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Toxicological and Regulatory Information Supporting the Registration of VAPORMATETM As a Grain Fumigant for Farm Storages

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Toxicological and Regulatory Information Supporting the Registration of VAPORMATETM As a Grain Fumigant for Farm Storages From: E.J. Wright, M.C. Webb and E. Highley, ed., Stored grain in Australia 2003. Proceedings of the Australian Postharvest Technical Conference, Canberra, 25–27 June 2003. CSIRO Stored Grain Research Laboratory, Canberra. Toxicological and regulatory information supporting the registration of VAPORMATETM as a grain fumigant for farm storages V.S. Haritos,1 K.A. Damcevski and G. Dojchinov Stored Grain Research Laboratory, CSIRO Entomology, GPO Box 1700, Canberra, ACT 2601 Abstract. VAPORMATETM, a BOC Ltd product composed of ethyl formate 16.7% by weight in carbon dioxide, is cur- rently under evaluation as a grain fumigant for farm silos. The research has aimed at devising an application system for the mixture that will maximise the concentration of ethyl formate in the bin but minimise the loss to grain sorption. Also, we are investigating the optimal amount and exposure period to achieve high mortality of a range of tolerant stored grain pests. VAPORMATETM appears very favourable in terms of data to support registration of the product, such as mamma- lian toxicology, residue analysis methods, low risk of environmental impacts, and occupational health and safety aspects of ethyl formate, and its natural occurrence. Ethyl formate is far less acutely toxic to mammals, including humans, than dichlorvos and phosphine, two of the main treatments that are currently available for farm storages. Ethyl formate also has a higher occupational exposure limit (100 ppm versus 0.3 ppm for phosphine and 0.1 ppm for dichlorvos). Ethyl for- mate is a natural component of many foods and the hydrolysis products formed in the human body are formic acid and ethanol which are identical with products formed endogenously. Residue methods for ethyl formate on grains have been established. The high sorption of ethyl formate and its consequent breakdown mean that little is left to ventilate from a bin at the end of fumigation. Nevertheless, ethyl formate has a short half-life in the atmosphere. Ethyl formate poses a low risk of environmental damage, even in the unlikely case of a spill of liquid into waterways or soil. Ahead in the project, we expect to establish a VAPORMATETM application rate and apply for experimental-use permits to enable field trials to be conducted. Also, we are investigating the potential of insects to form resistance to the fumigant. Introduction • Rapid sorption to grain—ethyl formate has a great affinity for grain and grain has a large capacity to sorb New treatments for stored grains are continuously needed ethyl formate. This reduces the amount of fumigant because the currently used fumigants and protectants are available to control insects, as it is the vapour phase of under threat from either insect resistance, or loss of regis- the fumigant that is thought to be most effective. tration or manufacturer support. On-farm or small-scale • Application system for farm storages—we have tested storers are at a greater disadvantage as phosphine is the ‘forced-flow fumigation’ with VAPORMATETM in a only fumigant in routine use available to them. Phosphine model silo system. In this system, the fumigant is is used on approximately 80% of Australian grain and blown through the grain, using an aeration/drying fan throughout the storage chain and there is a strong need to at a relatively fast flow rate, until the air in the bin is provide an alternative, especially for on-farm use in a replaced by fumigant. The forced flow reduces the res- phosphine resistance management strategy. The avail- idence time of fumigant near grain, thus reducing sorp- ability of ethyl formate as a disinfestant would also benefit tion and leading to an even distribution of fumigant. the farm-scale grain storer as an alternative to dichlorvos • High concentrations of fumigant required—to achieve as a fast-acting treatment. a high level of insect control, relatively high concen- A mixture of ethyl formate in carbon dioxide (16.7% trations of ethyl formate are required. The insect mor- by weight), called VAPORMATETM, has been developed talities obtained for a variety of application rates of by BOC Ltd as a postharvest treatment for horticulture VAPORMATETM are described by Damcevski et al. and stored grains. The main challenges that we see for (these proceedings). VAPORMATETM becoming a fumigant for stored grains • Registration—regulatory approval for a grain fumigant include: still remains one of the largest challenges for any new treatment. While ethyl formate is not a new fumigant 1 Corresponding author: <[email protected]>. and is currently registered in Australia for insect con- 193 Stored grain in Australia 2003 trol in dried fruit, it has not been evaluated by a pesti- 16% and presents a considerable flammability risk when cide regulatory agency to modern