration). Degradation of a pesticide may be by routes, including microbial degradation (breakdown by microorganisms), chemical degradation (breakdown due to reactions with air, water and oxygen, or other chemicals), and photodegradation (breakdown of pesticides by sunlight). The half-life may be established under different conditions, varying pH or soil type or in matrices other than soil (i.e. in water). The resultant values can therefore cover a large range and may only be of use as a comparative or relative description, and can vary greatly due to differences in soils, biota, climate and other factors. For this reason, soil half-life values should be interpreted with caution. Generally: • • • Termiticides described as “persistent” have half-lives of >100 days Termiticides described as “moderately persistent” have half-lives of 30–100 days Termiticides described as “non-persistent” termiticides have half-lives of <30 days The mobility of a pesticide in soil, air and water is influenced by its persistence and can be defined by parameters, including sorption, water solubility and vapour pressure. S orption is the attraction between a chemical and soil, vegetation, or other surfaces, but often simply refers to the binding of a chemical to soil particles. The sorption constant Koc describes the potential to bind to soil particles, based on organic carbon content. Put simply, the higher the Koc value, the greater the sorption. Differences in termiticide formulations and soil types can influence sorption. Pesticides may also volatilise, with rates determined by the moisture content of the soil, and the pesticide’s vapour pressure, sorption and water solubility. Volatilisation from moist soil is described by the Henry’s Law Constant, calculated by the ratio of the vapour pressure of the chemical to its solubility in water, which characterises the tendency for a pesticide to move between the air and the soil water. The higher the Henry's law constant, the more likely it is that a pesticide will volatilise. Vapour pressure is the tendency of a chemical to volatilise – a -8 termiticide with a vapour pressure of less than 1.0 x 10 mm Hg has a low tendency to -3 volatilise, while those with vapour pressures of more than 1.0 x 10 mm H g have a high tendency to volatilise. S olubility in water describes how much of a chemical will dissolve in water, usually measured at 20oC or 25oC. Termiticides with high solubility are more likely to be mobile in the soil, they are likely to leach to groundwater and be involved in runoff. The Groundwater Ubiquity S core (GUS is a value derived from persistence (half-life) and sorption (Koc ). It is used to rank the potential for chemicals to leach and move into groundwater. It is calculated from the formula GUS = log10 (half-life) x [4 – log (Koc )]. Termiticides with a GUS of less than 0.1 are extremely unlikely to move toward groundwater, whereas those with a GUS of more than 4 have a very high tendency to leach and move towards groundwater. Pesticide movement ratings are derived from the GUS: values of 1.0 to 2.0 are low, 2.0 to 3.0 are moderate, 3.0 to 4.0 high, and values greater than 4.0 are very high. v Bioaccumulation, the capacity of a chemical to be stored in fatty tissue from environmental uptake depends on animal metabolism and the Octanol water coefficient (Log Kow) of the chemical in question. Log Kow is the Octanol water partition coefficient, which describes the ability of a chemical to partition between an aqueous and a lipid phase. It is a measure of a chemical’s potential for bioconcentration. A Log Kow value of greater than 3 indicates a propensity for a chemical to bioaccumulate in fat. Toxicity refers to how poisonous a pesticide is. Acute toxicity describes effects that appear within 24 hours after short-term exposure. Acute toxicity measures are used to compare different pesticides. Acute toxicity is usually measured by the response of test animals to oral, dermal and/or inhalation exposures. Chronic toxicity results in delayed effects, after continual or repeated exposure over a long period of time. The effects measured for pesticides are reproducti ve effects (effects on reproductive systems or reproductive ability); teratogenic effects (effects on unborn offspring); carcinogenic effects (producing cancer); oncogenic effects (causing tumours); mutagenic effects (permanent effects on inheritable genetic material); neurotoxic effects (effects on the nervous system) and immunosuppression (suppression of the immune system). Toxicity levels are derived from animal studies (usually rats or mice) and therefore may or may not be directly applicable to humans. The LD50 doses are usually expressed as the amount in milligrams of pure active ingredient per kilogram (kg) body weight of test animals. The lower the LD50, the more toxic the chemical is. Pesticides are packaged with “signal words” depending on how toxic they are. They are labelled “Danger–Poison”, “Warning” or “Caution” accordingly and grouped from slightly toxic to highly toxic as described below: • Highly toxic – “Danger–Poison”, Oral LD50 mg/kg <50; dermal LD50 mg/kg <200; inhalation LC50 mg/L <0.2 • Moderately toxic – “Warning”, Oral LD50 mg/kg 50–500; dermal LD50 mg/kg 200– 2000; inhalation LC50 mg/L 0.2–2 • Slightly toxic – “Warning”, Oral LD50 mg/kg 500–5000; dermal LD50 mg/kg 2000– 20,000; inhalation LC50 mg/L 2.0–20 • Slightly toxic – “Warning”, Oral LD50 mg/kg >5000; dermal LD50 mg/kg >20,000; inhalation LC50 mg/L >20 vi Acknowledgments The authors thank the following people for their assistance and advice in the preparation of this report. John Cheadle (retired, formerly of Arrest-a-Pest), John Field (AEPM A, formerly of Amalgamated Pest Control), Shaun Hale (Amalgamated Pest Control), M ichael Ball and Bill Wiersma (Department of Public Works and Housing, Queensland), Peter Dobson (Brisbane City Council), Ben Foster (Dow Agrosciences), Brenton Peters and John Fitzgerald (Queensland Department of Primary Industries – Forestry Division), John French (University of the Sunshine Coast), John M ott (University of Queensland), Ian M arshall and Steven Begg (Queensland Health). vii Executive summary In response to the emerging huge cost to buildings and other wooden structures of termite damage, and concerns about the environmental and public health consequences of the large quantity and frequent reapplication of termiticides as a result, government and industry research personnel, pesticide suppliers and applicators from organisations in Queensland has identified a need to have appropriate information, reflecting local conditions, on the environmental and health effects of the currently used chemicals for the treatment of termites. Current literature was reviewed on the subject of environmental effects of termiticides together with a review of previous, current and future uses of termiticides in the context of appropriate techniques for termite control and treatment priorities. Currently in Australia, we may be enjoying a period of overlap where older buildings are still being protected by the organochlorines while new structures are treated with organophosphates. Houses built before 1985 may still be protected to some extent by the organochlorine termiticides applied to them. However, the effectiveness of the residual organochlorines will have been reducing over time, and older houses may be at risk of termite infestation. The potential costs of re-treatment and repairs are likely to increase dramatically in the future as older slab-on-ground dwellings become susceptible due to the eventual failure of the organochlorine termiticides. The phasing out of organochlorine termiticides in Australia was undertaken to minimise impact to the environment and, to a lesser extent, public health. It was seen to be a positive step to replace long-persistent chemicals as barriers to termites with those having high activity but a shortened persistence in soil. The transition from 1995 when the organochlorine termiticides were phased out has led to the realisation that significant information gaps and limitations have arisen from the application of replacement chemicals as termite barriers. Information on the migration of currently used termiticides through the soil has been examined, where available, and found to be closely related to soil type. There is limited publicly accessible information, and specific studies are warranted to investigate the behaviour and environmental fate of termiticides under Australian soils and environmental conditions. A review of information on termite behaviour shows that more information is required to understand the foraging activity of Australian termites. Several requirements are apparent: • M ore information is required on Australian termite biology, taxonomy, ecology and behaviour. • The problem of termite infestation needs to be defined, locally and nationally, and highrisk structures and building types identified so that preventive measures can be taken in terms of design and construction. • Further education is required for homeowners, builders, designers, legislators and landscape designers so that they can reduce the risk of infestation through the avoidance of practices in landscaping and design that inadvertently favour termites. 1 • There needs to be a specific focus on the creation of alternative barriers, that takes into account the limitations of currently available physical barriers. An innovative approach to barrier design is needed that incorporates the specific features of slow-release chemicals that are more acceptable to the environment and public health. • Best practice guidelines for minimising the environmental and public health effects of termite control applications need to be developed. 2 Preamble There are huge costs associated with the prevention and treatment of termite infestation in wooden structures and reapplication of chemical barriers is required every 2 to 10 years depending on the products used and local conditions. Following reports in the Australian press of fraudulent operators, and subsequent failure of termiticide treatments, coupled with poor building practices, public confidence in the termite management industry has waned. In addition, there have been incidences of contamination of potable water with solvents following treatment of existing buildings with termiticides, and reports of fish kills as a result of pesticides contaminating waterways. There are also concerns about the environmental and public health consequences about the application and reapplication of large quantities of toxic chemicals over time. For example, in the USA, there has been a partial ban on the use of chlorpyrifos since 2000, with most home and outdoor use of the chemical stopped, and a total phase-out planned. The ban is a result of public concern about pesticide exposure in children following the detection of developmental effects in rats. This document addresses the concerns of individual stakeholders and the public by providing a single reference pertaining to termite management options available in Australia. The purpose of this report is to collate available information of importance to as wide a representation of stakeholders as possible, and to examine whole-of-ecosystem issues. Recognising gaps in knowledge of each component of termite management, from termite ecology through to present and future uses of termiticides in the context of appropriate techniques, is critical in terms of identifying information for acceptable industry practice for termite management and public concerns. This report identifies such knowledge gaps in terms of industry, public and client priorities and provides a basis for planning to address those needs. This report seeks to provide a review on aspects of environmental effects of currently used termiticides, along with a review of previous, current and future termiticides in the context of appropriate techniques for termite management and client priorities. The report provides a basis for developing best practice guidelines. 