and Control

KPS6-1 New global challenges to the use of gaseous treatments in stored products

S. Navarro1

Abstract registration procedure before they can be employed in practice. Among the new gaseous application Concerns over the adverse effects of fumigant technologies that have successfully replaced residues in food and the environment have led fumigants are the manipulation of modified regulatory agencies to take actions by imposing (MAs) alone or at high temperatures, strict limitations on fumigant registration. Of the and high pressure that needs to be long list of fumigants two decades ago, very few further explored for specific applications. A recent remain today. MB has a relatively quick killing development is the use of MAs in a low-pressure effect on insects, but because of its contribution environment. These niche applications of MAs that to stratospheric depletion has been phased have resulted in very promising application treatments out in developed countries since 2005, and in with market acceptability, should serve as models developing countries phase out will take place for global challenges for new application methods. by 2015. In contrast, remains popular, even though insects have developed resistance Key words: fumigation, methyl bromide to it. These restrictions on the use of fumigants alternatives, phosphine, gaseous treatments, have posed new global challenges to the food modified atmospheres. industry, and have resulted in efforts to register new fumigants, and in the development of new technologies as alternative control methods. Introduction Among the newly considered fumigants are sulfuryl fluoride, carbonyl sulphide, propylene Fumigants are widely used for pest oxide, methyl iodide, ozone, , and elimination in all stored products that include . Sulfuryl fluoride seems to cereals, oilseeds, pulses, spices, dried , tree emerge as a promising candidate fumigant for nuts and their processed foods, to prevent disinfesting stored food commodities, food- economic and quality losses due to insect pest processing facilities and as a quarantine fumigant. attack. Fumigants may be used; a) as a hygienic Other registered fumigants suffer from the measure during storage; b) to provide wholesome limitation that they may be useful for treating a food for the consumer; and c) as a mandatory particular type of commodity or for application requirement in trade and in quarantine in a specific situation only. The potential use of (Rajendran, 2001). volatiles of botanical origin shows promise but Increased public concern over the adverse requires both commercial scale trials and effects of pesticide residues in food and the

1 Department of Food Science, Agricultural Research Organization, the Volcani Center. P. O. Box 6, Bet Dagan 50250, Israel. Fax: +972-3-5582069. e-mail: [email protected]

495 9th International Working Conference on Stored Product Protection environment has led to the partial substitution by hand, and the need to find and the cost involved alternative control methods. Therefore, non-chemical in adopting alternative control measures on the and environmentally user-friendly methods of pest other. They have resulted in efforts to register control in the post harvest sector are becoming new fumigants in several countries, and in the increasingly important. It is worth noting that of the development of new technologies as alternative 16 fumigants listed in common use some 22 years control methods. ago by Bond (1984), only very few remain today. Most of these fumigants have been withdrawn or discontinued on the grounds of environmental safety, The gaseous treatments cost, carcinogenicity and other factors. Methyl bromide (MB) has been phased out in developed The gaseous treatments may be categorized countries since 2005 and will be phased out in into three groups; a) residue-leaving fumigants developing countries by 2015, because of its that are synthetically produced volatile contribution to stratospheric ozone depletion chemicals; b) volatile essential oils of botanical (UNEP, 2002). Although there are exemptions for origin; and c) non-residual modified atmospheres quarantine and pre-shipment purposes, as well as (MAs). the possibility to apply for exemptions where no alternative exists, the applicant has to demonstrate a) Fumigants and their current status: that every effort is being made to research alternative The chemical treatments discussed in this treatments. In contrast; phosphine remains popular, presentation are categorized under structural particularly in developing countries, because it is treatments and commodity fumigations. Among easier to apply than MB. However, many insects the synthetic chemical treatments, the list today have developed resistance to phosphine over the is limited to MB, phosphine, sulfuryl fluoride, last decade (Cao et al., 2003; Savvidou et al., propylene oxide, carbonyl sulphide, ethyl 2003). formate, hydrogen cyanide, carbon disulphide, Food industries and particularly exporters are methyl iodide, ozone, and carbon dioxide. dependent on fumigation as a quick and effective tool for insect pest control in food commodities. Following on the WTO and Free Trade Policies, The current most commonly used trade traffic of foodstuffs across the world has fumigants been considerably increased. Consequently, fumigation for disinfesting stored food Methyl bromide commodities has been playing a significant role. Some developed countries have adopted the One of the main features that make MB a approach of zero tolerance of insect pests in food commercially desirable fumigant is its speed of commodities. On the other hand, the fumigation action. In addition, MB has a number of technology that is required to obtain this zero additional desirable features including its infestation has been facing threats/constraints recognition by quarantine authorities, and its because of regulatory implementation and the broad registration for use; it also has good development of resistance (Arthur and Rogers,. penetration ability, and the commodity airs 2003). rapidly after exposure. When considering The aim of the present paper is to elucidate alternatives, the above properties need to be the new global challenges to the use of gaseous viewed against a background of MB as a highly treatments in stored products. These challenges toxic, odorless gas with substantial ozone- derive from the increased demand of competitive depleting potential and adverse effects on a markets for quality in food commodities free number of durables, particularly loss of viability, from pest and pesticide contaminants on the one quality changes, taint and residues. 496 Fumigation and Control Atmosphere