standards. A modern used as a grain fumigant. The cylinderised formulation of grain treatment has to be safe for consumers, applica- VAPORMATETM provides a delivery system for ethyl tors, the environment and the commodity, and should formate which substantially reduces handling and poten- not cause issues in the trade of grain. The emphasis of tial exposure to the applicator. No handling of liquid ethyl this paper is on whether ethyl formate can meet these formate is carried out with this formulation. expectations and obtain Australian registration as an insect treatment for stored grains. Although VAPORMATETM presents many challenges, Acute toxicology of ethyl formate it has some distinct advantages that are encouraging for its registration. The main active ingredient, ethyl formate, has The acute toxicity of ethyl formate has been tested in a low mammalian toxicity but rapidly kills grain insect number of animal species following oral and inhalation pests. Ethyl formate occurs naturally in foods and when exposure, as summarised in Table 1. The acute toxicity of applied to grain, particularly warm and wetter grain, the ethyl formate is low by the oral route with an LD50 (lethal residues break down rapidly to natural products. The dose to kill 50% of experimental animals) of around 2 g/ VAPORMATETM formulation has many advantages over kg bodyweight (Table 1). Although the toxicity data are neat liquid ethyl formate. We have shown previously that not as comprehensive for the inhalation route as that for the addition of carbon dioxide from 5% volume/volume the oral route of exposure, it is clear that ethyl formate is and above enhances the toxicity of ethyl formate toward much less acutely toxic than dichlorvos or phosphine, as adults and most juvenile stages of stored product insects demonstrated in Table 2. The 4-hour LC50 (concentration (unpublished data). This means we can reduce the amount of vapour that results in the death of 50% of test rats after of fumigant needed for an efficacious treatment, resulting 4 hours of inhalation exposure) is a measure for in lower residues in the grain after fumigation. comparing the acute toxicity of volatile chemicals. Using The flammability risk of ethyl formate is virtually this measure of toxicity, dichlorvos is approximately 100- eliminated by the presence of high concentrations of fold more acutely toxic and phosphine 1000-fold more carbon dioxide in the VAPORMATETM formulation (Ryan toxic than ethyl formate as shown in Table 2. The much and Bishop, these proceedings). Pure ethyl formate has a lower acute mammalian toxicity of ethyl formate is lower flammability limit of 2.8% and an upper level of reflected in its occupational exposure limit compared with Table 1. Acute toxicology of ethyl formate in experimental animals. Species Route Lethal dose or concentrationa Reference Rat Oral LD50 1850 mg/kg NTIS (1974) Rabbit Oral LD50 2072 mg/kg Anon. (1978) Rat Oral LD50 4290 mg/kg Smyth et al. (1954) Guinea pig Oral LD50 1110 mg/kg NTIS (1974) Rat Inhaled No deaths 24 g/m3, 5 min Smyth et al. (1954) 3 Rat Inhaled LC83 24 g/m , 4 h Smyth et al. (1954) 3 Cat Inhaled LC100 32 g/m , 90 min Von Oettingen (1959) 3 Dog Inhaled LC100 30 g/m , 4 h Anon. (1978) a LD50 (or LC50) = lethal dose (or concentration) that kills 50% of test organisms. Table 2. Comparison of toxicity and regulatory data for ethyl formate, dichlorvos and phosphine. Endpoint Ethyl formate Dichlorvos Phosphine a b c d 4 h rat LC50 inhalation Approx. 20 0.2 0.015 toxicity (g/m3) Australian occupational 100 0.1 0.3 exposure limit (ppm)e Acceptable daily intake 3f 0.001g Not set (mg/kg/day) a LC50 = lethal dose (or concentration) that kills 50% of test organisms. b extrapolated from Smyth et al. (1954); cWHO (1989); dWHO (1988); eNOHSC (1995); fJEFCA (1997); g TGA (2003). 194 Toxicological and regulatory information supporting registration of VAPORMATE™ the other two treatments (Table 2). Ethyl formate has the Metabolism and degradation of highest occupational exposure limit of all the current commodity fumigants and of the candidates being consid- ethyl formate ered as alternatives to phosphine or methyl bromide, The most common pathway in the breakdown of ethyl excluding modified atmospheres. formate is hydrolysis to formic acid and ethanol. The rate As part of the registration package for VAPOR- of hydrolysis can be catalysed in acidic and basic condi- MATETM, a comprehensive evaluation of ethyl formate tions. Also, enzymes such as esterases that are present in toxicology is required. A toxicological review has been plants and animals facilitate the breakdown. Formic acid conducted for ethyl formate (Haritos 2000) and much of and ethanol themselves are further metabolised by many the data that can support registration are available in the organisms to be incorporated into cellular components or public domain. used as sources of energy. In water, ethyl formate undergoes slow hydrolysis to Regulatory levels relating to intake of formic acid and ethanol and this process is also thought to occur in grain, but more rapidly.
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