3 1. Introduction Termites consume wood and cellulose and serve an important ecological function by converting dead trees into organic matter. Unfortunately, the wood in buildings and other structures such as wooden power poles and bridges is equally appealing to termites and infestation can cause considerable damage. On a local level, the Queensland Department of Housing spent $410,000 managing termite infestations in public housing during the 1999–2000 financial year. In the Ipswich, Woodridge and Capalaba areas in southeast Queensland the estimated cost of repairs for termite damage ranged from $18,000 to $60,000 per property (Department of Public Works’ Built Environment Research Unit figures, January 2000). On average, termite infestations cost approximately $1500 in treatment, and repairs of $5000 for each building affected (Caulfield, 2002). It is estimated that 10% of Australian houses have had or will have termite infestations, with that figure rising to 65% in some areas – a resulting per annum cost of $4 billion (Caulfield, 2002). M anagement of termites, and eradication of exotic species is also costly – a campaign to eradicate drywood termite Cryptotermes brevis (Walker) in Queensland is estimated to have cost $4.2 million by 1998 (Peters and Fitzgerald, 1998). Worldwide, damage caused by termites is estimated at U.S $22 billion per annum in terms of damage to wooden structures (La Fage et al., 1988). Treatment and prevention of termite damage is therefore needed, and may give rise to unwanted side effects. Until 1995, effective chlorinated hydrocarbon (organochlorine) termiticide treatments were used to create barriers to termites in Australia. These have since been replaced with other, less persistent, chemicals and physical barriers. As a consequence, chemical termiticides need to be reapplied on a regular basis, averaging every 3 to 5 years depending on local conditions. There is a relative lack of knowledge of the consequences of repeatedly using these replacement chemicals under Australian conditions. Currently, chlorpyrifos (Dow Agricultural Products) and bifenthrin (FM C Chemicals Pty Ltd) are the termiticides in most common usage in Australia, with varying formulations of chlorpyrifos, permethrin, alpha-cypermethrin, bifenthrin, imidacloprid and fipronil registered for use in Australia by the National Registration Authority (NRA). With the withdrawal of chlorpyrifos from use in applications in the US, the use of chlorpyrifos in Australia has also reduced, with a corresponding increase in bifenthrin and imidacloprid use. The major use of termiticides in Australia is for preventative treatments applied to buildings before and during construction, and to existing structural features such as timber power poles and bridges. Treatments of infestations in existing buildings, preventative and remedial applications to wooden power poles and other wooden structures such as timber trestles and bridges are also significant. 4 2. Termite ecology Australia’s termite fauna is diverse, represented by five families (M astotermitidae, Termopsidae, Kalotermitidae, Rhinotermitidae and Termitidae). Within these families there are 40 known genera and more than 266 described species. Termites may be grouped as dampwood, drywood or subterranean, depending on their habits. As suggested by the name, dampwood termites live in rotten wood, particularly in logs or in damp sections of trees. Although they sometimes inhabit rotten wood in structures they are not considered to be of economic concern. The drywood termites have no contact with the ground, and obtain their moisture requirements from the wood in which they live. Drywood termites are considered of economic importance, with the exotic West Indian drywood termite Cryptotermes brevis Shiraki identified as the most destructive species (Peters and Fitzgerald, 1998). Subterranean termites are those that require contact with the ground or moisture and they are responsible for damage to timber structures in buildings and in trees. Termites play a key role in the nutrient cycles of tropical ecosystems. Whitford (1991) recorded long-term negative effects on soils, vegetation and organic material following removal of termites from desert rangelands in New M exico, USA. Soils without termites had lower infiltration and water content and higher nitrogen levels. The changes in soil characteristics resulted in different plant species composition and vegetation productivity. In Australia, the majority of pest termites are native (the exception is C. brevis), which means they are well adapted to local conditions and may be quite resistant to treatments when compared to situations in the USA where the major pest species, Coptotermes formosanus Shiraki, are exotic and restricted in range and habitat and therefore potentially easier to control. In addition, the majority of baseline studies conducted into the effectiveness of chemical treatments have been conducted in North America on C. formosanus and therefore may not be directly transferable to Australian conditions and species. Of the termites that exist in Australia, relatively few are considered to be pests of sound timber, with the most economically important being C.acinaciformis (Froggatt), C.acinaciformis raffrayi Wasmann, C. michaelseni Silvestri, Mastotermes darwiniensis (Froggatt), Nasutitermes exitiosus (Hill) and Schedorhinotermes reticulatus (Froggatt). Subterranean termites forage for food by means of covered runways (galleries), which extend from the central nest to food sources above or below ground. They communicate by secreting pheromones. Colonies consist of distinct castes, each performing a specialised task within the colony. Workers provide food for the colony, feed the other caste members and excavate galleries, while soldier termites defend the colony and tend to be equipped with mandibles or a proboscis (depending on the species) for defence. Reproductives are winged, and tend to swarm after summer rains to establish new colonies. On returning to the ground the reproductives shed their wings and search for food and moisture in the soil. After digging a chamber near a food source, the pair mate and a colony is begun. Supplemental reproductives can be formed in some species within 3 to 4 months after separation from the founding colony (Pawson and Gold, 1996), making it important not to fractionate the colony during management procedures. 5 The management of social insects differs from that of other pests. The complex social interactions of termites (grooming, chemical communication, caste differentiation) should be taken into account, and can be exploited when treating colonies. For example, worker castes gather food and return it to the colony, therefore by providing poison baits or dusting workers with a slow acting toxin, termiticides can be transported to, and spread within, the nest. Grooming behaviours by termites within the nest can result in the toxic dusts that coat returning workers, being spread quickly to other colony members. There is some evidence that social interactions help termite colonies to overcome physiological stresses such as starvation and disease, and possibly the effects of poisons. For example, Ledoux et al. (2001) exposed Cornitermes cumulans (Kollar) workers to chlorpyrifos in order to evaluate any effects of group size on tolerance to poisoning. Survival of poisoned and control termite groups depended on the numbers of individuals in the group. The significance of this is that there is some “socially-induced” ability to overcome physiological stress. Social functions may enhance mechanisms that can help in the detoxification of termites exposed to poisons. The mechanisms by which this occurs are not understood and require further investigation. There is much variation in the breeding strategies of termite species, which in turn may influence the effectiveness of chemical treatments. Tunnelling behaviours of termites through soil treated with pesticides need to be understood, and the ability of a termite colony to tunnel through pesticide-treated soil may be affected by population density. For example, Jones (1990) found that C. formosanus at high population levels were able to construct more and longer tunnels and therefore potentially able to cross termiticidal barriers. Other factors influence tunnelling, e.g. studies of C. formosanus indicate that the size, length and complexity of search tunnels excavated by termites is dependent upon available food sources (Hedlund and Henderson, 1999). When food size (the amount of food available in the feeding chamber) is large, feeding activity and survival are increased, but search tunnel volume is reduced. Termite foraging activity appears to be influenced by seasonal variation in temperature. Evans and Gleeson (2001) found that C.lacteus in artificial feeding stations foraged further from their mounds in summer, whereas in winter they were more likely to be found clustered close to the mounds. Variations in foraging activity also occurred according to air and soil temperature changes, demonstrating that seasonal and daily changes influence activity and foraging behaviour. This indicates that, for these species at least, termites adjust search activity in response to available food supply and environmental conditions. An understanding of these behaviours may be of use for increasing the efficacy of baiting for termite management. At present bait and monitoring systems rely on termites finding and feeding on the baits provided, in a hit or miss fashion. 6 3. Historical termite management in Australia In Australia prior to 1962 arsenic dusting was the most common means of small-scale termite management. Nests were located and dusted directly with arsenic trioxide powder. Before 1995, subterranean termite management in Australia was based on the use of highly persistent organochlorine insecticides (Peters and Fitzgerald, 1998), such as aldrin, dieldrin, chlordane and heptachlor (known collectively as cyclodienes, because of their particular chemical structure), which were well suited to slab-on-ground housing construction. Because of their chemical stability, they were extremely effective Australia-wide, and had no immediate adverse health effects at the levels of exposure arising from the approved use. Due to increasing environmental and public health concerns (primarily with their persistence in the environment and their tendency to accumulate in the fat of animals and humans), these chemicals were voluntarily withdrawn from the market in 1995 (Figure 1) and alternative strategies for termite management have been developed. Organochlorines came into common usage after 1962, and provided long-term protection against termites. Organochlorines used under slabs offered protection from termites for up to 30 years, and pre-treated wood for up to 10 years. For some species organochlorine baits (M irex) were used with success e.g. M irex packed into baits with Eucalyptus regnans and agar gel was effectively used against M. darwiniensis in the Northern Territory (John Cheadle, pers com.). The Northern Territory and Western Australia received an extension to its use of organochlorines in the form of M irex and M irant baits for M. darwiniensis management only, currently registered until June 2003. These products are largely used for prevention of termite infestation of fruit trees in orchards. M ethyl bromide gas is still used to fumigate buildings, timber and furniture for drywood termites, such as C. brevis. Organophosphates and pyrethroids have since been offered as alternatives to the organochlorines, however they are effective against termites for a much shorter time, due to the shorter lifetimes of these chemicals which break down relatively quickly and therefore do not provide long-term protection. The need for more regular applications of the newer, lesspersistent chemicals results in an increased chance that householders and the pest control operators will be more frequently exposed to the chemicals. 4. Current chemical termite management in Australia The withdrawal of the organochlorines as termiticides in Australia has by necessity encouraged the introduction and investigation of new products and methods for termite management. Previously, because the organochlorines were so effective, there was apparently little commercial incentive to develop new chemicals or barrier controls. Chemical control can be divided broadly into preventative and curative. New buildings are treated with a chemical barrier beneath and surrounding their slabs. Where access to slabs is not practical for underslab termiticide application, reticulation systems can be installed pre-construction, enabling repeated application of termiticides over time. Where a termite infestation has occurred, chemicals may be applied as spot treatments, sprays, baits or gases. There are termiticides registered for use in Australia as varying formulations of synthetic pyrethroids (e.g. permethrin and bifenthrin), organophosphates (chlorpyrifos), the chloronicotinyls (imidacloprid), arsenic trioxide (as a dust for spot treatments), and recently a phenyl pyrazole (fipronil), along with wood preservatives such as boron, copper, fluorine and creosote that are also used alone or in combination to prevent termite attack. 