MB plays an important role in pest control in or altered rates of phosphine release have been durable and perishable commodities and developed and tested in Australia (Waterford and particularly in quarantine treatments. The Asher, 2000) and India (Rajendran, 2001). Montreal Protocol, an international treaty Improved application techniques such as the developed to protect the earth from the “Closed Loop System” in the USA, SIROFLO® detrimental effects of ozone depletion and signed and SIROCIRC® in Australia and PHYTO by 175 countries, is now phasing out ozone EXPLO® in Europe have been developed for depleting compounds including MB on a application in different storage situations. Insect worldwide basis. Accordingly, legislative resistance is a serious concern that threatens the changes have been made in different countries continued effective use of phosphine. Phosphine to control the use of MB, which has an average fumigation protocols have been revised in ozone depleting potential of 0.4. The ban on MB different countries to tackle the problem of insect currently exempts quarantine and pre-shipment resistance to the fumigant. Two major restrictions (QPS) treatments, emergency uses and certain of phosphine are that it requires several days of critical uses where no alternatives have yet been exposure to achieve the same level of control as developed (TEAP, 2000). However, these that of MB, and that it corrodes copper and its exemptions will be reviewed periodically in alloys and therefore electrical and electronic international meetings and they might not items need protection from exposure to the continue forever. In the absence of suitable fumigant. Phosphine also reacts to certain alternatives, this loss of MB as a fumigant could metallic salts, which are contained in sensitive seriously affect the protection of stored and items such as photographic film and some exported food commodities from pest organisms. inorganic pigments. To combat this situation, one approach has been to accept the use of MB where no alternatives exist, but, after fumigation, to absorb the gas for Newly considered fumigants recycling or to destroy it instead of releasing it to the atmosphere. There has been some limited Sulfuryl fluoride implementation of recovery and recycling for MB, mainly in North America and Europe. Sulfuryl fluoride has been used as a structural Recovery and recycling systems are generally fumigant for dry wood termite control for the complex and expensive to install compared with past 45 years, but it also has potential applications the cost of the fumigation facility itself. These in disinfesting flour mills and food factories (Bell systems would also require a level of technical et al., 1999). Although it can be used effectively competence not normally found at fumigation for insect pest control in dry tree nuts and food facilities. Therefore, examples of recovery and grain, data are scarce on the effect of sulfuryl recycle in current commercial use are few. fluoride on quality of the treated commodity and persistence of residues. The fumigant is more Phosphine penetrative into treated commodities than MB. Insect eggs are the most tolerant stage for sulfuryl Phosphine is available in solid preparations fluoride. The relative egg tolerance can be of aluminium or magnesium phosphide and in overcome by increasing the exposure period and cylinders containing carbon dioxide ECO2 by raising the treatment temperature (Bell et al., FUME® or FRISIN®. Lately, on-site 1999). Sulfuryl fluoride has been registered and phosphine generators that can release the used as a structural fumigant in Germany, fumigant up to the rate of 5 kg h–1 are available Sweden and the USA. Sulfuryl fluoride is in some countries (Argentina, Chile, China and available under the trade name “Vikane” USA). Metal phosphide formulations with slow containing 99.8 % sulfuryl fluoride and 0.2 % i nert 497 9th International Working Conference on Stored Product Protection materials. Apart from the USA, China has been spp.) and cheese. Research work on carbonyl producing sulfuryl fluoride (trade name sulfide in Australia, Germany and the USA reveal “Xunmiejin”) since 1983 (Guogan et al., 1999). that the egg stage is highly tolerant to the Also, sulfuryl fluoride can be applied under fumigant. Reports from Australia indicate that reduced pressure so that the exposure period can the fumigant does not affect the quality of wheat, be drastically reduced (Zettler and Arthur, 2000). and germination is not affected. However, The fumigant was noted as highly toxic to investigations on carried out in diapausing larvae of the codling moth, Cydia China showed contradictory results. Xianchang pomonella in stored walnuts (Zettler et al., et al. (1999) reported that carbonyl sulfide affects 1999). Sulfuryl fluoride is now registered under germination of cereals except sorghum and the new trade name “ProFume®” for the protection barley, and imparts off-odour. Milled rice after of stored food commodities (Schneider et al., treatment of paddy rice with carbonyl sulfide at 2003). ProFume® is registered in the US to allow the above dosages had an undesirable odour. virtually all mills and food processing facilities to Change in colour was also observed in fumigated test, adapt and consider adoption as an alternative soybeans. Zettler et al. (1999) also noticed an to MB. Additionally, registration coverage in EC off-odour during the first 24 h of aeration in countries for numerous milling and food walnuts that were fumigated with carbonyl processing applications is broad, and increasing sulfide. It is suspected that (TEAP, 2006). present in the supplied product, as an impurity, is partly responsible for the off-odour problem Propylene oxide (Desmarchelier, 1998).

Propylene oxide (PPO) is a colorless and Ethyl formate flammable liquid, and is used as a food emulsifier, surfactant, cosmetics and starch Ethyl formate is known as a solvent and is modifier. Under normal temperature and pressure used as a flavoring agent in the food industry. It PPO has a relatively low point (35 oC) is naturally present in certain fruits, wine and and a noticeable ether (Weast et al., 1986). honey. In India, extensive laboratory tests against It is a safe fumigant for use on food; it is insect pests of food commodities and field trials registered and used in the USA as a sterilant for on bagged cereals, spices, pulses, dry fruits and commodities such as dry and shelled walnuts, oilcakes have been carried out on the fumigant spices, cocoa powder and nutmeats (Griffith, (Muthu et al., 1984). Currently ethyl formate is 1999). A disadvantage of PPO is that it is being used for the protection of dried fruits in flammable at from 3 to 37 % in air, and therefore, Australia. It has been found suitable for in- to avoid flammability it should be applied under package treatment of dried fruits. Studies in low pressure or in CO2 -enriched atmospheres. Australia indicate that, unlike phosphine, ethyl Griffith (1999), in preliminary tests on some formate is rapidly toxic to storage insects stored product pests, indicated that PPO has including psocids (Annis and Graver, 2000). insecticidal properties under vacuum conditions as a fumigant. Navarro et al. (2004) studied the Hydrogen cyanide relative effectiveness of PPO alone, and in combination with low pressure or CO2. Hydrogen cyanide (HCN) is currently registered only in India, New Zealand and with Carbonyl sulphide severe restrictions in Germany. HCN was one of the first fumigants to be used extensively under Carbonyl sulfide (COS) is naturally present “modern” conditions. Its use for treating trees at low levels in food grains, vegetables (Brassica under tents against scale insects was developed 498 Fumigation and Control Atmosphere in California in 1886 (Woglum, 1949). The high less-expensive MB. dermal toxicity of the gas makes it hazardous to Methyl iodide was found to be very effective applicators. HCN is one of the most toxic of as a space fumigant (Shaaya et al., 2003; Zettler insect fumigants; it is very soluble in . HCN et al., 1999), being most toxic to eggs and least may be employed for fumigating many dry toxic to adults of Tribolium confusum (Tebbets foodstuffs, grains, and seeds. Although HCN is et al., 1986). Yokoyama et al. (1987) showed strongly sorbed by many materials, this action is that methyl iodide could prove valuable as a usually reversible when they are dry, and, given quarantine treatment for Carpocapsa pomonella time, all the fumigant vapours are desorbed. With in fresh fruits and as a rapid commodity many foodstuffs, little, if any, chemical reaction disinfestation treatment of 24h or less. The fact occurs, and there is no detectable permanent that the US Environmental Protection Agency has residue. Because of the high degree of sorption listed methyl iodide as a possible human at atmospheric pressure, HCN does not penetrate carcinogen could preclude registration in the US, well through the bulk of some commodities. particularly in California where it is listed as a compound known to cause cancer (EPA, 1998). Carbon disulphide

