Theoretical Prediction of the Water Activity of Standard Saturated Salt Solutions at Various Temperatures DORA KITIC, DENISE C. PEREIRA JARDIM, GUILLERMO J. FAVETTO, SILVIA L. RESNIK, and JORGE CHIRIFE ABSTRACT A theoretical approach was used to predict the water activity (a,) at 15°C and 35°C of selected saturated salt solutions used as standards in the range of microbial growth (20.57-0.97). For this purpose a rigorous thermodynamic model to predict osmotic coefficient was used. The results agreed very well with experimental measurements at 15°C and 35°C for most salts studied, which included NaBr, NaCl, (NH&S04, KCl, BaC12, and KzS04. For KNOs the agreement at the higher temperature was somewhat less satisfactory and the reasons for this behavior are discussed. INTRODUCTION IT IS WELL KNOWN that adjustment of the water activity (a,) of foods is an important method of controlling spoilage by microorganisms (Troller and Christian, 1978). This has been recognized by regulatory agencies in several countries who have incorporated the a, principle in the definition of standards for various preserved foods. The U.S. Food & Drug Administration has adopted the water activity specification in the definition of low-acid foods (FDA, 1973) as has the FAO/WHO Codex Alimentarius Commission (FAO/WHO, 1979) and the European Community for the trade of meats products (EEC, 1976). The reliability of most a, measuring devices such as electric or fiber-dimensional hygrometers, strongly depends on proper calibration using reference sources of a,. Saturated salt solutions are used by a large number of people as a convenient way to provide solutions of known a,. They are reproducible reference standards because no measurement of concentration is needed and if the salts are properly chosen no interfering vapors are present (Stoloff, 1978; Gal, 1981). Considerable data and several reviews are available on the a, of standard salt slurries (Stokes and Robinson, 1949; Wexler and Hasegawa, 1954; Young, 1967; Rockland, 1960; International Critical Tables, 1926; Labuza et al., 1976; Greenspan, 1977). Unfortunately, most reports in the literature do not agree on the exact a, of each saturated salt solution. Considerable doubt has arisen about the accuracy of water activity of saturated salt solutions in view of the recent review by Greenspan (1977). His work reflects very well the uncertainties of literature values from various workers. Recently, Resnik et al. (1984) reported the results of a world survey of a, values at 25°C of selected saturated salt solutions used as standards in the range of a, 0.57-0.97, which is of most interest to microbial growth. Their results confirmed the discrepanciesbetween laboratories regarding the correct a, to assign to each salt. The Authors Kitic, Favetto, and Chirife are with PRO/PA (CONICETFCEyN), Depto. de Industrias, Facultad de Ciencias Exactas y Naturales, Univ. de Buenos Aires, 1428 Buenos Aires, Republica Argentina. Author Pereira Jardin is with lnstituto de Tecnologia de Alimentos (ITAL), Campinas, S.P., Brasii. Author Favetto is a member of CONICET, Argentina. Author Resnik is a member of Comisi& de lnvestigaciones Cientificas de la Provincia de Bue- nos Aires, Argentina. survey was limited to 25°C but it was expected that the discrepancies would be even larger if other temperatures were considered. It is obvious that for different regulatory agencies to adopt an a, specification for foods, and for different researchers to reproduce each others a, measurements, there must be an “universal” agreement on the values to be assigned to reference standards of saturated salt solutions. This agreement should include not only 25°C but also other temperatures of interest of microbial growth. The purpose of this study was to use a theoretical approach based on the thermodynamic properties of strong electrolyte aqueous solutions to calculate the a, of selected saturated salt solutions in the temperature range 15-35°C. The study covered the range of a, of most interest to microbial growth (=0.570.97). The predicted results were compared with experimental data obtained with an electric hygrometer previously calibrated with unsaturated salt solutions for which agreement on their a, at 15°C and 35°C