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Radiation Protection Dosimetry Vol. 101, Nos. 14, pp.

137140 (2002) Nuclear Technology Publishing

APPLICATION OF A THERMOLUMINESCENCE METHOD FOR THE DETECTION OF IRRADIATED SPICES


lum, I. Osuna, R. Mele ndrez, E. Cruz-Zaragoza, V. Chernov, S. Gaste n and M. Barboza-Flores T. Caldero a en Ciencias (F sica), Universidad de Sonora Programa de Maestr xico Apartado Postal 5-088, Hermosillo, Sonora 83190, Me n en F sica, Universidad de Sonora Centro de Investigacio xico Apartado Postal 5-088, Hermosillo, Sonora 83190, Me Instituto de Ciencias Nucleares de la UNAM xico, D. F. Ciudad Universitaria, Me mica-Agr cola-Geolog a-Geoqu mica Departamento de Qu noma de Madrid, Cantoblanco, Madrid, 28049 Spain Universidad Auto
Abstract Food irradiation is extremely effective at reducing food-borne illness as well as losses caused by infestation and contamination. Despite the well-established regulations that permit irradiation to control pathogens in spices, there are no widespread methods to detect previously irradiated food. Therefore, it has become necessary to develop new detection and dose determination methods for food subjected previously to irradiation. The present work deals with the application of the thermoluminescence (TL) phenomenon to detect irradiated spices. The process is based upon the thermoluminescence properties exhibited by the polymineral content of the irradiated specimen. After separating the organic material, it is possible to extract some polymineral substances that are suitable for thermoluminescence analysis due to interaction of the spice to ionising radiation. The method was successfully applied to examine irradiated and non-irradiated paprika of Mexican origin. The spice was irradiated with gamma rays at doses of 5, 10 and 15 kGy. The separated thermoluminescent polymineral was found to be composed mainly of quartz and feldspar. The thermoluminescence glow curve of the irradiated specimen shows a wide band peaked 228, 268 and 336C, resembling closely the combined TL of quartz and feldspars. The method allows for the determination of the retrospective dose exposure.

INTRODUCTION Irradiation through gamma rays has been widely used to protect spices and herbs from insect infestation and microbial contamination during storage. Most spices are dried in the open air and become severely contaminated by air- and soil-borne bacteria, fungi and insects. Commercial food processors fumigate spices with methyl bromide and ethylene oxide to eliminate insects and bacteria (and mould), respectively. Both chemicals are extremely toxic and their use has been banned in many countries for treatment of ground spice and herbs. Gamma irradiation is replacing the use of these chemicals; it is more effective and safer, and it does not leave chemical residues on food products. The recommended irradiation doses are of the order of 130 kGy depending upon the desired nal effect. Despite the well-established regulations related to irradiation of spices, herbs and dry condiments, there are no widespread methods to detect previously irradiated spices and herbs. Therefore, it has become necessary to develop new detection and dose determination methods for this type of food subjected previously to irradiation. The present work deals with the application of the thermoluminescence (TL) phenomenon to detect irradiated spices. The process is based on

the existence of some natural polymineral content in the spice and the thermoluminescence properties exhibited by the polymineral after exposure to irradiation. The method has been successfully applied to detect commercial irradiated paprika of Mexican origin, which shows a polymineral content made mainly of quartz and feldspars, which are excellent thermoluminescent materials. METHODS AND MATERIALS The gamma-irradiated commercial paprika was mixed with carbon tetrachloride in order to separate the organic part by agitation and centrifugation. After a few hours the polymineral dust was separated and afterward repeatedly washed with H2O2 to remove residues of organic matter. Finally the polymineral dust samples were washed with distilled water, dried and stored at room temperature under dim light conditions. The extracted polymineral dust sample was then precipitated onto stainless steel discs forming homogenous polymineral lm, suitable for thermoluminescence studies in our TLD system. The TL measurements were performed under a nitrogen atmosphere with a modied Harshaw 2000 C TLD system using a linear heating rate of 5C.s1. The TLemitted light was guided through an optical bre to the entrance of an f/2 imaging spectrograph model CP-140 Jovin-Yvon. The light spectrum at the exit of the spectrograph was measured with an intensied diode array

Contact author E-mail: mbarbozacajeme.cifus.uson.mx 137

N and M. BARBOZA-FLORES LUM, I. OSUNA, R. MELE NDREZ, E. CRUZ-ZARAGOZA, V. CHERNOV, T. CALDERO S. GASTE

detector system, Princeton Instrument model RY7000 S/RB, providing a three-dimensional registration of TL intensity as a function of temperature and emission wavelength. RESULTS AND DISCUSSION After separation of the inorganic polymineral content of irradiated and a non-irradiated paprika sample, X ray diffraction analyses were carried out. The results revealed the presence of quartz (80%), feldspars (12%) and clay minerals (8%). Since the main purpose was to look for minerals capable of showing thermoluminescence properties after irradiation of the irradiated spice, a detailed investigation of all the minerals present was not performed. It is important to note that the polymineral content of the Mexican paprika possesses quartz as the main polymineral content and similar quartz content is found in Spanish paprika(1). Several polymineral samples prepared for thermoluminescence measurements were selected from previously irradiated paprika at doses of 5 and 10 kGy. It should be said that the irradiated specimen remained in the dark for 24 months before the polymineral extraction procedure was performed. Therefore, it is possible that some acquired TL as consequence of irradiation has been lost through thermal and optically induced fading. Also, one may be concerned about the possibility that the irradiated spice could gather extra irradiation dose due to the environmental background during the 24 months of storage. The measured thermoluminescence of 5 and 10 kGy irradiated paprika is displayed in Figure 1. The TL glow curve shows quite well the dose difference effect of the examined specimen. It also inidicates that the thermal bleaching in storage does not prevent a good and adequate TL reading. Then the trapped electron charge seems to be very stable at room temperature, although there was no evidence that the TL fading occurred after irradiation of the spice. As regards the environmental or natural dose acquired by the sample,
1.0 0.9 0.8
TL Intensity (a. u.)