Carbon disulfide (CS2), an old fumigant, is used at the farm level in some parts of Australia Cyanogen (C2N2) is a colorless gas with and to a limited extent in China (TEAP, 2000). like odor and was patented as a new The major advantage of carbon disulfide is its fumigant effective against insects and small effect on seed germination. However, microorganisms (Yong and Trang, 2003). It is residues of carbon disulfide persist in treated highly toxic to stored product insects and is fast commodities for a longer period than that of other acting. It has a good penetration through the grain fumigants (Haritos et al., 1999). The reduction mass and it desorbs quickly. It is phytotoxic and in baking quality of wheat treated with this affects germination of treated seeds. But, it has fumigant was shown by Calderon et al. (1970). potential for space and flour/rice mill fumigations Some of the limitations of the fumigant include and disinfestations. Yong and Trang, (2003) high flammability, long exposure period, compared the contrasting characteristics of persistence in the treated commodity, lack of cyanogen, MB and phosphine as fumigants. residue limits set by Codex Alimentarius and high human toxicity. Ozone

Methyl iodide Ozone, a known sterilant, can be used as an insect control agent in food commodities at levels Methyl iodide has been patented as a pre-plant less than 45 ppm. Ozone is readily generated soil fumigant for control of a broad range of from atmospheric and is safe to the organisms including nematodes, fungi, and environment when used for fumigation. weeds (Grech et al., 1996) and the patent has However it is highly unstable and breaks down subsequently been expanded to include structural to molecular oxygen quickly. A major fumigation against termites and wood rotting disadvantage with ozone is its corrosive property fungi (Ohr et al., 1998). Methyl iodide’s potential towards most of the metals (Mason et al., 1999). as a fumigant for postharvest pest control has Active research is going on to exploit ozone as a been known for more than 68 years (Lindgren, potential quarantine treatment for controlling 1938). However, economic considerations at that stored-product pests (Hollingsworth, and time precluded its development in favor of the Armstrong, 2005).