existed. MATERIALS & METHODS Materials Saturated salt solutions were prepared by mixing a large excess of each salt and distilled water and stored at 15°C (?0.2”C) or 35°C (kO.2”C) in a forced convection low-temperature incubator for various days before using. Seven reagent grade salts were used: sodium bromide, sodium chloride, ammonium sulfate, potassium chloride, barium chloride, potassium nitrate and potassium sulfate. These salts have been used extensively as reference standards of water activity in the range of interest to the present study. Unsaturated solutions of sodium chloride and lithium chloride were prepared using anhydrous reagent grade salts for calibration of the hygrometer at 15°C and 35°C. Measurement of a, The a, of the six saturated salt solutions at 15°C and 35°C was measured using a Novasina Humidat-TH2 Thermoconstanter hygrometer (Novasina AC, Ch-8050 Zurich, Switzerland). This instrument has a built-in accurate temperature control device which maintains the sensor and the sample at constant temperature in the range 0-50°C. The hygrometer was operated following the procedure described in detail by Kitic et al. (1986). Each a, measurement represents the average of three determinations. As shown previously (Kitic et al., 1986), three replicates are enough to obtain a precision of f 0.005 a, when using the Novasina Thermoconstanter for measuring the a, of saturated salt solutions in the range of interest of this study. To measure the a, of saturated salt solutions at 15°C and 35°C the instrument was first calibrated at these temperatures using other standards for which agreement exists on their a, at 15°C and 35’C. Chirife and Resnik (1984) and Kitic et al. (1986) proposed the use of unsaturated solutions of NaCl and LiCl as isopiestic standards for calibration of a, measuring devices at various temperatures and showed that there was excellent agreement (theoretical and experimental values) on the exact value of the a, of these solutions; thus these values were used for the calibration of the Novasina Thermoconstanter at 15°C and 35°C. Table 1 shows the data used for the calibration; at least six points were used at each temperature. NaCL solutions are useful as standards only for values of a, of about 0.75 and above (saturation value); for this reason LiCl solutions were used as standards for lower a, values. Equilibration times for measuring a, of each saturated salt were previously determined and ranged between 30-90 min. Volume 51, No. 4, 1986JOURNAL OF FOOD SCIENCE-1037 a, OF SALT SOLNS AT VARIOUS TEMPS . . . Table l--Unsaturated salt solutions used as isopiestic standards for calibration of the Novasina Thermoconstanter hygrometer at 15°C and 35°C Salt LiCP Concentratio+ % (w/w) a, a, (15°C) (35°C) 0.505 0.536 0.568 0.597 0.598 0.612 0.732 0.744 0.745 0.748 0.756 0.770 25.97 25.00 23.98 23.00 22.98 22.51 18.01 17.49 17.48 17.36 16.98 16.39 0.521 0.550 0.581 0.609 0.609 0.623 0.739 0.751 0.751 0.754 0.762 0.775 NaCIc Concentratior@ % (w/w) (15°C) 0.795 0.808 0.821 0.833 0.850 0.857 0.864 0.872 0.889 0.906 0.920 0.929 0.948 0.962 0.986 0 Kitic et al. 0966) bg of anhydrous salt per 1OOgof solution CChirife and Resnik (1964) RESULTS & DISCUSSION Theoretical prediction of the a, of aqueous strong electrolyte solutions The thermodynamic properties of aqueous strong electrolyte solutions have been extensively studied both experimentally and theoretically. Excellent examples may be found in the standard monographs by Hamed and Owen (1958) and Robinson and Stokes (1965) or in the more recent works of Scatchard (1968), Scatchard et al. (1970), Pitzer (1973) and Bromley (1973). One of the most useful and accurate theoretical models to predict the a, of salt solutions is that of Pitzer (1973), (Pitzer and Mayorga, 1973). Pitzer (1973) developed a system of equations (ion-interaction model) for the thermodynamic properties of strong electrolytes which yield agreement within experimental error up to concentrations of several mol/kg (in numerous cases very close to saturation). It is interesting to note that the fit was particularly good for l-l and 2-l electrolytes, which are those of concern in the present study. The osmotic coefficient, 4, is defined as -55,51 In a, Vi ml (1) where vi