7 2002 • 2001 • • 2000 • • 1995 • • • 1993 • 1990 • 1988 • 1987 • 1986 • Fipronil registered for use as a termiticide in October. AS 3660.1 added to BCA, specifies procedures for chemical soil barriers. January 2001, the Queensland provisions of BCA amended to address installation of termite management systems in houses and buildings to incorporate durability of termite management systems in new buildings. AS 3660 parts 2 (existing buildings) and 3 (termite management systems assessment) are added to BCA. Queensland government reviews and tightens regulations. Organochlorine. Withdrawn from use AS 3660.1 incorporates new barrier systems. NRA approves chlorpyrifos and bifenthrin for use under slabs during construction. Federal government inquiry into the use of organochlorines in Australia. NHM RC review of organochlorines as termiticides. Organochlorines under increasing international pressure from environmental, health and union groups. Organochlorines withdrawn from agricultural use. Draft BCA legislation considers structural components only. < 1986 • Building regulations apply to “whole-ofhouse”. Figure 1. Key changes in termite management practices in Australia. 8 Repairs for termite damage potentially up to $18,000 to $60,000 per property (Qld. Dept. Housing figures). Average figures are approximately $1500 in treatment, with repair costs of $5000 per building (Caulfield, 2002). An estimated 10% of Australian houses have had or will have termite infestations, with that figure rising to 65% in some areas, with a resulting per annum cost of $4 billion (Caulfield, 2002). M ovement of volatiles into the air and photodegradation Original application UV degradation in exposed areas Possible uptake by animals Possible plant uptake Possible runoff Vertical movement into soil and groundwater Degradation – chemical Leaching Figure 2. Generalised possible fate of termiticides after application to soil. Clipart sourced from http://www.free-clipart.net 9 4.1 The organophosphate termiticides Chlorpyrifos (Dow Agricultural Products) – Trade names internationally include Pyrinex, Brodan, Detmol UA, Dowco 179, Dursban, Empire, Eradex, Snare, Lorsban, Paqeant, Piridane, Scout, Deter and Stipend. Chlorpyrifos is a widely used organophosphate insecticide, which is active against insect pests. The toxicity of chlorpyrifos results from the action of the metabolite chlorpyrifos oxon, which inactivates acetylcholinesterase (AchE) at neural junctions. Overstimulation of the peripheral nervous system then results in death. Chlorpyrifos acts on insects primarily as a contact poison, and has some action as a stomach poison. The solvents used in formulations are usually hexane or xylene. The environmental fate of chlorpyrifos, including comprehensive solubility, sorption and degradation data, has been extensively reviewed by Racke (1993). Chlorpyrifos [CAS 2921-88-2] C 9 H11 Cl3 NO3 PS 0,0-diethyl 0-(3,5,6-trichloro-2pyridyl) phosphorothioate. Property Group Physical state (at 25o C) Melting point Vapour pressure (mm Hg at 25o C) Solubility in water (mg/L) Value Organophosphorothiote compound Solid 41.5–43.5o C 2 x 10-5 Source EXTOXNET 20.4 Average sorption coefficient (Koc) Log Kow Metabolites 8498 4.7 – 5.3 TCP 3,5,6-trichloro-2-pyridinol in rats and humans; TMP -3,5,6-trichloro-2ethoxypyridinein in soil CPF-oxon OSU Ext. Pesticide Properties Databas e Racke 1993 EXTOXNET EXTOXNET Half-life (under different conditions) • • • Pesticide movement rating • • • Very 11– 141 days in 7 soils loamy sand to clay, soil pHs from 5.4 – 7.4 16 – 72 days in distilled water (pH 5 – 9) irrigated loam 69 – 90 days non-irrigated loam 48 days 62 hours in humans low Racke et al. 1992 Racke et al. 1993 Pike and Getzin 1981 Pike and Getzin 1981 EXTOXNET OSU Ext. Pesticide Properties Databas e Table 1. Summary of the physicochemical properties of chlorpyrifos Chlorpyrifos has low solubility in water and partitions readily from aqueous to organic phases (Racke, 1993). Because it is tightly adsorbed by soil, it is not expected to leach significantly and movement through soil is limited. Volatilisation from the soil surface due to its intermediate vapour pressure can contribute to loss. Cleavage of the phosphorothioate ester bond to form 3,5,6-trichloro-2pyridinol (TCP) is the major path to degradation. Once this occurs TCP is degraded by photolysis. The vapour phase of chlorpyrifos can be destroyed by hydroxyl radicals. Alternatively, it may be adsorbed by airborne particles, and may be reactivated and taken up by local biota. High soil temperature, low organic content and low acidity increase the degradation of chlorpyrifos. 10 Chlorpyrifos has a half-life soils ranging from 2 weeks to over 1 year, depending on the soil type, climate, and other conditions. As documented by Racke et al. (1993), depletion rates for chlorpyrifos in soil increase with temperature, with each 10oC rise in temperature approximately doubling the depletion rate (M urray et al., 2001). Chlorpyrifos dissipates more rapidly from water than from soil, with half-lives of 16 to 72 days in distilled water (pH 5 to 9) (Racke 1993). Volatilisation is the primary route of loss of chlorpyrifos from water. However, it partitions from the water column to sediments, and as a result desorption from sediments can cause long-term residual contamination of the water column. 4.2 The natural pyrethrin and synthetic pyrethroid termiticides Pyrethrins are natural insecticides derived from the flowers of certain species of Chrysanthemum plants. The plant extract (pyrethrum) contains pyrethrins (pyrethrin I and II). Pyrethroids are synthetic analogues of pyrethrins. They are used to form chemical barriers to repel and/or kill termites and are used in the control of many insect pests. Pyrethroids act by inhibiting the nervous system of insects inhibiting ATPase enzyme production, and affecting sodium ion channels, and in some cases affecting GABA (gamma-aminobutyric acid) action. Permethrin [CAS 52645531] C 21 H20 Cl2 O3 3-(2,2-dichlorethenyl )-2,2-dimethyl-, (3phenoxyphenyl) methyl ester Property Group Physical state (at 25o C) Value Synthetic pyrethroid Pale brown liquid or crystalline colourless Melting point Vapour pressure (mm Hg at 25o C) Solubility in water (mg/L) 34 – 35o C 0.045 Average sorption coefficient (Koc) Log Kow 100,000 Half-life (under different conditions) Pesticide movement rating Figure: Ware 1999 Source EXTOXNET 0.2 6.1004 • < 2.5 days in near-estuarine water exposed to sunlight • 4.6 days in soil 30 to 38 days Extremely low OSU Ext. Pesticide Properties Databas e Table 2. Summary of the physicochemical properties of permethrin Permethrin is the active ingredient in broad-spectrum insecticides, including termiticides. In most cases permethrin (25:75 CIS:TRANS) is present at 500 g/L and mixed with hydrocarbon solvents. Example products internationally include Dragnet (FM C (Chemicals) Pty Ltd), Perigen 500 (Bayer Cropscience Pty Ltd) Imperator (Syngenta Crop Protection Pty Ltd) and Pestgard (Ecolab Pty Ltd). Permethrin is currently available in Australia as a dust, or liquid used to treat active infestations. Elsewhere, it is also used in wood preservatives to prevent 11 termite attack, for example in Rurply industrial plywood protectant (Bayer Cropscience Pty Ltd) the active ingredient is permethrin combined with benzalkonium chloride. Bifenthrin (FMC Chemicals Pty Ltd) – Trade names internationally include Biflex, Talstar, Bifenthrine and Brigade. Bifenthrin (Biflex) is used in Australia as a barrier termiticide as well as for treatment of active infestations. Bifenthrin (Bistar) is also used as a wood preservative in Australia. As with other pyrethroids, bifenthrin is an insecticide and acaricide, which causes paralysis in insects by affecting the nervous system. Property Group Physical state (at 25o C) (2-methyl-1, 1-biphenyl-3-y1)-m ethyl-3- (2chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethyl cyclopropanecarboxylat e or (2-methylbiphenyl3-ylmethyl (Z)-(1RS, 3RS)-3-(2-chloro-3,3,3trifluoroprop-1-enyl)-2,2dimethylcyclopropanecarboxylate. Value Synthetic pyrethroid Light brown viscous oil Melting point 57 - 64oC Vapour pressure (mm Hg at 25o C) Solubility in water at 25o C (mg/L) 1.8x10-7 Average sorption coefficient (Koc) 1,000,000 131,000 to 302,000 >6 Bifenthrin [CAS 82657-04-03] C 23 H22 ClF3 O2 Octanol-water coefficient (Log Kow) Metabolites Half-life (under different conditions) Pesticide movement rating Source EXTOXNET 0.01 • In soil: 2-methyl-3-phenyl-benzyl alcohol, 2-methyl-3-phenylbenzoi c acid, 2-methyl-3-phenylbenzaldehyde, 4-hydroxy bifenthrin, and cis, trans-4(2-chloro-3, 3,3-trifluoro-1-propenyl)3,3-dimethylcyclopropanecarboxylic acid • By photolysis: 4’hydroxyl bifenthrin • Anaerobi c 97 – 156 days • Aerobic 65 – 125 days • 7 days – 8 months in soil • 65 – 125 days in soil • Photodegradation >100 days Extremely low OSU Ext. Pesticide Properties Databas e Table 3. Summary of the physicochemical properties of bifenthrin The Koc values of bifenthrin indicate that it is likely to be immobile in soil (Table 3). Bifenthrin is relatively insoluble in water. However, because it is attached to colloidal particles it may be transported with them into waterways and groundwater. Bifenthrin will exist in the atmosphere in particulate and vapour phases, where vapour phase bifenthrin is degraded by hydroxyl radicals and ozone. Because pyrethroids are readily degraded by microorganisms, it is likely that microbial degradation of bifenthrin will occur. Alpha-cypermethrin (BASF Australia Ltd; FM C Chemicals Pty Ltd) is a racemic mixture of two of the four cis isomers – the (1R, cis)S and (1S, cis)R isomers of cypermethrin. Example 12 products are Stedfast and Prevail, which are registered in Australia for use as a chemical barrier. Alpha-cypermethrin C 22 H19 C12 NO3 [CAS 67375-30-8] (S)- alpha-cyano-3-phenoxy benzyl (1R,3R) 2,2-dichlorovinyl)-2,2- dimethylcyclopropane carboxylat e and (R) - alpha cyano - 3-phenoxy benzyl (IS,3S)-3-(2,2 dichlorovinyl) cyclopropane carboxylate Property Group Value Synthetic pyrethroid ester Physical state (at 25o C) White, cream yellow or colourless crystalline powder, solid or liquid (EC) 155–180o C (EC) 78o C (powder) Melting point Figure: Meghmani Organics Fact Sheet Source Alpha-Cypermethrin MSDS 1999 -7 Vapour pressure (mm Hg at 25o C) 1.7×10 Solubility in water at 25o C (mg/L) Octanol-water coefficient (Log Kow) Metabolites Half-life Pesticide movement rating 0.005–0.01 5.16 cis-cyclopropane carboxylic acid hydrolysis half-li fe 20 – 29 days Extremely low OSU Ext. Pesticide Properties Databas e Table 4. Summary of the physicochemical properties of alpha-cypermethrin 13 Deltamethrin (AgrEvo Environmental Health, Inc.) – Trade names internationally include Butoflin, Butoss, Butox, Cislin, Crackdown, Cresus Decis-Prime. Deltamethrin (Table 5) is used in Kordon-impregnated barrier products. In Australia deltamethrin is sometimes, but not often, used in termiticides. Deltamethrin C 22 H19 Br2 NO3 [CAS 52918-63-5] (S)-cyano-3-pehoxybenzyl (1R)-cis-3-(2,2dibromovinyl)-2,2-dimethylcyclopropane carboxylat e Property Group Physical state (at 25o C) Melting point Vapour pressure (mm Hg at 25o C) Solubility in water (mg/L) Octanol-water coefficient (Log Kow) Value Synthetic pyrethroid Powder - white or colourless, crystalline 98-101o C 1.5 x 10--8 Source EXTOXNET WHO Data Sheet EXTOXNET <0.1 4.6 Table 5. Summary of the physicochemical properties of deltamethrin 4.3 The chloronicotinyls (nicotinoids) The nicotinoids are a relatively new class of insecticide, modelled on natural nicotine. Imidacloprid (Bayer Cropscience Pty Ltd) products internationally include Admire, Condifor, Gaucho, Premier, Premise, Provado, and M arathon. Only Premise is registered for use against termites in Australia. Imidacloprid is a systemic, chloro-nicotinyl that works by interfering with the transmission of stimuli in the insect nervous system. Specifically it causes blockage of the nicotinergic neuronal pathway, leading to acetylcholine accumulation – resulting in the insect's paralysis, and/or death. Imidacloprid-based insecticide formulations are available as dustable powder, granular formulations, seed dressing (flowable slurry concentrate), soluble concentrate, suspension concentrate, and wettable powder. It is currently registered in Australia for post-construction applications only. 14 Hydrolysis and aerobic soil metabolism data indicate that imidacloprid is persistent and mobile with a tendency to leach. Under some circumstances contamination of groundwater is possible (EPA Imidacloprid Pesticide Fact Sheet 1994). Imidacloprid can be translocated via plant roots. When used to form applied termiticide barriers, consideration should be given to the risk of product losses due to plant uptake, and possible ingestion by grazing animals. Imidacloprid C 9 H10ClN5 O2 [CAS 13826-41-3] 1-(6-chloro-3-pyridylmethyl)-Nnitroimidazolidin-2-ylideneamine, 