499 9th International Working Conference on Stored Product Protection

b) Volatile essential oils of botanical origin: or low pressures to define the same method of The application of botanical extracts as treatment but using different means. fumigants in the protection of stored products from insect attack is in its infancy (Cox, 2002). There have been many plant extracts tested for their New application technologies that fumigant toxicity effect on stored product insects. have successfully replaced fumigants Pascual-Villalobos (2003) studied the insecticidal effects of a group of plant essential oils (caraway, Cereal grain preservation coriander, sweet basil, and garland chrysanthemum) against the damaging legume and cereal storage The initial research carried out during recent pests. Essential oils containing monoterpenoides decades was concentrated first on the possible were noted to be toxic to some stored product application of the MA technology to cereal grains insects and comparable to MB (Isman, 2000; Shaaya (Adler et al., 2000; Banks and Annis, 1990; et al., 2003; Tunc et al., 2000; Weaver and Navarro, 2006a). Subramanyam, 2000). The tested volatile plant extracts have the characteristics of essential oils with Tree nuts and dried fruits preservation a typical aromatic scent from the plant from which they were extracted. Therefore, because of their The possibility of applying MAs to control insects aromatic nature, plant extracts may be applied in in dried fruits and tree nuts has been reviewed by empty premises or to commodities such as seeds Soderstrom and Brandl (1990). The influence of low where the scent of the volatile essential oil would O2 or high CO2 atmospheres as alternatives to not present a restriction after the treatment. Most fumigation of dried fruits has also been investigated by studies on volatile plant extracts have shown their Soderstrom, and Brandl (1984); and Tarr et al. (1994). efficacy in empty fumigation chambers. Due to their Ferizli and Emekci (2000) applied CO2 for treating strong absorption, their application in bulk stored dried figs in a gastight flexible storage unit loaded with commodities is associated with poor penetration 2.5 tonnes of dried figs in perforated boxes. ability into the deep layers. Large scale These conditions resulted in complete mortality of both applications that demonstrate the penetration insects and mites. Full scale commercial application of capacity of these volatile oils are lacking in the organic raisins is being applied in California since 1984 literature. A major delaying factor to the use of (Navarro, 2000). these oils is that such alternatives of plant origin require toxicological and safety data for Disinfestation of dates registration for use as fumigants. As a potential alternative to MB fumigation, c) Non-residual gaseous treatments, the influence of different CAs in causing modified atmospheres (MAs): emigration of Carpophilus spp. larvae from dates The objective of MA treatments is to attain a was compared with that of MB by Donahaye et al. (1991) and Navarro et al. (1989). A composition of atmospheric gases rich in CO2 and low concentration of 35 % CO2 was found to cause a in O2, or a combination of these two gases at normal or altered atmospheric pressure within the treatment similar emigration to that by MB. This method enclosure, for the exposure time necessary to control has been in use in a large packing house in Israel the storage pests and preserve the quality of the (Navarro, 2006b). commodity. Terms used in reference to MA storage for the control of storage insect pests or for the Application of MAs at elevated preservation of food have appeared in the literature as temperatures CA, as sealed storage, or atmospheres used at high The influence of temperature on the length of time 500 Fumigation and Control Atmosphere necessary to obtain good control with MAs is as important as with conventional fumigants. Navarro and Calderon (1980) compared the effect of temperature on the exposure time required to produce the mortality of adults of three storage insects in MAs. Donahaye et al. (1994) reported on responses of larval, pupal, and adult stages of two nitidulid beetles exposed to simulated burner- gas concentrations at three temperatures of 26, 30, and 35 °C. Soderstrom et al. (1992) examined the influence of temperature over the range of 38–42 °C on the effects of hypoxia and hypercarbia on Figure 1. A V-HF CocoonTM holding cocoa beans Tribolium castaneum adults. Their results clearly in bags, under a pressure of 50 mm Hg connected indicate that raised temperatures could be used to to the vacuum pump in a trial site in Boston, reduce treatment duration. Navarro et al. (2003) Massachusetts (courtesy of GrainPro Inc.). showed the strong influence of temperatures of 35 o, 40 o, and 45 oC on mortality of all four development stages of Ephestia cautella when the insects were exposed to CO concentrations varying from 60 2 High pressure carbon dioxide treatment to 90 % in air. Bell and Conyers (2002) (HPCT) investigated the potential to kill pests using MAs at raised temperatures to increase their speed of Carbon dioxide still remains slower-acting action. These works led to the application of MAs and more expensive than phosphine or MB. CO at elevated temperatures by ECO in Holland 2 2 treatments can be significantly shortened to with the objective to reduce the exposure times exposure times that may be measured in hours commercially to control pests in imported using increased pressure (10-37 bar) applied in tobacco products, cocoa beans, rice, cereals, specially designed metal chambers that withstand grains, nuts, peanuts, pulses, seeds and spices, the high pressures. Prozell et al. (1997) exposed as well as furniture and artifacts. cocoa beans, hazel nuts and tobacco to a quick disinfestation process of exposure to carbon Vacuum treatment and V-HF technology dioxide under pressure of 20-40 bars. Because of the high initial capital investment, these high- In a low-pressure environment, there is a close pressure chamber treatments are practical for correlation between the partial pressure of the high value products such as spices, nuts, remaining O2 and the rate of kill. Until recently, this treatment could only be carried out in medicinal herbs and other special commodities. specially constructed rigid and expensive vacuum A number of countries have adopted the use of chambers. A practical has been proposed this technology; among them are Germany and named the vacuum hermetic fumigation (V-HF) Turkey. process that uses flexible liners (Finkelman et al., 2003). To achieve this, sufficiently low Modified Atmosphere Packaging (MAP) pressures (25-50 mmHg absolute pressure) can be obtained (using a commercial vacuum pump) Modified Atmosphere Packaging (MAP) is a and maintained for indefinite periods (Figure1). technique used for prolonging the shelf- period This technology is currently in use at commercial of fresh or minimally processed foods. In this level for pest treatment of organic soybeans and preservation technique the air surrounding the flours in Israel. food in the package is modified to a composition 501 9th International Working Conference on Stored Product Protection of low oxygen or a combination of low oxygen material and equipment for the use of nitrogen. and high carbon dioxide. The interest in modified atmosphere packaging (MAP) has grown due Fresh storage of fruits and vegetables consumer demand. This has led to advances in the design and manufacturing of polymeric films suitable Fresh fruits and vegetables may be shipped for MAP. Under MA, products such as bakery or stored in controlled atmospheres. This topic goods, and dried foods are packaged. The effects is covered in depth in the book of Calderon and of storage temperature and packaging atmosphere Barkai-Golan (1990) and in a more recently (air and N2) on the quality of were studied published chapter by Ben-Yehoshua, et al. by Garcia-Pascual et al. (2003). Guidelines for using (2005). modified atmospheres in packaged food, with special emphasis on microbiological and nutritional aspects, Narcissus bulbs treatments have been published by the Council of Europe (Anonymous, 1999). The large narcissus fly Merodon eques F. attacks narcissus bulbs and also bulbs of other Museum Artifacts geophytes. This species is a quarantine pest where complete mortality is required prior to The possibilities of controlling pests in export from Israel. Fumigation with MB has artifacts using inert gases were reported by been used to eliminate narcissus fly infestation Reichmuth et al. (1991, 1993). Museums in flower bulbs due to its rapid killing time throughout the world face the challenge of (4 h). However, MB is also known for its finding non-toxic methods to control insect pests. phytotoxic effect on the bulbs and its use is Recently several publications focus on practical discouraged even for quarantine purposes in rather than theoretical issues in the use of oxygen- developed countries. free environments, presenting a detailed, hands- In experimental procedures, Donahaye et al. on guide to the use of oxygen-free environments (1997) found that there was an extremely rapid in the eradication of museum insect pests depletion of O2 within the sealed gastight (Maekawa and Elert, 2002; Selwitz and enclosures in which the narcissus bulbs were Maekawa, 1998). placed for fumigation, due to the respiration As interest in modified atmospheres for food of the newly harvested bulbs. This procedure preservation peaked, conservation scientists also revealed the significant anoxia achieved began to study how this technology could be within less than 20 hours (less than 0.1 % O2 adapted to museum needs (Selwitz and and about 15 % CO2) during treatment at 28 °C Maekawa, 1998). Although a carbon dioxide to 30 °C and the possibility of using it alone atmosphere had been favored for the as a control measure. The possibility of preservation of foodstuffs, conservators saw obtaining a bio-generated modified more advantages in using nitrogen with low atmosphere utilizing the bulb respiration alone oxygen concentrations to treat museum was adopted by Israeli farmers as a practical artifacts, collectively termed “cultural property” solution using specially designed flexible because anoxia provides a higher degree of treatment chambers (Figure 2) (Navarro and inertness and is easier to establish for small- Donahaye, 2005; Navarro, 2006a). This MA scale operations. The technology of MA has method has been successfully applied by the received the specific terminology of “anoxia” narcissus bulb growers in Israel and fully for the treatment of museum-artifacts, libraries, replaced the use of MB since 2003. and among the manufacturers and suppliers of