is the number of particles into which each solute of molality mi dissociates. The osmotic coefficient is given by the equations developed by Pitzer (1973) as: BMX \ - I + m*2 03/2 V cMx (2) where, w and ux are the number of M and X ions in the formula and ZM and Zx give their respective charges in elec1038-JOURNAL OF FOOD p 0.0973 0.0785 0.0409 0.04835 0.2628 -0.0816 0.04995 in Eq. (2) for some selected pll, 0.2791 0.2664 0.8585 0.2122 1.49825 0.0494 0.77925 CMX 0.00116 0.00127 -0.00116 - 0.00084 -0.01938 0.00660 __- salt sommaxb 4 8 5.5 4.8 1.8 3.8 0.7 a Pitzer and Mayorga (1973) b Maximum molality for which agreement with experimental data was attained to 0.01 in $ (or for which data were available). tronic units; also v = u, + x; the other quantities have the form: (35°C) 0.795 0.808 0.821 0.833 0.852 0.859 0.867 0.874 0.891 0.908 0.921 0.930 0.949 0.963 0.986 4= NaBr NaCl NW,)304 KCI BatI& KNOB K.S.0, of the parameters aw a, 23.50 22.50 21.50 20.50 19.02 18.38 17.70 17.01 15.25 13.42 11.98 10.71 8.25 6.18 2.44 Table 2-Values lutions at 25”Cs SCIENCE-Volume 51, No. 4, 1986 BMX =. p& + p& exp (- ~1I)“2 (0) (1) pMx, pMx and CMx are parameters which are fixed for each electrolyte, A, is the Debye-Hiickel coefficient for the osmotic function, I is the ionic strength % Z miZi*; b is equal to 1.2 for all solutes and (Y = 2.0 was found to be satisfactory for all solutes considered by Pitzer and Mayorga (1973). The ion-interaction model of Pitzer (1973) has been very successful in describing osmotic results, both at 25°C (Pitzer and Mayorga, 1973) and at elevated temperatures (Silvester and Pitzer, 1977; Holmes and Mesmer, 1983) for different electrolyte solutions. Table 2 shows .the values of the parameters which describe the a, at 25°C of the salt solutions considered in this work, namely NaBr, NaCl, (NH4)*S04, KCl, BaC12, KN03 and K2S04, as reported by Pitzer and Mayorga (1973). These values were mostly obtained from careful isopiestic deterrninations of vapor pressures in such a way that they would allow accuracy to the third (or even fourth) decimal figure in predicted a,. In order to predict the a, of the corresponding saturated salt solution at 25”C, one only needs to have a precise knowledge of the molality at saturation (m,), and then the a, at saturation may be calculated through the relationship (aJsat = exp( - 4 0.018 m,v) (3) Tran and Lenzi (1974) demonstrated that Pitzer’s equation may be safely extrapolated even to predict a, of various supersaturated salt solutions. Chirife et al. (1983) successfully applied Pitzer’s model to predict the a, of saturated NaCl, (NH&S04, KCl, BaC12, KN03, and K2S04 at 25°C. a, of saturated salt solutions at temperatures other than 25°C Chirife et al. (1983) have shown that the a, of certain saturated salt solutions at 25°C may be predicted accurately. In order to predict the a, at different temperatures two aspects have to be taken into account: (1) the effect of temperature on the salt solubility, usually, an increase of temperature will increase the amount of soluble salt thereby decreasing a, if other temperature effects are absent; (2) the thermodynamic effect of temperature on a, at constant concentration of the solution; this im lies that the temperature dependence of parameters p(O), p( P) and C MX in the predictive equation (Eq. 2) must be known. Thus, the effect of a temperature change on the a, of a saturated salt solution will be the result of these two factors. Silvester and Pitzer (1977) extended the ion-interaction model (Eq. 2) for the calculation of activity and osmotic coefficients of NaCl in a wide range and applied the equations to an extensive array of the thermodynamic data of aqueous NaCl from 0” to 300°C. The general forms to describe the temperature Table 3-Prediction of a,,, of NaCI solutions Coefficients for Eq. (4), (5) and (6) q1 q2 q3 q4 % 0, = = = = = = at different 0.0765 - 777.03 - 4.4706 0.008946 -3.3158 x 10-e 0.2664 temperatures* 6.1608 x IO-5 1.0715 x 10-e 0.00127 33.317 0.09421 -4.655 x 10-s = = = = = = q9 %o 911 cl12 q13 0.” - * Silvester and Pitzer (1977) Table 4-Prediction of a, of KCI solutions at different Coefficients for Eq. (7) p(l) pw Pl P2 P3 P4 P5 on 0.04808 -758.48 -4.7062 0.010072 -3.7599 x 10-s ___ temperaturese - CMX -7.88 x 1O-4 91.270 0.58643 -0.0012980 4.9567 x lO-7 _-- 0.0476 303.9 1.066 --_ ___ 0.0470 B Holmes and Mesmar (1983) dependenceof B(O),B(l) and C&x for NaCl solutions are given as: p(O) = qt + 92 (: - f) = q6 + q9(T - Salt NaBr NaCl W ’W,SOa KCI BaCI, KNO, KzSQ, = $1 + %2($ - T,) + qlo(T’ - ‘L2, (4) Table S-Solubility oeratures NaBr q13 ln f + qdT - Tr) (6) NaCI r standard mbmax 9 6 ___ 4.5 1.8 2.4 0.1 46.58 26.35 42.53 24.64 25.68 20.50 9.21 it f k k f f + 0.10 0.03 0.17 0.20 0.10 0.15 0.04 salt solutions at various tem- Solubilitya salt par IOOg of solution) 25°C 35°C (g of anhydrous 15°C Temp I%) 15 25 35 15 25 35 where Tn is 298.15”C and the values of the parameters qr . . . . q14 are given in Table 3. These values, along with Bq. (3), (4), (5), (2) and (1) allow a rigorous and accurate prediction of the a, of NaCl solutions for the whole concentration range (up to saturation) and any desired temperature. The values of the Debye-Htickel parameters(Eq. 2) at different temperaturesare given by Ananthaswamy and Atkinson (1984) and those of b and 01are taken as temperature independent. Recently, Holmes and Mesmer (1983) applied the ion-interaction model of Pitzer (1973) to aqueous solutions of the alkali metal chlorides to 250°C. Their resulting set of equations provide a thermodynamic description within the accuracy of the reported experimental data. The parameters B(O),B(l) and CMx are described by arbitrary functions of temperature, f(T) of the form + p3 ln f in Eq. (7) for some acMx x 105 7 -9.30 -10.54 --_ - 5.095 -2.3 39.7 -__ 48.61 26.50 43.42 26.44 27.04 27.54 10.73 f f e k f + + 0.10 0.10 0.10 0.10 0.15 0.24 0.06 Table 7-Comparison of predicted and measured saturated salt solutions at various temoeratures r f(T) = pl + PZ ($ - f) apfl) x 104 7 10.7s 7.005 ___ 10.71 4.3, 64.5 8.g3 of selected Salt NaBr NaCl W-L&SO., KCI BaCI, KNO, KzSO4 (5) f) + ap@) x 104 7 7.6g2 7.159 ___ 5.794 0.854 2.06 1.92 derivatives a Silvester and Pitzer (1978). b Maximum molalities to which the enthalpy equations were fined. Salt CMX of the temperature 50.48 26.61 44.22 27.93 27.90 34.84 12.17 f f + k f -c + 0.48 0.05 0.20 0.10 0.15 0.24 0.05 s Literature mean value (calculated from several different sources) and estimated standard deviation. + q3 ln(+) ; q4(T - '6 + qs(T* - T,*, p(l) Table 5-Parametersa selected salt solutions + ~4 (T - ‘G) (7) + ps (T2 - Gr2) + p6 ln;T - 260) where p,,. . . ., p6 are parameters. with the exception of the term envolving p6 this equation is identical with the form used by Silvester and Pitzer (1977). The values of the parameters pt, . . . ., p6 for aqueous solutions of potassium chloride are listed in Table 4; they allow a very accurate calculation of the a, of KC1 solutions for the whole concentration range (up to saturation) at any temperature . Silvester and Pitzer (1978) gave the change with temperature of the activity and osmotic coefficients. They reported results for 84 electrolytes of 1- 1, 2- 1, 3- 1 and 2-2 valence types. The parameters allow the convenient calculation of properties at other temperatures not too different from 25°C. The values of B(O),B(l) and CMX at temperaturesnot too different from 25°C Predicteda Ib1 0.562 values of a, of selected Predicted* lc) ___ f 0.002 --- 0.752 k 0.001 0.751 +- 0001 0.750 .._. f 0.001 __--. Measured Id1 0.601 f 0.002 ___ 0.525 T 0.008 0.603 ___ 0.537 0.753 0.753 ___ 0.751 k 0.001 ___ 0.749 I 0.001 PJH&S04 15 25 35 0.803 --_ ___ ___ __- 0.804 ___ 0 797 KCI 15 25 35 0.858 0.842 0.827 + 0.002 + 0.001 + 0.001 0.859 0.842 0.827 f 0.002 -+ 0.001 f 0.001 0.860 --0.828 BaCls 15 25 35 0.903 ___ f 0.001 --_ 0.910 f 0.001 ___ 0.894 k 0.002 0.908 ___ 0.893 KNOs 15 25 35 0.926 --_ IT 0.001 ___ 0.948 f 0.001 -__ 0.889 f 0.002 0.943 ___ 0.898 KzSQI 15 25 35 0.975 ___ -c 0.000 ___ 0.979 0.977 ___ 0.971 k 0.001 ___ -+ 0.000 -__ 0.972 f 0.000 OThe fluctuations in a, values arise from the standard deviation of the solubility data. b Predicted using Pitzer’s model (Eq. 2) with parameters for 25°C or with the rigorous temperature dependence for 15’C and 35°C [Eq. (4). (5). 