1-[(6-chloro3-pyridinyl)methyl]-N-nitro-2imidazolidinimine Property Group Physical state (at 25o C) Melting point Vapour pressure (mm Hg at 25o C) Solubility in water at 20o C (mg/L) Value Chloronicotinyl Colourless to light yellow crystals or powder 136.4-143.8oC 1.5 X 10-9 Octanol-water coefficient (Log Kow) Average sorption coefficient (Koc) Metabolites 3.7 at pH 7.8 Half-life (under different conditions) • • High Pesticide movement rating 510 132–310 6-chloronicotinic acid – eventually breaks down in soil to CO2 Soil photolysis half-li fe 38.9 days 355 days in water (pH 9) Table 6. Summary of the physicochemical properties of imidacloprid 15 Figure: Bloomquist 1999 Source EPA Fact Sheet 4.4 The phenyl pyrazoles (fiproles) Fipronil (Bayer Cropscience Pty Ltd.) - is a phenyl pyrazole, a new class of chemical (Table 7). Products internationally include Termidor SC and Termidor 80 WG. Fipronil has been under consideration by the NRA for registration in Australia as termiticide and gained registration for protection of structures from subterranean termite attack in October 2002. It was previously used in Australia only for topical flea and tick control on dogs (and in agriculture e.g. Regent). Fipronil is a disruptor of the insect central nervous system via the GABA (γ-aminobutyric acid) channel, acting with contact and stomach action. It blocks the GABA-gated chloride channels of neurons in the central nervous system, resulting in neural excitation and death of the insect. Fipronil C 12 H4Cl2 F6 N4 O4 S [CAS 120068-37-3] 5-amino-1-[2,6-dichloro-4(tri fluoromethyl)phenyl]-4[(tri fluoromethyl)sul finyl]-1H-pyrazole-3carbonitrile Property Group Physical state (at 25o C) Melting point Vapour pressure (mm Hg at 25o C) Solubility in water (mg/L) Average sorption coefficient (Koc) Octanol-water coefficient (Log Kow) Metabolites Value Phenyl pyrazole White powder 195.5 to 203oC 2.8 x 10-9 1.9 (distilled water), 2.2 (pH 9) 803 4.01 • • • Half–life (under different conditions) Figure: Ware 1999 Reference NRA Fipronil Evaluation In soil: RPA 20076 (amide), MB46513 (fipronil-desul finyl), and RPA 104615 In water: MB 45950 (sulphide) Under aerobic conditions RPA 200766 and MB 46136 (sulfone) • • • 10–130 hours in water 45–530 hours in soil 122–128 in oxygenated soil • 116 – 130 days in anaerobic conditions Table 7. The physicochemical properties of fipronil summarised. 16 Mulrooney et al. 1998 Mulrooney et al. 1998 National Telecommunication Network (NTPN)Fact Sheet NTPN Fact Sheet 4.5 Growth (chitin synthesis) inhibitors Hexaflumuron (Recruit II termite bait – Dow Agrosciences) (C16H8Cl2F6N2O3) [CAS 8647906-3]: A benzoylurea insecticide, which is a chitin synthesis inhibitor, used in bait stations. Hexaflumuron binds tightly to soil particles. Similar are Triflumuron (Intrigue termite dust – Bayer Cropscience) (C15H10ClF3N2O3) [CAS 64628-44-0], and Chlorfluazuron (Requiem termite bait) (C20H9Cl3F5N3O3) [CAS 71422-67-8], chitin synthesis inhibitors used in bait stations. 4.6 Other chemicals Arsenic trioxide (As4O6) [CAS 1327-53-3], is used in bait and switch management programs, and for direct dusting onto nests. The arsenic content in these dusts ranges from 379 g/kg to 500 g/kg. Methyl bromide (H3Br) [CAS 74-83-9] gas is used to fumigate drywood termite infestations. It is pumped into sealed buildings or wooden articles. Boron – new boron complexes for wood protection are being developed with some success by CSIRO and the Centre for Green Chemistry at M onash University in Australia. With leachresistant boron binding to wood as the ultimate aim, high levels of mortality for C. acinaciformis have been recorded for particular boron formulations (Humphrey et al., 2002). Boron products include Boracol (Osmose Australia Pty Ltd), which is registered for use for pre-treatment and remedial treatment of timber against decay (fungal) and insects. Constituents include M ono ethylene glycol (886 g/kg). Boron is present in the form of disodium octoborate tetrahydrate (52 g/kg) and benzalkonium chloride (12 g/kg). Boron-impregnated rods (Preschem Rail Rods) are inserted into wooden railway sleepers as a slow release preservative and termite repellent. Impregnated wood preservatives include mixtures of copper, arsenic and other chemicals (i.e. chromium) used for protection against termite and borer attack. Generally, these are used in pressure impregnation of new wood e.g. Tanalith CP Paste is a mixture of arsenic (95.8 g/L), chromium (135.199 g/L) and copper (75.699 g/L). Other products approved for use in Australia include Protim 70, a mix of white petroleum spirit (613 g/L), copper naphthenate (170 g/L) and permethrin (2.599 g/L). Combinations of disodium octoborate tetrahydrate and benzalkonium chloride are also used in formulations of insecticidal wood preservative. Creosote (creosote, coal tar) external timber preserving oil (Davco; Koppers Arch Wood Protection Australia Pty Ltd; Protectex Chemicals Pty Ltd.) is also used to preserve wood, and is painted onto external timber as a means of preservation and a termite deterrent. Creosote was typically used in combination with aldrin. Mirex (C10Cl12) [CAS 2385-85-5] (M irant Pty Ltd). M irant (M irex 2.0 g/kg) and M irex 6 g/kg baits are the only organochlorine cyclocompounds termiticide currently used for termite control in Australia. They are registered for use only in the Northern Territory and Western Australia for M. darwiniensis control (registered currently to June 2003), primarily for use in the prevention of termite infestations of fruit trees under cultivation. 17 5. Migration and behaviour of currently used termiticides in soils Environmental variables are important, particularly in terms of transport, degradation and volatilisation of termiticides. Following application, termiticides can be lost from the original application site via lateral and vertical movement into surrounding soil and groundwater. It is possible that these chemicals will also be transferred to local biota and animals (Figure 1). The movement of pesticides through soil largely depends on the physical properties of individual chemical actives, the presence of water and biota and organic material, as well as the solvent/s that have been used in the pesticide formulation. Soil characteristics, pH and the presence of organic matter play major roles in determining the persistence and efficacy of chemicals. The half-life of a chemical in the soil will depend on a combination of these factors and will be influenced by the biota present. Sandy soils with low biota/low organic content and wet conditions generally result in increased transport, whereas those with high clay and organic content tend to not allow chemical migration as readily. The mineral content of the soil will influence degradation, by affecting adsorption rates or catalysing decomposition. Termiticides, in particular the organophosphates, can be lost from the soil through movement of volatiles into the air due to their significant vapour pressures at ambient temperatures. Soil properties – organic content, silt and clay content, pH and cation exchange capacity – may affect the bioavailability and dispersal of pesticides. In comparisons of different soil types treated with imidacloprid, pesticide effects on R. flavipes were greatest in sand and reduced in silty clay loam soils (Ramakrishnan et al., 2000). Testing of four soil types with six termiticide formulations indicate that soils have a significant influence on the efficacy of the chemicals (Forschler and Townsend, 1996). Of the termiticides tested (including chlorpyrifos, fenvalerate, cypermethrin and permethrin), all had concentrations lethal to termites that were at least seven times lower in sandy soils than in sandy loam or sandy clay loam (Forschler and Townsend, 1996). M urray et al. (2001) examined the stability of chlorpyrifos in six Australian soil types. Soil pH had no effect on the rate of degradation. In contrast, acidic soils with low clay and organic content in Texas, USA, were found to be the most stable in terms of remaining bioavailability of pesticides, while alkaline soils with high clay content and organic compositions higher than 1% were least effective in retaining termiticide residuals over time (Gold et al., 1996). 18 6. The efficacy and persistence of currently used termiticides The physicochemical properties of termiticides directly influence their behaviour, persistence and bioavailability after application (see tables in section 4 for summaries of physicochemical properties). Australian evaluations of the organophosphates in soils suggest an effective life for chlorpyrifos of 7 to 12 years if covered, to as little as 4 years when exposed to the elements (Lenz et al., 1988), and suggest that in tropical Australia, the chemical be reapplied at 3-year intervals. A field study of leaching and degradation of pesticides (including chlorpyrifos, chlorthal dimethyl, fenamiphos, fenamiphos plus metabolites, linuron, metalaxyl, metribuzin, prometryne, propyzamide and simazine) in coastal sandy soils (pH 5.3) in Western Australia demonstrated that degradation rates vary widely between pesticides (Kookana et al., 1995). In this study, chlorpyrifos degraded significantly, but did not move considerably, and it was concluded that it was unlikely to reach groundwater (Kookana et al., 1995). A study of 6 termiticides (bifenthrin, chlorpyrifos, cypermethrin, fenvalerate, permethrin and isofenphos) applied to different soil types in Texas, USA, demonstrated significant differences in effectiveness (as measured by termite activity), bioavailabilty and residue. The most stable over 5 years were permethrin and fenvalerate. Isofenphos was the least stable with significant loss of activity within 24 months after application (Gold et al., 1996). Barrier efficacy tests of a range of termiticides (Dursban, Equity, Dragnet, Prevail, Biflex, Pryfon, Demon, PP321 and Sumithion) in the USA indicate that while all formulations provide equal protection against R. flavipes, C. formosanus was able to tunnel deeper into sand treated with organophosphates than in sand treated with pyrethroids (Su et al., 1993). Isofenphos lost effectiveness within 1 year, and rapidly degraded – probably as a result of alkaline sand (pH 8.1), microbe activity and high rainfall (Su et al., 1993). Pyrethroids (bifenthrin, cypermethrin, lambda-cyhalothrin and permethrin) appear to provide longer protection than organophosphates (chlorpyrifos, fenitrothion and isofenphos). According to 5-year field trials in Florida, USA, against R. flavipes (Su et al., 1999), permethrin had the longest half-life (21.9 months) of the pesticides examined. M icroencapsulated formulations generally result in longer persistence. Little published Australian data is publicly available on the persistence and efficacy of other termiticides. 7. S olvents The solvents used to formulate commercially available termiticides are of interest, since alone or in combination with other chemicals they may have significant effects on the active ingredients and their environmental fate. In some cases, solvents may cause toxic effects. Unfortunately, the solvents used in pesticide formulations are often treated as inerts, and not listed in detail on pesticide labels. It is often difficult to obtain information about the exact mix of adjuvants and solvents used in formulations because of commercial in confidence. Solvents and adjuvants used may include a range of petroleum distillates, isopropanol, methanol, toluene, xylene, penetrants, stickers (film extenders), surfactants, detergents, dusts, emulsifiers and anticaking agents. Because particular combinations of solvents and adjuvants used in formulations may give companies a competitive advantage, their inclusion in labelling is often sparse. In many cases continuous subtle changes to the formulations of products are made to suit particular purposes, resulting in several non-identical products sharing the one original name. Because of the varied requirements for termiticides, solvents may not always be suited to 19 all applications and “boutique” formulations may be needed for specific uses. For example, around power poles, a formulation is required to remain in a restricted area and not spread away from the pole when applied, whereas under the slabs of houses it is desirable that the termiticide be distributed evenly underneath the slab. It is possible that there may be interactions leading to additive or reduced-level effects, between pesticides and the components of their formulations. For example, Axelrad et al. (2002) found synergism between chlorpyrifos and regular spirit solvent and also with chlorpyrifos and pyrethrum, but additive effects (in terms of neurological toxicity) in other combinations of chlorpyrifos and pyrethrum with individual components of a commercial formulation. In addition, solvents may influence the movement and action of the active ingredient through soils and water. There is some evidence that solvents alone may affect termites. For example, sand treated with solvents alone may be toxic to termites – with 24 to 86% of Reticulitermes hesperus Banks killed after 24 hours of exposure to the air-dried solvent treated sand (Rust and Smith, 1993). 