502 Fumigation and Control Atmosphere

Figure 2. Narcissus bulbs in standard boxes before loading on pallets (upper left), loading the pallets containing the narcissus bulbs (left), and the general view of two sealed V-HF CocoonsTM under treatment (right) (courtesy of GrainPro Inc.).

registration for use as fumigants. The only gaseous Conclusions treatment that retains the special capacity of fumigation for in-situ treatment of stored No fumigant that has a broad spectrum of action commodities, as well as offering a similar diversity like MB, and is inexpensive like phosphine, is of application technologies, is the MA method. MAs presently available. Although there is no doubt that offer an alternative that is sustainable, safe, and fumigation technology is extremely important for the environmentally benign to the use of conventional protection of stored products, many demands are residue-producing chemical fumigants. The required from potential alternative fumigants, from application of MA in several fields of application the sensitivity and lack of resistance of target pests has already received recognition and successfully to requirements for registration of new fumigants and replaced MB and phosphine. The major fields re-registration to maintain the use of old fumigants. of application of MAs are: grain and pulses stored However, there is increasing public concern over in bulk, protection of organic products, use of the adverse effects of pesticide residues in food and anoxia for museum artifacts, and libraries, and the environment. Existing gaseous alternatives to MB use of MAP for the food packaging industry. and phosphine suffer from the limitation that they Newly developed MA methods for niche may be useful for treating a particular type of applications, have resulted in very promising commodity or for application in a specific situation applications such as for the treatment of seeds, only. Sulfuryl fluoride seems to emerge as a narcissus bulbs, cocoa beans, dried fruits and promising candidate fumigant for disinfesting stored nuts. The global challenges in stored products food commodities, food-processing facilities and as are the development of new and safer gaseous a quarantine fumigant. Other fumigants are suitable treatments, and new application methods of MAs to specific uses, such as propylene oxide for dry that are commercially feasible. and shelled walnuts, spices, cocoa powder and nutmeats, ethyl formate can be suitable for dried fruits, carbon disulfide for seed materials, and Acknowledgements carbonyl sulfide for grains. Plant extract essential oils and other volatiles of plant origin will need large The author thanks his colleagues Dr. E. scale demonstration of their penetration capacity, in Donahaye, Dr. S. Finkelman, and Dr. S. Angel addition to toxicological and safety data for former researchers at the Volcani Center, the Israel

503 9th International Working Conference on Stored Product Protection

Agricultural Research Organization, and currently, atmospheres at raised temperatures for FTIC (Food Technology International Consultancy) treatment of durable commodities. In: Ltd. for reading the manuscript and making valuable Obenauf G.L., Obenauf, R. (Eds), Annual comments. International Research Conference on Methyl Bromide Alternatives and Emissions Reductions, Orlando, Florida, USA, pp 52, References 52-2.

Adler, C., Corinth, H.G., Reichmuth, C., 2000. Bell, C.H.; Savvidou, N.; Smith, T.J.W., 1999. Modified atmospheres. In: Subramanyam, The toxicity of sulfuryl fluoride (Vikane) to Bh., Hagstrum, D.W. (Eds), Alternatives to eggs of insect pests of flourmills. In: Pesticides in Stored-Product IPM. Kluwer Zuxun, J., Quan, L., Yongsheng, L., Academic Publishers, Boston, pp. 105-146. Xianchang, T., Lianghua, G. (Eds), Proceedings of the Seventh International Annis, P.C., Graver, J.E., Van, S., 2000. Ethyl Working Conference on Stored Product formate – a fumigant with potential for Protection, Beijing, China, October 1998. rapid action. In: 2000 Annual International Sichuan Publishing House of Science and Research Conference on Methyl Bromide Technology, Chengdu, pp. 345–350. Alternatives and Emissions Reductions, Orlando, 6–9 Nov, 2000, pp. 70-1; 70-3. Ben-Yehoshua, S., Beaudry, R.M., Fishman, S., Jayanty, S., Mir, N., 2005. Modified Anonymous, 1999. Guidelines for Packaging Atmosphere Packaging and Controlled in Modified Atmospheres with Special Atmosphere Storage. In: Ben-yehoshua, S. Emphasis on Microbiological and (Ed), Environmentally Friendly Nutritional Aspects, Council of Europe Technologies for Agricultural Produce Publishing, 26 p. Quality, CRC Press, Taylor & Francis Group, Boca Raton, Florida, pp. 61-112. Arthur, F.H.; Rogers, T., 2003. Legislative and regulatory actions affecting insect pest Bond, E.J., 1984. Manual of fumigation for management for postharvest systems in the insect control. FAO Plant Production and United States. In: Credland, P.F., Armitage, Protection Paper No. 54, 432 p. D.M., Bell, C.H., Cogan, P.M., Highley, E. (Eds), Advances in Stored Product Calderon, M., Barkai-Golan, R., 1990. Food Protection, Proceedings of the 8th Preservation by Modified Atmospheres. International Working Conference on CRC Press Boca Raton, Florida. Stored-product Protection, York, CAB International, Oxon, UK, pp. 435-438. Calderon, M., Navarro, S., Lindner, Z., 1970. Effect of common fumigants on the baking Banks, H.J., Annis, P.C., 1990. Comparative quality of wheat. Cereal Chemistry 47,