10 kGy 5 kGy

0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 50 100 150 200 250 300 350 400 450 Temperature ( C)

Figure 1. Thermoluminescence glow curve of polymineral dust extracted from 5 and 10 kGy irradiated paprika. 138

this is negligible. Assuming a 100 120 nGy.h1 natural background dose rate, about 2 mGy is estimated as a total dose during the 24-month storage period. Detailed investigations on the thermoluminescence of polymineral dust from irradiated herbs and spices have determined a TL of irradiated samples 104106 greater than the TL of non-irradiated herbs(23). The TL glow curve of a 5 kGy irradiated sample was analysed and the temperature maximum Tm (C), activation energy E (eV), maximum intensity Im (a.u.) and the frequency factors s (s1) were determined for each peak component by means of a home-made deconvolution program. The program is capable of simultaneously processing as many as ten rst- or secondorder kinetics TL peaks. The deconvoluted TL glow curve and the calculated parameters are shown in Figure 2 and Table 1, respectively. All the TL glow peaks were considered to be second-order kinetic processes. The computer deconvolution shows the existence of three well-dened TL peaks at 228, 268 and 336C. Several TL peaks are known to exist in laboratory-irradiated quartz, and Bailey (4) in a recent review article discusses a kinetic model considering TL peaks located at 110, 230 and 330C. Through examining the data obtained from irradiated paprika the TL peaks at 228 and 336C related to quartz may be immediately identied. Of course it is easy to explain the absence of the 110C TL due to its strong characteristic fading and it is also not present in the natural glow curve of quartz because of its short lifetime (56). Therefore, in the samples used it will vanish due to the long period of time between radiation exposure and TL measurement. However, if the sample is subjected to a 1 min exposure with UV light, a TL band around 110C appears. The effect of the UV light is to eject electrons from the deep traps and re-trap some of these electrons in shallow traps giving rise to the known phenomenon called phototransferred thermoluminescence. As far as the 268C TL peak is concerned, it can be ascribed to the potassium feldspars content of the polymineral sample, which have been reported to exist at 274 283C and measured in extracted polymineral dust of irradiated herbs and spices (7). Additional information about the identity of the specic type of mineral participation in the thermoluminescence process may be found by analysing the spectral composition of the thermally stimulated light emission. A three-dimensional TL glow curve is shown in Figure 3. The picture shows the results of recording simultaneously the heating temperature, TL light intensity and wavelength of the emitted TL emission. A broad TL emission band is found in the 300 650 nm ranges with main components around 425 and 550 nm. Quartz emissions have been reported at 380, 420 and 460 nm for which the 110C TL peaks count for some of the 380 nm-observed emission (4). On the other hand, potassium-rich feldspars show a wide band in the 300 550 nm range (89). Polymineral dust from irradiated

THERMOLUMINESCENCE OF IRRADIATED SPICES


1.1 1.0 0.9 0.8
Normalised TL intensity

0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 50 100 150 200 250 300 Temperature ( C) 350 400 450

Figure 2. Deconvolution of the thermoluminescence glow curve of polymineral dust belonging to a 5 kGy irradiated sample. The TL peaks are located at 228, 268 and 336C.

TL (a.u.)

560

640

480

50

Temp 160 erature (

C)

80

Figure 3. Three-dimensional TL glow curve with spectral response of the thermostimulated light emission. The sample corresponds to a polymineral of 10 kGy irradiated paprika. 139

30

240

40 W 0 av el en g

th

(n

60

N and M. BARBOZA-FLORES LUM, I. OSUNA, R. MELE NDREZ, E. CRUZ-ZARAGOZA, V. CHERNOV, T. CALDERO S. GASTE

herbs identify the potassium feldspar emission at 285 750 nm (7). CONCLUSIONS The thermoluminescence analyses performed in gamma-irradiated paprika have illustrated the success of the TL technique as a way to detect irradiated spices. The method requires rst a separation of the inorganic polymineral content, which in this particular case of Mexican paprika was found to be composed mainly of quartz and feldspars. The polymineral samples handled in dim laboratory light seem to bleach slightly with negligible TL losses. The TL trap levels, as well as the radiative recombination occurring during thermal stimulation, correspond to those already observed and reported in the literature. An extensive investigation is

expected in order to fully characterise and understand the trapping and recombination mechanisms involved and to be able to determine the retrospective doses. Beside further exploring TL as a technique to detect irradiated spices and herbs, it is advisable to investigate the optically stimulated luminescence (10) because of its close relationship with thermally stimulated phenomena. ACKNOWLEDGEMENTS The authors wish to acknowledge nancial support xico, Grant No. 489100-5-32069from CONACyT (Me E, FOMES, PROADU, DGICSA-SEP). V. Chernov is tedra Patrimonial Grant. Our grateful to Conacyt for a Ca deepest appreciation is extended to the Instituto xico) Nacional de Investigaciones Nucleares (ININ, Me for providing us with commercial irradiated paprika samples.

Table 1. Thermoluminescence kinetic parameters obtained by deconvolution of the TL glow curves. The deconvolution program calculates the temperature maximum Tm (C), activation energy E (eV) and the frequency factors s (s1). Peak 1 2 3 Tm(C) 228 268 336 E(eV) 1.09 1.00 0.74 s(s1) 2.54 1010 4.13 108 1.45 105

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