0%. and (7)l. c Predicted using Pitzefs model with approximation for the temperature dependence IEq. WI. d Measured with the Novasina Thermoconstanter (average of triplicate determinations). (i.e., 15°C or 35°C as is the case in the present paper) can be approximated by fcr, = 4x-c) + -&CAT (8) where f(r) is the value of the function at temperature T. The values of the corresponding derivatives for the salts of interest to the present study are given in Table 5. The most important conclusion is that for almost all salts considered here the temperature derivatives are relatively small. Thus, for NaBr, NaCl, KCl, BaC12, and K2S04 where B(O)and B(l) at 25°C had a magnitude of about 0.05 or a few tenths (Table 2), the derivVolume 51, No. 4, 1986--JOURNAL OF FOOD SCIENCE-1039 a, OF SALT SOLNS AT VARIOUS TEMPS . . . Table 8-Prediction of the a,,, of selected saturated salt solutions at 15°C and 35°C neglecting the effect of temperature on the thermodynamic parameters of the ion-interaction model8 b a, a, Salt (35°C) NaBr NaCl 0.601 0.752 0.808 0.856 0.910 0.944 0.979 N-L&S04 KCI BaCI, KNOB K&L, ‘- 0.002 k 0.001 f 0.002 AZ 0.002 f 0.001 k 0.001 e 0.000 0.522 0.750 0.798 0.830 0.895 0.907 0.972 f f e e k f 55 0.008 0.001 0.002 0.001 0.002 0.002 0.000 a Pitzer (1973) b Fluctuations in the predicted aw values arise from the standard deviation of the solubility data. Table *The 37-c a, of selected Temp (“a NaCl 15 17 19 21 23 25 27 29 31 33 35 37 0.753 0.753 0.752 0.752 0.751 0.751 0.750 0.750 0.750 0.749 0.749 0.748 saturated NL,LSOz, 0.808 0.806 0.805 0.804 0.803 0.803 0.802 0.801 0.800 0.799 0.798 0.797 salt solutions between 15°C and KCI BaCI, WOa 0.859 0.856 0.852 0.849 0.846 0.842 0.840 0.836 0.833 0.830 0.827 0.823 0.910 0.909 0.907 0.906 0.905 0.903 0.902 0.900 0.899 0.898 0.895 0.894 0.979 0.978 0.977 0.977 0.976 0.975 0.975 0.974 0.973 0.973 0.972 0.971 atives were the order of 1O-4 to 10-3. Hence, a temperature change from 25°C of lO-20°C will cause little change in these parameters and thus in a,. A different picture was observed for KN03 where the temperature derivatives were relatively more important. An important prerequisite for the prediction of the a, of saturated salts at different temperatures is precise knowledge of the salt concentration at saturation. For this purpose a compilation of solubility data for NaBr, NaCl, (NH4)2S04, KCl, BaC12, KN03, and K2S04 at various temperatures, was made. Table 6 gives the results of the literature review on the solubility of the salts examined at 15”C, 25°C and 35°C (sources of data are not reported here due to the very large number of references considered). The solubility of salts studied showed a significant increase with increasing temperature, with KNO, showing the largest increase. The exception was NaCl where solubility increased only slightly with increasing temperature (1% change between 15°C and 35°C). Considering the small temperature dependence of the parameters for the ion-interaction model (Table 5), it could be anticipated that the a, of saturated NaCl solutions will be only slightly affected by temperature (in the range studied). It is now possible to combine the data of solubilities at various temperatures with the concentration dependence of the osmotic coefficient for each salt (calculated from the ion-interaction model) at different temperatures and to predict the a, of saturated salt solutions at 15°C and 35°C. For NaCl and KC1 the ion-interaction model of Pitzer with the rigorous temperature dependenceof parametersp(O), /3(l) and Cm [as given by Eq. (4), (5), (6) and (7)] were used. For NaBr, BaCl,, KN03 and K2S04 the temperature derivatives (Eq. 8) were used. No information is available on the temperature dependence of ion-interaction parameters for (NH4)$S04. The results of the prediction are shown in Table 7 which compares predieted values at 15°C and 35°C with those experimentally determined using the Novasina Thermoconst$nter previously calibrated as described. For all salts studied, the a, (either predicted or measured) decreased with increasing temperature; this effect has been 104O-JOURNAL Of FOOD SCIENCE-Volume 51, No. 4, 1986 experimentally found in the literature for several salts slurries; however, as reported by Scott and Barnard (1983), the “physicochemical reasons for the decrease in a,,, were not fully understood.” The a, of saturated NaCl remained almost constant between 15°C and 