advantages of high CO2 and low O2 types 422-428. of controlled atmospheres for grain storage, In: Calderon, M., Barkai-Golan, R. (Eds), Cao, Y., Song, Y., Sun, G., 2003. A survey of Food Preservation by Modified psocid species infesting stored grain in Atmospheres, CRC Press, Boca Raton, China and resistance to phosphine in field Florida, pp. 93-122. populations of Liposcelis entomophila. In: Credland, P. F., Armitage, D.M., Bell, C.H., Bell, C.H., Conyers, S.T., 2002. Modified Cogan, P.M., Highley, E. (Eds), Advances in

504 Fumigation and Control Atmosphere

Stored Product Protection, Proceedings of the fumigation as a methyl bromide alternative for 8th International Working Conference on the dried fig industry, In: Obenauf, G.L., Stored-product Protection, York, CAB Obenauf, R. (Eds), Annual International International, Oxon, UK, pp. 662-667. Research Conference on Methyl Bromide Alternatives and Emissions Reductions, Cox, P.D., 2002. Potential for using Orlando, Florida, pp. 81. semiochemicals to protect stored products from insect infestation - A review. Journal Finkelman, S., Navarro, S., Isikber, A., Dias, R., of Stored Products Research 40, 1-25. Azrieli, A., Rindner, M., Lotan, Y., Debruin, T., 2003. Insects control of cocoa pests using Desmarchelier, J.M., 1998. Potential new a novel vacuum approach. In: Credland, P.F., fumigants. In: Stored Grain in Australia: Armitage, D.M., Bell, C.H., Cogan, P.M., Proceedings of the Australian Postharvest Highley, E. (Eds), Advances in Stored Technical Conference, Canberra, Australia, Product Protection, Proceedings of the 8th 26-29 May, 1998, pp. 133-137. International Working Conference on Stored- product Protection, York, CAB International, Donahaye, E., Navarro, S., Rindner, M., 1994. Oxon, UK, pp. 579-582. The influence of temperature on the sensitivity of two nitidulid beetles to low Garcia-Pascual, P., Mateos, M., Carbonell, V., oxygen concentrations. In: Highley, H.E., Salazar, D.M., 2003. Influence of Storage Wright, E.J., Banks, H.J., Champ, B.R., Conditions on the Quality of Shelled and (Eds), Proceedings 6th International Roasted Almonds. Biosystems Engineering Working Conference on Stored-Product 84, 201-209. Protection. (Canberra.) CAB International, Wallingford, U.K., pp. 88-90. Grech, N.M., Ohr, H.D., Sims, J.J., 1996. Methyl iodide as a soil fumigant. U.S. Donahaye, E., Navarro, S., Rindner, M., Dias, Patent No. 5,518,692, May 1996. U.S. R., 1991. The influence of different Patent and Trade-mark Office. treatments causing emigration of nitidulid beetles. Phytoparasitica 19, 273-282. Griffith, T., 1999. Propylene oxide, a registered fumigant, a proven insecticide. Donahaye, E.J., Navarro, S., Dias, R., Rindner, In: Obenauf, G.L., Williams, A. (Eds), M., Azrieli, A., 1997. Sensitivity of Annual International Research Conference narcissus flies (genera: Eumerus and on Methyl Bromide Alternatives and Merodon) to Methyl Bromide. In: Emissions Reductions, November 1-4 Donahaye, E.J., Navarro, S., Varnava, A. 1999, UNEP and USDA, San Diego, (Eds), Proceedings of an International California, pp.71. Conference on Controlled Atmosphere and Fumigation in Grain Storages. PrintCo Guogan, X., Zhongmei, C., Zhao, S., Nengzhi, Ltd., Nicosia, Cyprus, pp. 25-29. Q., 1999. The development of sulfuryl

fluoride (SO2F2), in China – a brief EPA, Environmental Protection Agency, 1998. introduction. In: Zuxun, J., Quan, L., Methyl iodide. United Air Toxics Website, Yongsheng, L., Xianchang, T., Lianghua, G. www.epa.gov/ttn/uatw/hlthef/ (Eds), Proceedings of the Seventh methylio.htlml International Working Conference on Stored Product Protection, Beijing, China, Ferizli, A.G., Emekci, M., 2000. Carbon dioxide October 1998. Sichuan Publishing House

