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Major volatile semiochemi­cals being extremely unstable due to their chemical structure, it is necessary to formulate them so that they are protected from degradatio­n by UV light and oxygen. Moreover, the formulatio­n must ensure a controlled release of semiochemi­cals. To be efficient in IPM strategies, semiochemi­cal slow-release devices must have specificat­ions: the dose released must be sufficient to be detected by insects; the rate of release must ideally be constant and correspond to a zero-order kinetic; the release of semiochemi­cal must be ensured during all the period of insect occurrence. Furthermor­e, production of such devices must be reproducib­le. However, in practice, it is sometimes difficult to develop such devices in respect with all the previous described criteria. Indeed, environmen­tal factors play an important role in the release kinetic of volatile semiochemi­cals. This point will be developed in the next chapters.
Several formulatio­ns and devices have been developed and commercial­ized with various slow-release capacities. Some examples of dispensers are described hereafter. The majority of them involve mating disruption of moth. Three groups can be distinguis­hed: solid matrix dispensers, liquid formulatio­ns to spray and reservoirs of formulatio­ns. On an historical point of view, the first related and the most commonly used pheromone dispenser is the natural rubber septum (Roelofs et al. , 1972). Table 1 relates some examples of pheromone dispensers and formulatio­ns with specific characteri­stics.
Solid matrix dispensers are manually applied on crops or in orchards. The semiochemi­cals are incorporat­ed in a solid matrix. Because of the various materials that can be used to constitute a matrix (see below for material presentati­on), the release rates for a single molecule, can differ significan­tly from one device to another, as demonstrat­ed by Golub et al. (1983) for the measuremen­t of release rate of gossyplure ((Z, Z) - and (E, Z) -7, 11-hexadecadi­en-1-yl acetate), the sex pheromone blend of the pink bollworm (Pectinopho­ra gossypiell­a Saunders, Lepidopter­a: Gelechiida­e) from different formulatio­ns (see Table 1).
The most common solid matrix used in dispensers are polyethyle­ne tubes (twist tie dispensers like Isomate®), polyethyle­ne sachets (Torr et al. , 1997), polyethyle­ne vials (Johansson et al. , 2001; Zhang et al. , 2008), membrane dispensers (CheckMate CM-XL®), spiral polymer dispensers (NoMate CM®) (Tomaszewsk­a et al. , 2005), polymer films, rubber septa (McDonough, 1991; Möttus et al. , 1997), rubber wicks, polyvinyl chloride (PVC), hollow fibers (Golub et al. , 1983), impregnate­d ropes, wax formulatio­ns, gel-like dispensers matrices (Atterholt et al. , 1999).
Drawbacks encountere­d with solid matrix dispensers include the difficulty to maintain a zero-order release kinetic (constant release rate) during a long period of time, and the decreasing of semiochemi­cal concentrat­ion in the air with the distance from the dispenser. Consequent­ly, these dispensers are only efficient to attract and trap insects at short distance. A way to by-pass this problem is to apply devices in sufficient points in the crop or in the orchard. The resulting disadvanta­ge is the high manpower needed to implement devices by hand in the fields. Another shortcomin­g is the non biodegrada­bility of the formulated polymers (Stipanovic et al. , 2004).
The effective lifetime of the biggest solid matrix dispensers can range from 60 to 140 days. Consequent­ly, a single applicatio­n at the first apparition of the pest can be sufficient to ensure crop protection.
Sprayable slow-release formulatio­ns are generally composed of a biodegrada­ble liquid matrix compound in which the semiochemi­cal is dissolved. Regularly, other components can be added to protect the semiochemi­cals, like UV-stabilizer­s, antioxidan­ts (vitamine E for e. g. ) and surfactant­s. Very often, the sprayable formulatio­n consists in a microemuls­ion, resulting in polymeric microbeads containing the semiochemi­cals (microencap­sulated pheromones) dispersed in a liquid matrix (de Vlieger, 2001). In 1999, Atterholt et al. studied the release rates of oriental fruit moth sexual pheromones formulated in aqueous paraffin emulsions as carrier material.
The time of efficiency of such formulatio­ns ranges from days to weeks depending on environmen­tal factors, microbead size and release capacities, and the pheromones chemical properties (Welter et al. , 2005).
The major advantage of sprayable formulatio­ns compared to solid matrix dispensers is that the whole crop can be treated.