35°C (ha, = 0.002) and this was expected on the basis of the solubility changes and very small effect of the temperature on the characteristic parameters in the model of Pitzer (1973). It was noteworthy that the predicted a, values at 15°C and 35°C were in very good agreement with the values measured with the Novasina Thermoconstanter previously calibrated with unsaturated NaCl and LiCl solutions; differences between theoretical and experimental values were only about 0.002 a,. The exception was KN03 for which a larger difference was observed, these differences being 0.003 at 15°C and 0.009 at 35°C. This may be attributed to the relatively large values of the temperatures derivatives (Table 5) which make more uncertain the accurate theoretical prediction of the effect of temperature. KN03 also exhibited a large increase of solubility with increasing temperature; extrapolation of Pitzer’s (1973) model to the saturation concentration at 35°C may be somewhat less reliable. Labuza et al. (1985) used the vapor pressure manometer to measure the a, of saturated NaCl and KC1 solutions and reported values of 0.765, 0.748 and 0.727 for NaCl and 0.846, 0.841 and 0.786 for KC1 at 25”C, 30°C and 45”C, respectively. The values for NaCl were not in good agreement with the theoretical predictions or with present experimental determinations; the values for KC1 at 25°C and 30°C are in better agreement but the value for 45°C seems to be somewhat low. A simplified theoretical approach was also tested to predict the effect of a temperature change (from 25°C to 15°C or 35°C) on the a, of salt slurries studied in this work. For this purpose it was assumedthat the effect of temperature may be accounted for by only considering the effect on solubility and neglecting the intrinsic variation of a, with temperature (i.e., the temperature derivatives of ion-interaction parameters are negligible). Thus, Eq. (2) with parameters p(O), p(l), CMx corresponding to 25°C was used to predict the a, values at saturation concentration at 15°C or 35°C. The Debye-Hiickel parameters were those at the corresponding temperature 15°C or 35°C (Ananthaswamy and Atkinson, 1984). The results are shown in Table 8. Predicted values for NaBr, NaCl, KCl, BaCl* and K2S04 agree quite well with the values obtained with the more rigorous approach (Table 7). This method allowed the prediction of a, at 15°C and 35°C of (NH&S04; there is a good agreement with measured values (Table 7). As found before, KN03 at a higher temperature (35°C) exhibited the greatest deviation. These results indicated that for the salts studied (with the exception of KN03) the increase in solubility was the dominant factor which regulated the change in a, when temperature shifted from 25°C to 15°C or 35°C. Having demonstrated the reliability of the theoretical predictions, the different equations and solubility data were used to calculate the a, of saturated NaCl, (NH&S04, KCl, BaCl* and K2S04 every 2°C between 15°C and 37°C (a slight extrapolation above 35°C was done because of the microbiological interest in the temperature 37°C). The results are shown in Table 9; it is believed that these data are accurate enough for almost all needs in food microbiology research or quality control. 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MS received g/13/85; revised 3/15/86; accepted 3/15/86. The authors acknowledgethe financial supportfrom Secretariade Cienciay T&znica de la RcptiblicaArgentina (ProgramaNational de Tecnologtade Alimentos).One of us (D.C.P.J.)acknowledgesthe financial support from CONICET (Argentine)and CNPa (Brazil). . .From page 1016 sealed lyethylene-lined boxes of apples, oranges and lettuce with hydrated p” ime mserta. Proc. Am. Sot. Hort. Sci. 82: 83. Hardenburg, R.E. 1971. Effect of in-package environment on keeping quality of fruits and vegetables. HortScience 6: 198. Honda, Y. and Ishiguro, 0. 1968. Studies on the storage of fruits and vegetables. II. On the keeping of some vegetables packaged with plastic bags. J. Jap. Sot. Hart. Sci. 37: 77. Kawada, K. 1982. Use of polymeric films to extend postharvest life and improve marketability of fruits and vegetables-Unipack: individually rsimmons and grapefruit. 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