505 9th International Working Conference on Stored Product Protection

of Science and Technology, Chengdu, pp. Jayaram, M., Majumder, S.K., 1984. Ethyl 562–566. formate as a safe general fumigant. In: Controlled Atmosphere and Fumigation in Haritos, V.S., Ren, Y.L., Desmerchelier, J.M., Grain Storages, Perth, Australia, 11-22 April, 1999. Regulatory toxicology of alternative 1983, pp. 369-393. fumigants. In: Zuxun, J., Quan, L., Yongsheng, L., Xianchang, T., Lianghua, G. Navarro, S., 2000. Storage of prunes under (Eds), Proceedings of the Seventh controlled atmospheres for quality International Working Conference on preservation and insect control. Sabbatical Stored Product Protection, Beijing, China, Report 1998-1999 submitted to the USDA, October 1998. Sichuan Publishing House ARS, Horticultural Crops Research of Science and Technology, Chengdu, pp. Laboratory, Fresno, CA. 356-363. Navarro, S., 2006a. Modified Atmospheres for Hollingsworth, R.G., Armstrong, J.W., 2005. the Control of Stored-Product Insects and Potential of Temperature, Controlled Mites. In: Heaps, J.W. (Ed), Insect Atmospheres and Ozone Fumigation to Management for Food Storage and Control Thrips and Mealybugs on Processing, Second Edition. AACC Ornamental Plants for Export. Journal of International, St. Paul, MN, pp. 105-146. Economic Entomology 98, 289-298. Navarro, S., 2006b. Postharvest treatment of Isman, M.B., 2000. Plant essential oils for pest dates. In: Sarig, Y. (Ed) Quality, Stewart and disease management. Crop Protection Postharvest Review (UK) Vol. 2, Issue 19, 603-608. Number 2, April 2006, pp. 1-9. http:// www.stewartpostharvest.com/April_2006/ Lindgren, D.L., 1938. Methyl iodide as a Navarro.pdf fumigant. Journal of Economic Entomology 31, 320. Navarro, S., Calderon, M., 1980. Integrated approach to the use of controlled Maekawa, S., Elert, K., 2002. The Use of atmospheres for insect control in grain Oxygen-Free Environments in the Control storage. In: Shejbal, J. (Ed), Controlled of Museum Insect Pests. Getty Atmosphere Storage of Grains. Conservation Institute. Proceedings International Symposium, 12- 15th May 1980, Rome, pp. 73-78. Mason, L.J., Strait, C.A., Woloshuk, C.P., Maier, D.E., 1999. Controlling stored Navarro, S., Donahaye, E., 2005. Innovative grain insects with ozone fumigation. In: Environmentally Friendly Technologies to Zuxun, J., Quan, L., Yongsheng, L., Maintain Quality of Durable Agricultural Xianchang, T., Lianghua, G. (Eds), Produce. In: Ben-Yehoshua, S. (Ed), Proceedings of the Seventh International Environmentally Friendly Technologies for Working Conference on Stored Product Agricultural Produce Quality, CRC Press, Protection, Beijing, China, October 1998. Taylor & Francis Group, Boca Raton, Sichuan Publishing House of Science and Florida, pp. 205-262. Technology, Chengdu, pp. 536-547. Navarro, S., Donahaye, E., Dias, R., Jay, E., Muthu, M., Rajendran, S., Krishnamurthy, T.S., 1989. Integration of modified atmospheres Narasimhan, K.S., Rangaswamy, J.R., for disinfestation of dried fruits. Final Scientific

506 Fumigation and Control Atmosphere

Report of Project No: I-1095-86, submitted Navarro, S., Varnava, A. (Eds), Proceedings to US-Israel Bi-national Agricultural Research of an International Conference on and Development Fund (BARD) 86 pp. Controlled Atmosphere and Fumigation in Grain Storages, PrintCo Ltd., Nicosia, Navarro, S., Finkelman, S., Sabio, G., Isikber, A., Cyprus, pp. 325-333. Dias, R., Rindner, M., Azrieli, A., 2003.

Enhanced effectiveness of vacuum or CO2 Rajendran, S., 2001. Alternatives to methyl in combination with increased temperatures bromide as fumigants for stored food for control of storage insects. In: Credland, commodities. Pesticide Outlook, pp. 249-252. P.F., Armitage, D.M., Bell, C.H., Cogan, P.M., Highley, E. (Eds), Advances in Stored Reichmuth, C., Corinth, H.G., Buchmüller, J., Product Protection, Proceedings of the 8th 1993. Vorratsschutz: Entwesen mit International Working Conference on Kohlendioxid. [Stored product protection: Stored-product Protection, York, CAB Disinfestation with carbon dioxide.] Mühle International, Oxon, UK,. pp. 818-822. Mischfuttertech 130, 667-671.

Navarro, S., Isikber, A.A., Finkelman, S., Reichmuth, C., Unger, W., Unger, A., 1991. Rindner, M., Azrieli, A., Dias, R., 2004. Stickstoffzur Bekampfung holzzerstorender Effectiveness of short exposures of Insekten in Kunstwerken. [Nitrogen for the propylene oxide alone and in combination control of wood destroying pest insects in with low pressure or carbon dioxide against artifacts.] Restauro 97, 246-251. Tribolium castaneum (Herbst) (Coleoptera: Tenebrionidae). Journal of Stored Products Savvidou, N., Mills, K.A., Pennington, A., Research 40, 197-205. 2003. Phosphine resistance in Lasioderma serricorne (F.) (Coleoptera: Anobiidae). In: Ohr, H.D., Grech, N.M., Sims, J.J., 1998. Credland, P.F., Armitage, D.M., Bell, C.H., Methyl iodide as a fumigant. U.S. Patent Cogan, P.M., Highley, E. (Eds), Advances No. 5,753,183, May 19, 1998. U.S. Patent in Stored Product Protection, Proceedings and Trade-mark Office of the 8th International Working Conference on Stored-product Protection, York, CAB Pascual-Villalobos, M.J., 2003. Volatile International, Oxon, UK, pp. 702-712. activity of plant essential oils against stored-product beetle pests. In: Credland, Schneider, B., Voglewede, C., Houtman, B., P.F., Armitage, D.M., Bell, C.H., Cogan, 2003. The technical foundation for P.M., Highley, E. (Eds), Advances in Stored precision stored-product-pest fumigation Product Protection, Proceedings of the 8th with ProFume™ gas fumigant. In: International Working Conference on Credland, P.F., Armitage, D.M., Bell, C.H., Stored-product Protection, York, CAB Cogan, P.M., Highley, E. (Eds),. Advances International, Oxon, UK, pp. 648-650. in Stored Product Protection, Proceedings of the 8th International Working Conference Prozell, S., Reichmuth, Ch., Ziegleder, G., on Stored-product Protection, York, CAB Schartmann, B., Matissek, R., Kraus, J., International, Oxon, UK, pp. 561-564. Gerard, D., Rogg, S., 1997. Control of pests and quality aspects in cocoa beans Selwitz, C., Maekawa, S., 1998. Inert Gases in and hazelnuts and diffusion experiments in the Control of Museum Insect Pests. The compressed tobacco with carbon dioxide Getty Conservation Institute, University of under high pressure. In: Donahaye, E.J., California, Riverside. 107 p.