8. Toxicology and risks to human health from termiticide usage In Australia, termiticides must be approved and registered by the NRA. Prior to registration for use in Australia, a proposed pesticide must undergo an assessment process, which includes assessment for possible effects on public health and on the environment. Toxicity and potential public health issues are assessed by the Commonwealth Department of Health, occupational health and the National Occupational Health and Safety Commission (NOHSC) assess safety issues, and Environment Australia (EA) assesses environmental safety. The NRA assesses chemistry and efficacy. Toxicology data for termiticides is derived largely from animal studies, and involve doses that are generally much larger than those for likely human exposures. Toxicity tests identify ‘no observable effect levels’ (NOELs) in animals, and these are used to establish acceptable limits for exposure in humans at which no adverse health effects would be expected – the Acute Reference Dose (ARD) and Acceptable Daily Intake (ADI). Because formulations are designed to enhance environmental persistence (in order to be effective against termites for longer periods of time), it is highly desirable that long-term effects on environmental and public health under Australian conditions be investigated with emphasis on long-term sublethal effects, which are not assessed in acute studies. When applied according to safety guidelines and manufacturers’ recommendations, the risk of poisoning or exposure to high levels of termiticides is minimal. Trace residues nonetheless can be sometimes found in water. Indoor air pollution caused by pesticides may be of concern in buildings with poor ventilation, resulting in long-term exposure to low levels of chemicals. Chlorpyrifos was recorded in indoor air in Japan, and did not decrease 5 years after application for termite control (Yoshida et al., 2000). Japanese investigators found that levels 3 3 of chlorpyrifos and S-421 in indoor air ranged up to 0.258 µ-g/m and 0.174 µ-g/m respectively in houses where chlorpyrifos had been applied to building timbers for termite control (Katsura et al., 1996). In Western Australia, 19 of 22 houses monitored for pesticide levels had detectable levels of pesticides in indoor air – in order of frequency: heptachlor; dieldrin; chlordane; aldrin and chlorpyrifos. Although chlorpyrifos was least frequently 3 detected, the mean concentration of 2554 µg/m was significantly higher than that of other pesticides (Dingle et al., 1999). These levels are well below the National Academy of Sciences 3 guideline level for ambient air of 10 µg/m and are considered not to pose an acute threat to public health. However, data on long-term exposure to low levels is limited 20 Chlorpyrifos (ADI 0.003 mg/kg/day, NOEL 0.03 mg/kg/day TGA, 2002) is moderately toxic to humans. Poisoning from chlorpyrifos can affect the central nervous system, the cardiovascular system, and the respiratory system. It is a skin and eye irritant. While some organophosphates are readily absorbed through the skin, studies suggest that skin absorption of chlorpyrifos is limited in humans. Symptoms of acute exposure to organophosphate (and other cholinesterase-inhibiting compounds) may include the following: numbness, tingling sensations, loss of coordination, headache, dizziness, tremor, nausea, abdominal cramps, sweating, blurred vision, difficulty breathing or respiratory depression, and slow heartbeat (EXTOXNET Chlorpyrifos Pesticide Information Profile). Very high doses may result in unconsciousness, incontinence, convulsions and fatality. Some organophosphates may cause delayed symptoms beginning one to four weeks after an acute exposure, which may or may not have produced immediate symptoms. In such cases, numbness, tingling, weakness, and cramping may appear in the lower limbs and progress to incoordination and paralysis. Improvement may occur over months or years, and in some cases residual impairment will remain. P lasma cholinesterase activity levels may be inhibited when chlorpyrifos particles are inhaled. The EPA (USA) analysis found exposure to Dursban (chlorpyrifos) on the skin, in food, or by inhaling it could be harmful to human health. The EPA said it had a “particular concern” with Dursban poisoning cases reported to federal officials. Repeated or prolonged exposure to organophosphates may result in the same effects as acute exposure, including the delayed symptoms. Chlorpyrifos is readily absorbed into the bloodstream through the gastrointestinal tract if ingested, through the lungs if it is inhaled, or possibly through the skin if there is dermal exposure. In humans, chlorpyrifos and its principal metabolites are eliminated rapidly. Chlorpyrifos primarily affects the nervous system through inhibition of cholinesterase. Animal studies suggest that chlorpyrifos is rapidly absorbed and metabolised (to TCP), and the parent compound and metabolite are rapidly excreted in urine. In orally dosed pregnant rats (at 14 to 18 days gestation) AchE and BuChE activities were inhibited significantly in both maternal and foetal brains one hour after ingestion (Ashry, K.M . et al., 2002). The dose used here was 50 mg/kg, which is 61% of the LD50 for female rats. In addition, neonatal rats orally administered much lower rates of chlorpyrifos, at 1 mg/kg or 5 mg/kg, demonstrated deficiencies in cataechloaminergic synaptic function persisting into adulthood (Slotkin et al., 2002). Current evidence indicates that chlorpyrifos does not adversely affect reproduction, and available evidence suggests that chlorpyrifos is not teratogenic. Chlorpyrifos is not considered to be a carcinogen, nor does it appear to have reproductive effects at levels of up to 2 mg/kg per day (EPA Pesticide Factsheet, Chlorpyrifos 1984). There is no available evidence that chlorpyrifos is mutagenic. However, Rahman et al. (2002) report dose-dependent DNA damage detectable in mice 24 hours after being fed chlorpyrifos at doses of 0.28 to 8.96 mg/kg body weight. Assessment of neurological function in a group of pesticide applicators exposed to chlorpyrifos (n=191) compared to non-exposed controls (n=189) revealed that there was no significant difference in clinical examinations. However, the exposed group under-performed in pegboard turning and postural sway tests and reported significantly more symptoms (memory problems, fatigue, loss of muscle strength). Eight exposed subjects who had reported prior chlorpyrifos poisoning had low performance on tests (Steenland et al., 2000). 21 The pyrethroids are not considered extremely toxic to humans. Exposure can cause skin, eye and respiratory irritation, and sometimes cause allergic reactions. Tingling sensations in the hands and face may follow exposure. Bifenthrin (ADI 0.01 mg/kg/day, NOEL 1 mg/kg/day TGA, 2002) and alpha-cypermethrin (ADI 0.05 mg/kg/day, NOEL 4.7 mg/kg/day TGA, 2002), can cause nerve damage, resulting in tremors, difficulty walking, agitation and abnormal gait. Bifenthrin is absorbed through intact skin if applied topically. It is moderately toxic to mammals when ingested, and large doses may cause incoordination, tremor, salivation, vomiting, diarrhoea, and irritability to sound and touch (EXTOXNET Bifenthrin Pesticide Information Profile). Bifenthrin has low dermal toxicity and is non-irritating to the skin and a low irritant to the eyes (FM C, 2000). Permethrin (ADI 0.05 mg/kg/day, NOEL 5 mg/kg/day TGA, 2002), a type I pyrethrum, affects the central and peripheral nervous system, and exposure may cause tremors, salivation, hyperexcitability and paralysis. Deltamethrin (ADI 0.01 mg/kg/day, NOEL 1 mg/kg/day TGA, 2002) poisoning results in different symptoms than those of other pyrethroids – mammals undergo salivation and writhing and rolling convulsions, and other type II motor symptoms. Symptoms of deltamethrin poisoning in humans include convulsions, ataxia, tremors and vomiting. Imidacloprid (ADI 0.06 mg/kg/day, NOEL 6 mg/kg/day TGA, 2002) poisoning is likely to cause similar signs to nicotinic poisoning such as fatigue, twitching, cramps, difficulty breathing and muscle weakness including the muscles necessary for breathing. Toxic effects are listed as reduced muscle tone, tremors, apathy and muscle cramps with associated difficulties breathing in severe cases (TGA, 2001). Imidacloprid is not irritating to the skin and does not cause skin sensitisation. Evidence of liver toxicity, tremors and weight loss were seen in animals fed high doses (TGA, 2001). Hexaflumuron (ADI 0.02 mg/kg/day, NOEL 2 mg/kg/day TGA, 2002) has a low oral LD50 in rats at >5000 mg/kg, indicating that it is not particularly toxic to mammals. Toxicity tests conducted in animals indicate that hexaflumuron is an irritant to eyes (in rabbits), and skin. The ingredients are not listed as carcinogenic, and it is not recorded to have caused reproductive damage in animals. Triflumuron has similar toxicological characteristics (TGA, 2001). The chitin synthesis inhibitors have the advantage of low levels of toxicity to mammals (oral LD50 in rats of >5000 mg/kg), but are very toxic to aquatic animals (NPTN), and should not be used in situations where it may enter waterways or groundwater. Fipronil (ADI 0.0002 mg/kg/day, NOEL 0.02 mg/kg/day TGA, 2002) is irritating to the skin and eyes. It is toxic by oral, dermal and inhalation routes. It can cause skin irritation in cats and dogs, and may cause reproductive effects such as decreased mating, reduced litter size and decreased postnatal survival. Fipronil is not mutagenic (PAN, 2000). The photodegradate M B 46513 has a higher acute toxicity to mammals than fipronil itself by a factor of approximately 10 (WHO, 1998). Fipronil and its breakdown products are neurotoxic to mammals. There is no evidence of fipronil causing birth defects, but it may cause a delay in development at high doses. Fipronil is carcinogenic to rats at doses of 300 ppm, causing thyroid cancer related to disruption in thyroid-pituitary status. It is classed as a possible human carcinogen based on the rat carcinogenicity study (PAN, 2000). Studies have shown that there is potential for bioaccumulation of the photodegradate M B 46513 in fatty tissues (PAN, 2000). Arsenic trioxide is highly toxic, but because it is used in bait stations or applied as a dust directly to nests, potential for exposure is limited. Signs of poisoning include stomach cramping, vomiting and diarrhoea, and long-term effects of exposure include increased 22 incidence of cancers of the liver, lung, skin, bladder and kidneys (TGA, 2001). Arsenic has also been identified as genotoxic and teratogenic. 9. Potential effects of termiticides on non-target species In most cases, termiticides are unlikely to cause significant environmental effects, providing that they are applied according to recommended application rates and methods and the recommended safety precautions are taken. Contamination of water surfaces and runoff should be avoided in all cases. Termiticides may present hazards to wildlife if they are absorbed or ingested. Unfortunately, as insecticides, termiticides are also toxic to beneficial insects such as bees. Acute affects include poisoning, resulting in a range of signs, from minor illness and behavioural or reproductive changes to death depending on the levels and means of exposure. The greatest hazards are posed to aquatic organisms through contamination of waterways via runoff or spills. Soil organisms, such as earthworms, which play a significant role in soil ecosystems are often exposed to termiticides, which may have lethal or sub-lethal effects depending on levels of exposure. Current guidelines for Australian organisms are largely derived from overseas data, sometimes with “correction factors” applied to suit Australian conditions. However, the differences in persistence between overseas and Australian soils indicate that experimental evidence needs to be gathered in order to support this approach. There are significant gaps in current knowledge regarding the long-term effects of termiticides in the Australian environment. Although considerable amounts of data have been accumulated for overseas species (see Tables 8 and 9), particularly for chlorpyrifos, in many cases these are not always easily related to local conditions. It is important to note that toxicity levels for pesticides are generally based on animal studies, usually at exposure levels much higher than people would be exposed to, and may not be directly applicable to humans. Chlorpyrifos is highly toxic to freshwater fish, aquatic invertebrates and estuarine and marine organisms. Because of its persistence in aquatic sediments, chlorpyrifos may represent a hazard to sediment feeders. Fish species are differentially affected by chlorpyrifos, with some species (e.g. Gambusia) surviving contaminations that killed several other species. Such differences in species susceptibility are likely to be the result of species differences in the sensitivity of brain acetylcholinesterase to inhibition by chlorpyrifos-oxon (Carr et al., 1997). The ecotoxicology of chlorpyrifos, including comprehensive LC50 data for many species, has been extensively reviewed by Barron and Woodburn (1995). Cladocera, Ceriodaphnia dubia (Richard, 1894), exposed to binary and tertiary mixtures of chlorpyrifos, profenofos and endosulfan were increasingly impaired reproductively than when exposed to single pesticides (Woods et al., 2001). In a mixed Australian zooplanktonic -1 community, chlorpyrifos at single (20 µg/L ), and multiple doses, decreased cladoceran densities in laboratory tests, but copepod densities increased commensurately, while phytoplankton density did not change in response to chlorpyrifos. Continuous, low doses of chlorpyrifos (1 µg/L-1) had no measurable effect (Simon and Helliwell, 1997). 