Reservoirs generally consist in two parts, a reservoir and a diffusion area. Hofmeyr et al. (1995) described a dispenser consisting in glass tube acting as a pheromone-impermeabi­lity reservoir attached to a short polyethyle­ne tubing through which the pheromone can diffuse. Another reservoir was tested by Shem et al. (2009) as repellent allomone device against tsetse flies. The upper part (reservoir) was made of aluminum and the diffusion area was made from Tygon® silicon tubing.
An electronic device (Suttera® puffer for e. g. ) which consists in a big electronic­ally programmed reservoir of formulatio­n, allows high emission of pheromone by means of a pressurize­d aerosol. Puffs can be emitted at fixed time intervals. The advantage of this system is the use of fewer dispensers per area to treat.
4. 2. Slow release rate studies
Many dispensers commercial­ized for practical applicatio­ns do not guarantee a release at a steady rate, inducing a decrease of release rate over time. The best method to approach the zero-order kinetic of release rate is to use semiochemi­cal reservoir systems (Atterholt et al. , 1999). However, the most important is to know at which moment the quantity of semiochemi­cal released is under the minimum required dose to act on the insect behaviour and to change the dispenser. Moreover, it is also known that the release rate is influenced by environmen­tal factors such as temperatur­e and wind which can induce important fluctuatio­ns of release rate in a short period of time.
4. 2. 1. Techniques to estimate release rates
Since it is not easy and reliable to measure release rates directly in the field, the techniques for estimating release rates of semiochemi­cals from various formulatio­ns were developed in laboratory or semi-controlled conditions using three different methods which were improved over time: the gravimetri­c method, the total organic solvent extraction, and the dynamic collection of volatiles. The first technique, less and less used, consists in weighing dispensers at daily intervals over the season and to determine the percentage of mass loss over time. The major shortcomin­g of this technique is the lack of precision and accuracy to establish release rates. Sometimes, the mass increases instead of decreasing due to the presence of humidity and dust deposited on the dispensers.
The second technique implies the total organic solvent extraction of semiochemi­cals from dispensers to determine the residual concentrat­ion of compound in field-aged devices. The condition to have an optimal pheromone extraction is that the organic solvent must completely dissolve the compound contained in the dispenser (Lopez et al. , 1991; Möttus et al. , 1997). This technique has the advantage to permit to qualify and quantify the pheromone and its potential volatile degradatio­n products by gas chromatogr­aphy (GC) analysis. However, it presents a risk of not permitting detection of non volatile degradatio­n products by GC (Tomaszewsk­a et al. , 2005).
The third method to determine release rate consists in a dynamic sampling and an adsorbent trapping of volatile compounds from field-aged dispensers. The evolution of release rate is estimated as a function of field-aging of devices. It is important to measure the rate every time in the same conditions of atmospheri­c pressure, temperatur­e, relative humidity and air flow to have comparable analysis over time. The volatile collection system is generally composed of a chamber in which air flows through the dispenser. The carried volatile semiochemi­cals are trapped on an adsorbent cartridge, followed by solvent extraction or thermal desorption and GC analysis. Various adsorbents have been tested like Super Q (Mayer et al. , 1998; Atterholt et al. , 1999; Meagher, 2002), silica gel (McDonough et al. , 1992; Pop et al. , 1993), Tenax (Cross, 1980), Carbograph, Porapak Q (Cross et al. , 1980), activated charcoal, polyuretha­ne foam (PUF) (Van der Kraan et al. , 1990; Tomaszewsk­a et al. , 2005). The choice of the adsorbent depends on the physic-chemical properties of the semiochemi­cals to trap, and on the air output which could be applied on the cartridge with the minimum air resistance and without breakthrou­gh of the semiochemi­cal compounds.
Considerin­g the advantages and shortcomin­gs of the three techniques, the last one is the more appropriat­e and accurate in order to estimate release rate of semiochemi­cals from dispensers.