507 9th International Working Conference on Stored Product Protection

Shaaya, E.; Kostyukovsky, M.; Demchenko, N., Report, Montreal Protocol on Substances that 2003. Alternative fumigants for the control of Deplete the Ozone Layer, United Nations stored-product insects. In: Credland, P. F., Environment Programme, Ozone Secretariat, Armitage, D. M., Bell, C. H., Cogan, P. M., May 2006, Nairobi, Kenya: http:// Highley, E. (Eds),. Advances in Stored www.unep.org/ozone/teap/Reports/ Product Protection, Proceedings of the 8th TEAP_Reports/ International Working Conference on Stored- product Protection, York, CAB International, Tebbets, J.S., Vail, P.V., Hartsell, P.L., Nelson, Oxon, UK, pp. 556-560. H.O., 1986. Dose response of codling moth (Lepidoptera: Tortricidae) eggs and Soderstrom, E.L., Brandl, D.G., 1984. Low- non-diapausing and diapausing larvae to oxygen atmosphere for postharvest insect fumigation with methyl bromide. Journal control in bulk- stored raisins. Journal of of Economic Entomology 79, 1039-1043. Economic Entomology 77, 440. Tunc, I., Berger, B.M., Erler, F., Dagli, F., Soderstrom, E.L., Brandl, D.G., 1990. 2000. Ovicidal activity of essential oils Controlled atmospheres for the from five plants against two stored-product preservation of tree nuts and dried fruits. insects. Journal of .Stored Products In: Calderon, M., Barkai-Golan, R. (Eds), Research 36, 161-168. Food Preservation by Modified Atmospheres, CRC Press, Boca Raton, UNEP - United Nations Environment Florida, pp. 83-92. Programme, 2002. Montreal Protocol on Substances that Deplete the Ozone Layer, Soderstrom, E.L., Brandl, D.G., Mackey, B., 2002 Assessment, Methyl Bromide 1992. High temperature combined with Technical Options Committee. Nairobi, carbon dioxide enriched or reduced oxygen Kenya. http://www.unep.org/ozone/teap/ atmospheres for control of Tribolium Reports/TEAP_Reports/ castaneum (Herbst)(Coleoptera: Curculionidae). Journal of .Stored Waterford, C.J., Asher, P.P., 2000. A new Products Research 28, 235-238. formulation of aluminium phosphide providing controlled release of phosphine. Tarr, C., Hilton, S.J., Graver, J. Van S., In: Obenauf, G.L., Obenauf, R. (Eds), Clingeleffer, P.R., 1994. Carbon dioxide Annual International Research Conference fumigation of processed dried on Methyl Bromide Alternatives and (sultanas) in sealed stacks, In: Highley, Emissions Reductions, Orlando, Florida, H.E., Wright, E.J., Banks, H.J., Champ, pp. 77-1. B.R., (Eds), Proceedings 6th International Working Conference on Stored-Product Weast, R.C., Astle, M.J., Beyer, W.H., 1986. Protection. (Canberra.) CAB International, CRC Handbook of Chemistry and Physics, Wallingford, U.K., pp. 204-209. 67th edition, CRC Press, Inc. Boca Raton, Florida. Teap, 2000. Report of the Technology and Economic Assessment Panel. In: KUIJPERS, Weaver, D.K., Subramanyam, B., 2000: L. (Ed), April 2000. UNEP, Nairobi. 193 p. Botanicals. In: Subramanyam, Bh.; Hagstrum, D.W. (Eds), Alternatives to Pesticides in Teap, 2006. Report of the Technology and Stored-Product IPM. Kluwer Academic Economic Assessment Panel, Progress Publishers, Massachusetts, pp. 303-320.

508 Fumigation and Control Atmosphere

Woglum, R.S., 1949. History of fumigation in D.M., Bell, C.H., Cogan, P.M. And Highley, California. California Citrouraph, 35, 46-72. E. (Eds),. Advances in Stored Product Protection, Proceedings of the 8th Xianchang, T., Xingwei, H., Lizheng C., Jianchun International Working Conference on Stored- W., 1999. Research on carbonyl sulfide as a product Protection, York, CAB International, fumigant for control of stored grain insects. In: Oxon, UK, pp. 651-653. Zuxun, J., Quan, L., Yongsheng, L., Xianchang, T., Lianghua, G. (Eds), Zettler, J.L., Leesch, J.G., Gill, R.F., Tebbets, Proceedings of the Seventh International J.C., 1999. Chemical alternatives for Working Conference on Stored Product methyl bromide and phosphine treatments Protection, Beijing, China, October 1998. for dried fruits and nuts. In: Zuxun, J., Sichuan Publishing House of Science and Quan, L., Yongsheng, L., Xianchang, T., Technology, Chengdu, pp. 567–571. Lianghua, G. (Eds), Proceedings of the Seventh International Working Conference Yokoyama, V.Y., Miller, G.T., Hartsell, P.L., on Stored Product Protection, Beijing, 1987. Methyl bromide fumigation for China, October 1998. Sichuan Publishing quarantine control of codling moth House of Science and Technology, (Lepidoptera: Tortricidae) on nectarines. Chengdu, pp. 554-561. Journal of Economic Entomology 80, 840- 842. Zettler, J.L., Arthur, F.H., 2000. Chemical control of stored product insects with Yong, L.R., Trang, L.V., 2003. Cyanogen: A fumigants and residual treatments. Crop possible fumigant for flour/rice mills and space Protection 19, 577-582. fumigation. In: Credland, P.F., Armitage,