23 Sarneckis and Kumar (2001) tested two commercial formulations of chlorpyrifos, Lorsban and wettable powder, on embryos and tadpoles of Littoria ewingii, the brown tree frog, and Xenopus laevis, the South African clawed frog. Lorsban was found to be more toxic than the wettable powder, and X. laevis was more sensitive than L. ewingii to both formulations. Pesticide-exposed embryos developed abnormalities varying from blistering, spinal curvature, reduced growth and oedema. The authors found that there was a dose-response relationship between AchE inhibition, malformations and chlorpyrifos exposure in tadpoles – 96h LC50/EC50 corresponded with 80–90% AchE inhibition. M ixture toxicity tests using chlorpyrifos plus profenfos/or endosulfan resulted in synergistic or additive effects when tested on X. laevis frogs (Woods and Kumar, 2001). Such mixtures may occur when aquatic systems become polluted, and thus mixture toxicity tests reflect actual pollution of aquatic systems in a more realistic way than do experiments using individual toxicants (Woods and Kumar, 2001). Cholinesterase activity in earthworms, and the stability of the lysosomal membrane, are sensitive to organophosphate exposures (Booth et al., 2000). For earthworms, chlorpyrifos in soils was toxic at LC50 of 104 to 1174 mg/kg of soil (M a and Bodt, 1993). However, the authors recorded wide variation in toxicity. The pyrethroids are relatively non-toxic to birds, but very toxic to mammals if swallowed. They are highly toxic to invertebrates, fish and aquatic organisms. The pyrethroids are much more toxic to aquatic than terrestrial organisms because they inhibit ATPase enzymes, which are essential for maintaining the concentration gradients required by cells for osmoregulation and the maintenance of ionic balances in an aquatic environment. Fish and other gilled animals are particularly at risk because of the large exposed surface areas that gills provide. Bifenthin has a high bioconcentration factor in bluegill sunfish (Bifenthrin M SDS) and as evidenced by its Log Kow of >6, and this along with its persistence might lead to exposure risks in apex species, particularly those that feed on sediment dwelling organisms. The pyrethroids are also extremely toxic to bees. Imidacloprid is highly toxic to some species of birds (e.g. house sparrows, and pigeons), but acute toxicity in birds varies widely between species. It has caused eggshell thinning, decreased weight and reduced egg production and hatching success in some bird species (EPA Fact Sheet; J. Pesticide Reform 2001, Imidacloprid Fact Sheet). Imidacloprid is also highly toxic to fish and other aquatic organisms, with LC50 levels for mysid shrimp of 37 ppb and behaviour effects noted in surviving shrimp (EPA evaluation data in Pesticide Reform 2001, Imidacloprid Fact Sheet). Imidacloprid is acutely toxic to earthworms, with LC50 levels of 2–4 ppm in soils for Eisenia foetida (Zang et al., 2000). Imidacloprid’s ability to move through soil relatively easily poses concerns for potential contamination of waterways and groundwater. Imidacloprid is absorbed by plants from the soil through roots and therefore there may be a risk of exposure to herbivores. Hexaflumuron has low levels of toxicity to mammals (oral LD50 in rats of >5000mg/kg), but is very toxic to aquatic animals (NPTN) and to bees (TGA, 2001). Fipronil is highly toxic to game birds, fish and aquatic invertebrates, and moderately toxic to waterfowl and mammals. The metabolites of fipronil are very much more toxic. The metabolite M B 461 is more highly toxic to birds, and the metabolites M B 46136 and M B 45950 are more highly toxic to freshwater invertebrates than fipronil itself (PAN, 2000). 24 10. Incidents involving termiticides in southeast Queensland Chlorpyrifos has been implicated in many chemical-related urban fish kills, and bifenthrin has been responsible for some. The increasing use of bifenthrin has resulted in an increasing number of incidents involving bifenthrin. Identifying the source of the chemical is often difficult. The following are incidents reported in the media during 2001 and 2002, and documented by EPA (Aust.) press releases. • January 2001: Swan Lake canal estate, Gold Coast – pest control company driver washing spillage into a stormwater drain. Chlorpyrifos (Dursban) subsequently identified at 100 times the lethal dose for fish in the canal water. Over 1000 fish killed. • February 2001: Bifenthrin (0.125 mg/kg) was found in oysters from Redcliffe waterways (Keys and M ortimer, 2001), at well above Food Standards Australia and New Zealand (FSANZ) food standards code for maximum residue levels (0.05 mg/kg). The source of this contamination is not known, but it is likely to be as a result of runoff from nearby canal estate building sites. • February 2001: Loders Creek, Southport – fish kill followed by tests revealing high concentrations of chlorpyrifos. The source of contamination is not known, but it is likely to be as a result of runoff from nearby canal estate building sites. • M arch 2001: Oxley Creek tributary, Brisbane – chemicals leaked through storm drains to the creek in runoff following a fire at Barmac Industries at Rocklea. Chemicals included insecticides and herbicides, requiring water to be pumped from the creek by the Queensland EPA, to prevent contaminated water reaching O xley Creek. • 2001–2002: Gold Coast – Complaints from residents about the taste and odour of tap water following termiticide treatment. Permeation through plastic water pipes by solvents is suspected as the cause. Analysis of water samples indicated the presence of volatile organics, C3 and C4 substituted benzenes and aromatic hydrocarbons. The termiticides chlorpyrifos and bifenthrin were also identified, but were not quantified and so it is difficult to make health risk assessments regarding them. In cases where the polyethylene pipes were replaced with copper pipes the contamination ceased, suggesting that there was some permeation of solvents through the polyethylene pipes. • Contamination of local waterways: A reported decline in the abundant species at the Boondall wetlands prompted an examination of local organisms for chemical contamination in 1995 (M ortimer et al., 1997). • As well as evidence of contamination by heavy metals, in some sites bifenthrin and chlorpyrifos were found in sediments around Brisbane waterways (Mortimer et al.,1997). Oysters in the Redcliffe area have tested positive for the presence of chlorpyrifos at every site tested, although the latest results were negative for bifenthrin (Keys et al., 2002). Termiticides were also in the news in 1999, and consumer confidence in the pest control industry was shaken when more than 5000 new homes were allegedly treated with watereddown termiticides instead of the required treatment. In 1999 the BSA launched a prosecution against the company involved for improper termite works as a result. 25 11. Potential new chemical treatments There are chemicals under consideration (or reconsideration) or being evaluated for use as termiticides in Australia that are currently used with varying success in other countries. One of the more interesting variations is Silafluofen (C25H29FO2Si), an insecticide (pyrethroid ether) containing silicon, used in Japan for soil and timber treatments against termites and other pests since 1991. It has become popular because it has low toxicity to fish and mammals, and it is highly stable chemically (Nakayama et al., 2001). Antitermitic plastic sheeting and antitermitic heat insulators have been developed by impregnating silafluofen into plastic film and polystyrene foam. 12. Biological control The protected underground nature of termite colonies makes them a poor candidate for biological control. A few parasitoids are known but they appear to have limited potential for controlling, preventing or treating termite populations. Viruses, bacteria, protozoa, nematodes, bacteria and most fungi have shown little promise in termite management (Culliney and Grace, 2000). Biological control attempts using bacteria, fungus (Metarhizium anisopliae (M etsch) and nematodes (Heterorhabdis spp. and Steinernema spp.) have had some success in experimental trials (Peters and Fitzgerald, 1998). Predators Ant species have been proposed as possible biological control agents for termites under certain conditions. Kenne et al. (2000) proposed the use of the generalist ant Myrmicaria opaciventris as a biological control agent for termites in sugarcane plantations. Semiochemicals Semiochemicals from Ochetellus (previously Iridomyrmex) glaber (M ayr) worker ants strongly repel C. formosanus termite workers. Dichloromethane extracts taken from extracts of whole ants used to treat sand, resulted in a barrier that was not penetrated by termites (Cornelius and Grace, 1994). It is possible that ant semiochemicals could provide a source of alternatives for future termite control. Monoterpenoids M onoterpenoids are potentially useful for the development of new insecticides because they have low mammal toxicity – may be plant or animal semiochemicals. Cornelius et al. (1997) found that monoterpenoid alcohols particularly eugenol were effective as termiticides against C. formosanus, and that termites would not tunnel through eugenol, or geraniol, treated sand barriers for 5 days. Entomopathic fungi The fungus Metarhizium, when ingested by an insect, penetrates the cuticle causing mortality. M. anisopliae has been isolated from diseased nests of R. flavipes in Canada. Subsequent bioassays have shown that the fungus is spread rapidly to healthy termites through contact, and is able to cause 100% mortality within 24 hours (Zoberi, 1995). In laboratory experiments with C. formosanus, where strains of Beauvaria bassiana (Balsamo) and M. anisopliae were exposed to foraging termites, termites did not avoid the fungal baits. 26 Exposure to M. anisopliae strains resulted in rapid termite mortality while the B. bassiana strain resulted in slower but increasing mortality (Delate et al., 1995b; Jones et al., 1996). C. brevis is susceptible to M. anisopliae, with mortality 4 weeks after exposure at 93 to 100% (Nsar and M oein, 1997). In Australia, some strains of Metarhizium have been identified by the CSIRO as potentially able to control termites (CSIRO M edia release 99/129 1999). The fungi are being produced and tested in conjunction with the company Seed, Grain and Biotechnology Australia in Victoria. It may be possible to infect forestry trees with fungi in order to control the termites that attack them. Suzuki et al. (1996) discuss field application of fungi, which resulted in no clear effects on the majority of trees (Pinus luchuensis). Aspergillus niger and Paecilomyces fumoroseus as well as B. bassiana and M. anisopliae show promise for control of termites (Suzuki et al., 1996). Entomopathic fungi hold promise as baits for termite management. Grooming and social interactions have potential to spread fungus infections throughout colonies. However, termites may avoid fungus conidia and remove and bury fungus-killed individuals, which along with defensive secretions may limit the spread of the fungus (Rath, 2000). Direct application to nests has resulted in complete mortality. However, feeding sites and bait stations have not shown similar success and effectiveness in the treatment of buildings and timber structures. There is currently a commercial product available in the USA. Bio-Blast uses fungal treatment, which is passed to other termites through a horizontal transfer effect. 