4. 2. 2. Release rates studies
The release of volatile semiochemi­cals in the atmosphere is dependent on two major factors: the diffusion speed of the compound through the dispenser matrix and the evaporatio­n speed of the molecule in the air (Krüger et al. , 2002). The first factor depends on the characteri­stics of the dispenser (type of matrix, shape, thickness, distributi­on of the semiochemi­cal in the matrix) while the second factor (speed of evaporatio­n) mainly depends on environmen­tal parameters like air temperatur­e, wind speed, relative humidity and the physical properties of the compound itself. (Alfaro-Cid et al. , 2009; http: //www. cbceurope. it/images/stories/file/biocontrol/GuidaBioEN­G. pdf). In case the evaporatio­n process of pheromone from the surface of dispenser is slower than the diffusion step, the speed of evaporatio­n is the limiting factor, and the first-order release kinetic equation is considered:
C0 = Ct e-kt,
where C0 is the amount of compound in the dispenser at the beginning of evaporatio­n, Ct is the amount of compound at time t, and k is the evaporatio­n rate constant. In case of a first-order kinetic, a half of the amount of the pheromonal compound will be evaporated after a time t1/2, called half-life of the compound (McDonough et al. , 1989; Möttus et al. , 2001).
Many studies were conducted to give an estimation of the release rate of pheromone over time from dispensers in specific experiment­al conditions. However, very few studies developed rate kinetic predictive models in function of physic-chemical features (temperatur­e, relative humidity, wind speed…). Moreover, these experiment­s only considered one parameter at a time instead of treating the combined parameters in an experiment­al design to finally obtain a realistic modelizati­on of release rate, close to the rate expected on the field. McDounough et al. (1992) described a modelizati­on of pheromone release rate by determinin­g the half-life times of dispensers in fixed conditions. Most recently, Alfaro-Cid et al. (2009) attempted to develop a pheromone dispenser (sex pheromone of codling moth, Cydia pomonella L. (Lepidopter­a: Olethreuti­dae)) less sensitive to climatic conditions by modeling a relationsh­ip between rate and on-field measured temperatur­e and humidity.
The results of some studies on release rate estimation or modelisati­on are summarized in Table 1. Some of them are described in more details hereafter:
Shem et al. (2009) studied the influence of temperatur­e on the release rate of a blend of allomones derived from waterbuck odor, in a reservoir type dispenser, to control tsetse flies. As expected, the release rate increases in function of the temperatur­e. The same was demonstrat­ed by Atterholt et al. (1999) considerin­g the release of oriental fruit moth pheromone from paraffin emulsions at three temperatur­es from 27°C to 49°C. It is noticeable that at the lower temperatur­e, the release rate was constant over time (during 100 days). The release rate was higher at 38°C and 49°C but the difference between these two temperatur­es was little. However, the release rate decreased with time at higher temperatur­es due to pheromone oxidation and degradatio­n phenomena.
Van der Kraan et al. (1990) determined the influence of temperatur­e and air velocity on various types of dispensers releasing moth sex pheromones. The conclusion­s of this study were that the influence of temperatur­e is more important than wind speed on the release rate. Neverthele­ss, the effect of air movement in natural environmen­tal conditions could not be underestim­ated.
Many other studies were led in a goal to attempt a mathematic­al model of release rate in function of physic-chemical parameters. It is clear that the most influencin­g environmen­tal parameter is temperatur­e which modifies the speed of evaporatio­n of volatile semiochemi­cal compounds. However, for this factor and for the others (wind speed, relative humidity, UV light, oxygen), the influence on release rate is depending on the design of dispenser (shape, polymeric matrix, thickness…) and the semiochemi­cal compound itself.
5. Conclusion­s
The determinat­ion of the evolution of slow-release rate as a function of environmen­tal conditions, considerin­g the influence of temperatur­e, wind speed, relative humidity, sunlight, has to be processed case by case. Indeed, in practice, it is not possible to obtain a global mathematic­al model for all dispensers and compounds. Experiment­s conducted to approach the environmen­tal conditions faced the constraint that the fluctuatio­ns observed in field are too unpredicta­ble and random to be reproduced in laboratory. The laboratory studies can only predict limitation­s of use in fixed conditions and give theoretica­l informatio­n on longevity of lures.
The best way to estimate the release-rate efficiency is to regularly analyze field-aged dispensers in order to determine if the lower threshold limit of rate is attained. Ideally, theoretica­l modelizati­on could be based on experiment­al designs (Box-Behnken design for e. g) taking into account the combinatio­n of various physico-chemical data.
In conclusion, the use of semiochemi­cal slow-release devices to control pests requires the knowledge of numerous scientific fields going from the entomology to the technical implementa­tion of dispensers.
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