13. Alternative treatments and management tools Soil insecticide barriers have been the single most important means of controlling termites over the last 50 years, however limitations of current soil termiticides and the popularity of slab-on-ground housing, along with increased awareness of potential environmental and health affects has led to a search for alternatives. Monitoring and baiting programs M onitoring stations are used to detect termite activity. When termite activity is detected, the monitoring station baits may be replaced with slow-acting poisons such as hexaflumuron. Bait Boxes The principle of baiting techniques is to have a susceptible substance in an aggregation device (bait station) on which the termites aggregate and continue to feed once they have found the bait stations. Bait stations can be placed in in-ground and aboveground situations. A bait toxicant in timber or a cellulose matrix can be placed in the station or dusting the termites may indirectly destroy the colony. Colony elimination or suppression should be followed by hazard reduction and regular inspection. In Australia the main problem with baiting against Coptotermes species has been inconsistency of termites locating and accepting baits. The method relies on termites finding bait stations, which often does not occur. Baiting is most beneficial when used as part of an integrated pest-management strategy. Bait stations buried in the soil might be found by foraging termites (e.g. CSIRO’s bait box technique). Aboveground bait stations are placed in direct contact with infested timbers where possible, and aggregation stations (plastic lunch 27 boxes containing bait) have been used successfully when placed in the hollow centres of infested trees or stumps. The advantages of using baiting as part of an integrated pestmanagement strategy are that they do not lead to widespread contamination of the soil, and require only a small amount of toxicant as opposed to other treatment systems which employ a saturation approach. Baits may be used via a “bait and switch” technique in which the original non-toxic bait used to aggregate termites is replaced by toxic bait. Alternatively, the aggregated termites may be poisoned by topical application of a pesticide (i.e. arsenic dust which is then carried back to the nest) or the baits may be toxic or contain metabolic, growth, moult or chitin inhibitors. In all cases, the toxin must be slow-acting to allow termites to feed and then move away from the bait and spread through the colony, as the presence of dead individuals can have a repellent effect. Example product: Sentricon (Dow Agrosciences). This is a monitoring and elimination system. When termites are found in the station, the wood is replaced with a tube containing bait toxicant. When termite activity ceases, the wood is returned to the bait station and monitoring resumed. The active ingredient in the bait is hexaflumuron, a chitin synthesis inhibitor (Recruit II). It is not suitable for low areas that may flood, as it is highly toxic to aquatic invertebrates and possibly fish. Dusting If termite colonies are accessible, they may be directly dusted using arsenic trioxide or permethrin dust, or alternatively aggregated individuals may be dusted so that they return the poison dust to the colony. This is the favoured method of spot treatment of wooden railway bridges and isolated and obvious nests. Heat o o In laboratory studies, increasing wood core temperatures to 46 C and 49 C resulted in 100% mortality of C. brevis nymphs (Woodrow and Grace, 1998). However, this was in small wooden blocks (13.5 x 13.5 cm). In larger wooden blocks where temperatures took longer to rise, termites were better able to tolerate the conditions, and it has been hypothesised that slow rates of thermal increase may lead to heat acclimation of termites. Cumulative effects of sublethal stresses due to gradual heating may increase mortality. Heat treatments can be used in whole-of building treatments by using a propane heating unit to blow hot air into the building which is sealed within a tent of tarpaulins or similar. Hot air is blown in and around o the building to heat interior and exterior walls and temperatures must be maintained at 45 C o to 50 C for 50 minutes to an hour. This practice is rarely used. Freezing This is a method that is not practical for infestations of buildings, but can be used for specific areas such as verandas and/or furniture. Liquid nitrogen is pumped into the sealed area to cool o the area to –20 C. Electricity Electricity has been used to spot-treat infested wood using an electrogun to deliver a low current and high voltage, which kills the termites in its path. 28 Microwaves Heat generated by microwaves can be used to kill termites. M icrowave generators are mounted against the infested wall. M icrowaves can be used to treat wood as a preventative measure. By passing wood through microwaves a change in structure may result. The palatability of the wood to termites can be changed this way. The addition of pesticides and/or preservatives in the early stages of the procedure is possible. Radioactive isotopes Techniques developed for tracing the movements of subterranean termites by feeding them radioisotopes could potentially be used to exterminate colonies. Isotopes fed to termites via insertion of a wooden dowel with an agar mixture of inert radioisotopes La-140 or Sc-45 were spread through the colony over 24 hours (Airey and Charlton, 1994), thus demonstrating the effectiveness of such a method. This technique poses technical and safety issues that render it unsuitable for general use. Carbon dioxide Carbon dioxide may be a viable alternative to conventional pesticides in some situations such as vault fumigation, and possibly for eradication of pests in structures. Significant mortality has been recorded for C. formosanus exposed to 95% or greater carbon dioxide atmospheres. However, 60 hours of exposure were required to produce 100% mortality (Delate et al., 1995a). Plant extracts The fruits, seeds and leaves of the plant Melia azedarach Linn have been investigated in Taiwan as an antitermite compound. When fed powdered fruits, leaves, bark and seeds termites suffered 100%, 90%, 85% and 67.5% mortality respectively (Lin and Wang, 1988). The oil from Neem trees, Azadirachta indica has antifeedant affects on Reticulitermes speratus Kolbe. Extracts from Neem oil have been evaluated for their potential in termite management (Isheda et al., 1992). Termite resistant wood Black cypress pine – Callitris endlicher i (and its latex) is resistant to termite attack. It grows south of Kingaroy and west of the Great Dividing Range in Queensland. It is durable, and also resistant to fungi. However, it is unpopular with builders because it is difficult to work with and is often knotty. Long-term use will depend on the timber being grown in commercial plantations. Some other Australian natives are described as “termite resistant”, with AS3360.2 (2000) listing 37 eucalypt, 9 non-eucalypt and 5 softwood species as suitable for minor construction purposes such as fencing and landscaping. Protozoicides Several protozoicides have been investigated for use as baits. Waller (1996) investigated urea, ampicillin and tetracycline fed to R. flavipes and R. viginica (Banks). The most effective of these was urea, which was palatable and decreased termite survivorship. 29 Physical barriers Sand, (12-grit) layered around the foundations of a house may act as a barrier against termites (Ebling and Forbes, 1988). Basalt barriers with 50% or more of the particles with diameters of 1.7–2.8 mm was not penetrated by formosan subterranean termites in laboratory and field trials (Tamashiro et al., 1991). Similarly, granite barriers were effective in some cases, for some species. Verkerk (1990), states that gravel barriers are an effective barrier against termites. A double barrier system, with a plastic membrane separating two different size gravels would have to be used North of the Tropic of Capricorn due to the presence of M. darwiniensis. Deltamethrin impregnated blankets (e.g. Kordon Blanket, Bayer Cropscience) may be a barrier against infestation, but any cracks, deformities or degeneration in the materials may allow termites access. S tainless steel mesh (e.g. Termimesh) can provide an effective barrier against infestation, but any cracks, deformities or degeneration in the materials may allow termites access. Water easily passes through this product. One of the major concerns with the use of Termimesh is its positioning in relation to weepholes and external paths. In many cases external paths are built above the level of existing weepholes. Aluminium termite barriers, flashing and damp-poof coursing (e.g. Alterm). The Alterm system is a combination monitoring and barrier systems. Baits are placed at the perimeter of the structure in brick mortar joints, and if termite activity is detected, the baits are replaced with toxins. For subterranean cables, there are a number of barriers that are used, or have been investigated for use, to prevent termites from damaging them. Welded stainless steel tubes are used for high voltage cables to provide an effective termite barrier. The stainless steel tubes are corrugated so that they are able to flex and bend to some degree without cracking. Power and utility cables can be taped, with either stainless steel, brass or copper tapes, in an overlapping fashion to form a seal that is impervious to termites. These cables are then usually finished with a PVC coating for extra protection. High Density Polyethylene (HDPE) cables are resistant to termite attack because they are too hard for termites to penetrate, are smooth and therefore are difficult for termites to grasp with their mandibles. Nylon is an effective termite barrier, used extensively to protect telecommunication cables. As with HDPE, the effectiveness of nylon is as a result of its smooth impermeable surface. Termite detection devices M onitoring and detection devices are potentially useful for finding the location of an infestation in a building. Borescopes are inserted into wall cavities to visually inspect for termites. Termatrac (Protec USA) electronically emits signals that penetrate walls; insect movement behind and within walls is detected by interrupted signals. 30 14. Future directions The future of termite management lies within an integrated approach that is able to take into account preventative and retrospective treatments for termites and that is not only effective, but is also economical, safe and environmentally friendly. Such treatments are likely to consist of physical and chemical barriers, used in combination with resistant or preserved wood or steel framing and according to the requirements of individual sites. For an integrated approach to be effective it must involve industry, government and consumer groups and combine treatment and prevention programs with education, monitoring and collating data, and research into new and better measures for termite management. There is a widely perceived need for improvements in building design in order to prevent or reduce termite infestation along with increased interest and demand for physical barrier systems. New building techniques and designs, along with novel barrier systems to reduce exposure to termites are warranted, and further research on termite foraging behaviour is required to facilitate the development of more effective bait and monitoring technology. Currently in Australia, we may be enjoying a period of overlap where older buildings are still being protected by the organochlorines while new structures are treated with organophosphates. Houses built before 1985 may still be protected to some extent by the organochlorine termiticides applied to them. However, the effectiveness of the residual organochlorines will have been reducing over time, and older houses may be at risk of termite infestation. The potential costs of re-treatment and repairs are likely to increase dramatically in the future as older slab-on-ground dwellings become susceptible due to the eventual failure of the organochlorine termiticides. The success of the organochlorines over long periods of time has added to the popularity of slab-on-ground housing in Australia, buildings which are much more susceptible to infestation by termites than older style above-ground housing. This means that the potential for termite damage is increased. The result of Australia’s previous reliance on the highly persistent organochlorines is that modern housing is quite susceptible to attack by termites, with termites entering buildings through weepholes, expansion joints, service ducts and cracks in brickwork which often extend several courses below ground. Simple alterations in building and property maintenance practices, such as providing exposed slab edges above ground and extending aprons of slab around slab-on-ground dwellings will allow termite incursions to be reduced and detected, providing that regular inspections take place. There are many areas in which the efficiency of different pesticide formulations needs investigating. Therein lies the potential for chemical companies to examine their formulations to suit specialised purposes. There are many areas in which different management techniques can be investigated, the electricity supply industry being an example. In Australia, there are approximately 8,000,000 wooden power poles, which are inspected (typically at 5-year intervals) for termite infestation and rot. These poles exist in a wide range of conditions, in urban and rural environments, in a range of soil types and climates, some adjacent to waterways or drainage areas. However, despite these substantial differences in circumstance, 31 all are treated by similar processes using commercial formulations where termiticides are applied. Biflex (bifenthrin) is most commonly used on wooden poles today. Previous treatment regimes included chemicals such as aldrin, creosote and chlorpyrifos treatments. M any wooden poles are fluoride treated to prevent rot and most wooden poles are now CCA pre-treated. Issues with current treatment include concerns about the uncertain potential of the chemical “cocktail” of treatments around each power pole. There are 54.5 km of timber railway bridges in Queensland alone and approximately 9500 km of rail corridor. Each bridge is susceptible to termite attack and undergoes inspection every 4 to 8 years. Treatment is on discovery of termite activity and is by arsenic dusting into nests and application of chlorpyrifos or bifenthrin to soil. Other chemicals sometimes used are fipronil and imidacloprid. Over the last 10 years, 40 km of timber bridges have been replaced with concrete structures, particularly those in tropical regions. However, many timber bridges are likely to remain. Construction of concrete footing to keep timber supports from contacting the ground is being considered as a means of reducing termite damage. There is potential for clients to work with termite managers and chemical companies to review their formulations to suit their specialised purposes, identify termite management strategies appropriate to the location of infrastructure, and potentially to develop chemicalfree physical barriers and/or more sustainable termite management practices. Future approaches based on integrated pest management principles require the cooperation of stakeholders in order to gather information and perform research into the problem in a holistic fashion. Several requirements are apparent: • M ore information is required on Australian termite biology, taxonomy and ecology. Ideally, an understanding of the way in which termites forage, how they locate food sources, what specifically attracts and repels them, and the mode and speed of infestations need to be gained. • The risks of termite infestation need to be evaluated, both locally and nationally so that susceptible or high-risk areas, structures and building types can be identified and preventive measures taken in terms of design and construction. Building regulations and designs need to be able to reduce or eliminate high-risk housing – and eliminate or reduce conditions that are attractive to termites and/or facilitate termite infestation. • Further education is required for homeowners, builders, designers, legislators and landscape designers so that they can reduce the risk of infestation through the avoidance of practices in landscaping and design that inadvertently favour termites i.e. ensuring good under-floor ventilation, which discourages termite activity, not stacking timber or building up soil against or near buildings, reducing timber use where inspection for termites is difficult, and not building wooden in-ground structures (e.g. untreated timber retaining walls) close to houses. • There needs to be a specific focus on the creation of alternative barriers for the range of wooden structures that need protection. The focus needs to take account of the current limitations of physical barriers and monitoring stations which may be avoided 32 by termites and overcome the loss of activity associated with short-term response chemicals which have replaced the more hazardous organochlorine compounds. An innovative approach to barrier design is needed that seeks to incorporate the specific features of slow release chemicals, e.g. based on natural products which are more acceptable to the environment and public health. • Since most termite-related damage to timber occurs from subterranean termites, preventative measures rely heavily on site housekeeping and the establishment of physical or chemical barriers to stop the termites getting into the premises or timber from the underlying soil. Once the termites have been found in wooden structures, a range of physical and chemical techniques are available to treat and eliminate (or control) the infestation. There is a need for a reliable long-term, maintenance-free method of preventing termite infestations that poses little or no risk to human or environmental health. Research is required into the behaviour of termiticides, current and potential, in Australian soils and under Australian conditions using rigorous, repeatable science, and open and collaborative communication between stakeholders needs to be maintained and widened so that the concerns of each group are addressed. 33 Recommended further reading AS 1604.1 (2000). Specification for preservative treatment – Part 1: Sawn and round timber. (Standards Australia, Sydney). AS 3660.1 (2000). Termite management – Part 1: New building work. Standards Australia, Sydney. AS 3660.2 (2000). Termite management – Part 2: In and around existing buildings and structures - Guidelines. Standards Australia, Sydney. AS 3660.3 (2000). Termite management – Part 3: Assessment criteria for termite management systems. Standards Australia, Sydney. AS 3660 (1993) Australian Standard relating to termite protection for existing buildings Protection of Buildings from Subterranean Termites – Prevention, Detection and Treatment of Infestation Standards Australia, Sydney. This standard was partially superseded by AS 3660.1 (1995). AS 3660 Supplements for use by Pest Control Operators: Standards Australia, Sydney. Supplement 1 (1993): Certification of Termiticide Application. Supplement 2 (1993): Certification of Completion of Treatment. Barron, M.G. and Woodburn, K.B. (1995). Ecotoxicology of chlorpyrifos. In Ware, G.W. (ed.). Reviews of environmental contamination and toxicology pp. 1-94. Volume 144. Continuation of residue reviews. Springer Verlag. New York Inc. U SA. Bloomquist, J.R. (1999). Insecticides: Chemistries and Characteristics. In E.B. Radcliffe and W.D. Hutchison (eds.), Radcliffe’s IPM World Textbook, URL: http://ipmworld.umn.edu University of M innesota, St. Paul, M N. International Programme on Chemical Safety (IPCS ). Chemical Safety Information from Intergovernmental Organizations. Website: http://www.inchem.org International Programme on Chemical Safety (IPCS ). Pesticide Data Sheets. http://www.inchem.org/pages/pds.html International Programme on Chemical Safety (IPCS ). Environmental Health Criteria 18 – Arsenic. Website: http://www.inchem.org/documents/ehc/ehc/ehc018.htm International Programme on Chemical Safety (IPCS ). Environmental Health Criteria 97 – Deltamethrin. Website: http://www.inchem.org/documents/ehc/ehc/ehc97.htm International Programme on Chemical Safety (IPCS ). Environmental Health Criteria 142 – Alpha-cypermethrin. Website: http://www.inchem.org/documents/ehc/ehc/ehc142.htm International Programme on Chemical Safety (IPCS ). Environmental Health Criteria 204 – Boron.Website: http://www.inchem.org/documents/ehc/ehc/ehc204.htm 34 International Programme on Chemical Safety (IPCS ). Health and Safety Guide No. 39 – M irex. Website: http://www.inchem.org/documents/hsg/hsg/hsg039.htm International Programme on Chemical Safety (IPCS ). Health and Safety Guide No. 86 – M ethyl Bromide. Website: http://www.inchem.org/documents/hsg/hs g/hs g86_e.htm Kookana, R.S ., Baskaran, S . and Naidu, R. (1998). Pesticide fate and behaviour in Australian soils in relation to contamination and management of soil and water: a review. Aust. J. Soil Res. 36: 715–764. Lenz, M., Watson, J.A.L. and Barrett, R.A. (1988). Australian efficacy data for chemicals used in soil barriers against subterranean termites. CSIRO Division of Entomology Technical Paper 27. National Registration Authority (2000). The NRA review of chlorpyrifos. NRA review series 00.5. National Registration Authority for Agricultural and Veterinary Chemicals. Canberra, Australia. National Registration Authority. Website: http://www.nra.gov.au/index.html Racke, K.D. (1993) Environmental fate of chlorpyrifos. In Ware, G.W. (ed.). 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M ycologia 87: 354–359. 43 Index Acceptable Daily Intake (ADI), 20 AchE inhibition, 24 Acute Reference Dose (ARD), 20 adjuvants, 19 aldrin, 7, 17, 20, 38 Alpha-cypermethrin, 12, 13, 22, 26 alternative treatments, 33 aquatic systems, 24 arsenic trioxide, 7, 17, 22, 34 Aspergillus niger, 33 Azadirachta indica, 35 bait stations, 17, 34 barriers, 1, 2, 3, 4, 6, 11, 32, 33, 35, 36 Beauvaria bassiana, 32, 33 bees, 23, 24, 28 benzoylurea, 17 Bifenthrin, 4, 7,11–13, 19, 22, 25, 26 biological control, 32 boron, 7, 17 C. acinaciformis, 17 cables, 36 carbon dioxide, 35 carcinogenic effects, vi, 31 castes (termite), 5, 6 chlordane, 7, 20 chloronicotinyls, 7, 14 Chlorpyrifos, 3, 4, 6, 7, 10, 11, 18–23, 26–31, 38 copper, 7, 17, 26 Coptotermes acinaciformis, 5 Coptotermes acinaciformis raffrayi, 5 Coptotermes lacteus, 6 Coptotermes michaelseni, 5 Cornitermes cumulans, 6 costs, 1, 3, 37 creosote, 7, 17, 37 cyclodienes, 7 cypress pine, 36 Daphnia, 28 degradation, 10, 13, 18, 19 Deltamethrin, 14, 22, 27–31, 36 dieldrin, 7, 20 drywood termites, 4, 5, 7, 17 dusting, 6, 7, 17, 33, 34, 38 dusts, 6, 17, 19 earthworms, 23, 24, 25 efficacy, 6, 18, 19, 20 electricity, 34, 37 44 entomopathic fungi, 32 EPA, 21, 26 experimental LD50 and LC50 values, 26 fate in humans and animals, 32 Fipronil, 4, 7, 16, 22, 23, 25, 26, 27, 28, 30, 31, 38 fluorine, 7 foraging, 1, 6, 33, 34, 37 formulations, 4, 7, 10, 14, 17, 18, 19, 20, 24, 38, 39 freezing, 34 fungi, 32, 33, 35 GABA, 11, 16 golden orfe, 28 grooming, 6, 33 groundwater, 13, 15, 18, 19, 22, 25 growth inhibitors, 17 heat, 35 heptachlor, 7, 20 Hexaflumuron, 17, 22, 25 high density polyethylene, 36 humans, 7, 10, 20, 21, 22, 23, 32 Imidacloprid, 4, 7, 14, 15,18, 22, 24, 26, 28, 29, 30, 31, 32, 38 impregnated wood preservatives, 17 incidents, 26 Introduction, 4 invertebrates, 23, 24, 34 Iridomyrmex glaber, 32 isofenphos, 19 Japanese quail, 27 Kalotermitidae, 5 Koc , 10, 11, 12, 13, 15, 16 Kordon, 14, 36 Kow, 12, 13, 14, 15, 16 landscaping, 1, 35, 38 LD50, 21, 23, 24, 26, 28 Log Kow, 10, 11, 12, 15, 16 Mastotermes darwiniensis, 5, 7, 17, 36 M astotermitidae, 5 Melia azedarach, 36 Metarhizium anisopliae, 32, 33 methyl bromide, 7, 17 microwaves, 35 M irant, 7, 17 M irex, 7, 17 monitoring and baiting, 33 monoterpenoids, 32 mutagenic effects, vi, 31 Neem oil, 36 nicotinoids, 14 NRA, 4, 20 nylon, 36 45 organic content, 11, 18 organochlorines, 1, 7, 17, 38 organophosphates, 1, 7, 18, 19, 21, 37 oysters, 26 Permethrin, 4, 7, 11, 17, 19, 22, 26, 28, 28, 30, 31, 32, 35 persistence, 7, 18, 19, 20, 23 phenyl pyrazoles, 7, 16 plant extracts, 35 power poles, 4, 20, 37 predators, 32 protozoicides, 35 PVC coating, 36 pyrethrins, 11 pyrethroids, 7, 11, 12, 13, 19, 22, 24 radioactive isotopes, 35 railway bridges, 34, 38 reproductive effects, vi, 30 resistant wood, 36 Rhinotermitidae, 5 runoff, 23, 26 Schedorhinotermes reticulatus, 5 semiochemicals, 32 Silafluofen, 32 solubility in water, 10, 11, 12, 13, 14, 15, 16 solvents, 3, 10, 12, 19, 20, 26 sorption, 10, 11, 12, 15, 16 sorption coefficient, 10, 11, 12, 15, 16 spills, 23 tap water, 26 teratogenic effects, vi, 30 Termimesh, 36 termite fauna, 5 Termitidae, 5 Termopsidae, 5 toxicity tests, 20, 22 Triflumuron, 17 tunnelling (termites), 6 volatilisation, 10, 11, 18 waterfowl, 25 wildlife, 24, 25 wood preservatives, 7, 12, 17 46
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