[Advances in Food Research] Advances in Food Research Volume 8 Volume 8 || Composition of Wines. II. Inorganic Constituents

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<ul><li><p>COMPOSITION OF WINES . I I . INORGANIC CONSTITUENTS BY MAYNARD A . AMERINE </p><p>Department of Viticulture and Enology. College of Agriculture. University of Califomin. Dauis. California </p><p>I . Introduction . . . . . . I1 . General Methods of Analysis . . </p><p>1 . Effect of Minerals . . . . 2 . Balance of Ions . . . . . 3 . Ash . . . . . . . </p><p>a . Methods . . . . . . b . Amounts . . . . . . </p><p>4 . Alkalinity of the Ash . . . a . Methods . . . . . . b . Amounts . . . . . . </p><p>I11 . Anions . . . . . . . 1 . Boron . . . . . . . </p><p>a . Methods . . . . . . b . Significance . . . . . c . Amounts . . . . . . </p><p>2 . Bromide . . . . . . a . Methods . . . . . . b . Amounts . . . . . . </p><p>3 . Carbon Dioxide . . . . . a . Methods . . . . . . b . Amounts . . . . . . c . Factors Affecting Solubility . . d . Forms of Carbon Dioxide Present </p><p>4 . Chloride . . . . . . a . Methods . . . . . . b . Amounts . . . . . . </p><p>5 . Fluoride . . . . . . a . Methods . . . . . . b . Amounts of Fluoride Prescnt . </p><p>6 . Iodide . . . . . . . 7 . Oxygen . . . . . . </p><p>a . Methods . . . . . . b . Amounts . . . . . . </p><p>8 . Phosphate . . . . . . a . Methods . . . . . . b . Amounts of Phosphate Present . </p><p>9 . Silicate . . . . . . 10 . Sulfate . . . . . . </p><p>133 </p><p>. Page . . . . . . . 135 . . . . . . . 136 . . . . . . . 137 . . . . . . . 138 . . . . . . . 138 . . . . . . . 138 . . . . . . . 139 . . . . . . . 139 . . . . . . . 139 . . . . . . . 140 . . . . . . . 141 . . . . . . . 141 . . . . . . . 141 . . . . . . . 142 . . . . . . . 142 . . . . . . . 142 . . . . . . . 142 . . . . . . . 143 . . . . . . . 143 . . . . . . . 143 . . . . . . . 144 . . . . . . . 148 . . . . . . . 149 . . . . . . . 150 . . . . . . . 150 . . . . . . . 150 . . . . . . . 151 . . . . . . . 151 . . . . . . . 152 . . . . . . . 152 . . . . . . . 153 . . . . . . . 153 . . . . . . . 153 . . . . . . . 153 . . . . . . . 154 . . . . . . . 1.54 . . . . . . . 156 . . . . . . . 156 </p></li><li><p>134 MAYNARD A . AMERINE </p><p>Page a . Methods . . . . . . . . . . . . . 156 b . Sources of Sulfate . . . . . . . . . . . 157 c . Amounts of Sulfate Present 159 </p><p>11 Sulfide and Mercaptans 159 a . Methods . . . . . . . . . . . . . 161 b . Source of Sulfide . . . . . . . . . . . 161 </p><p>12 . Sulfurous Acid . . . . . . . . . . . . 162 . Methods . . . . . . . . . . . . . 162 </p><p>164 171 </p><p>IV . Cations . . . . . . . . . . . . . . 172 1 . Aluminum . . . . . . . . . . . . . 172 2 . Arsenic . . . . . . . . . . . . . 173 3 . Cadmium . . . . . . . . . . . . . 174 4 . Calcium . . . . . . . . . . . . . 174 5 . Copper . . . . . . . . . . . . . 176 </p><p>a . Methods . . . . . . . . . . . . . 176 b . Sources and Effects . . . . . . . . . . 177 c . Effects of Copper . . . . . . . . . . . . 179 cl . Amounts of Copper . . . . . . . . . . 180 </p><p>6 . Iron . . . . . . . . . . . . . . 181 a . Methods . . . . . . . . . . . . . 181 b . Source . . . . . . . . . . . . . 183 c . Effects . . . . . . . . . . . . . 186 d . Amounts . . . . . . . . . . . . . 188 </p><p>7 . Lead . . . . . . . . . . . . . . 189 a . Methods . . . . . . . . . . . . . 189 b . Amounts . . . . . . . . . . . . . 189 </p><p>8 . Magnesium . . . . . . . . . . . . . 191 9 . Manganese . . . . . . . . . . . . . 191 </p><p>10 . Mercury . . . . . . . . . . . . . 193 11 . Molybdenum . . . . . . . . . . . . 193 12 . Potassium . . . . . . . . . . . . . 193 </p><p>u . Methods . . . . . . . . . . . . . 193 b . Amounts . . . . . . . . . . . . . 194 </p><p>13 . Radium . . . . . . . . . . . . . 195 14 . Rubidium . . . . . . . . . . . . . 195 15 . Silver . . . . . . . . . . . . . . 196 16 . Sodium . . . . . . . . . . . . . 196 </p><p>a . Methods . . . . . . . . . . . . . 196 b . Amounts of Sodium . . . . . . . . . . 196 </p><p>17 . Tin, Titanium, and Vanadium . . . . . . . . . 198 18 . Zinc . . . . . . . . . . . . . . 198 </p><p>a . Methods . . . . . . . . . . . . . 198 b . Amounts . . . . . . . . . . . . . 198 </p><p>V . Research Needs . . . . . . . . . . . . 199 Acknowledgments . . . . . . . . . . . . 200 </p><p>. . . . . . . . . . . . . . . . . . . . </p><p>. . . . . . . b . Sulfurous Acid in Musts and Wines 13 . Sulfur: Elemental and Organic . . . . . . . . </p><p>References . . . . . . . . . . . . . 200 </p></li><li><p>WINES: INORGANIC CONSTITUENTS 135 </p><p>I . INTRODUCTION </p><p>The inorganic constituents of wines have received less attention than the organic components. This may be because they appear to be of less biochemical and physiological importance. Nevertheless, the minerals are of considerable significance in enology. Some are needed in the process of alcoholic fermentation. Others, particularly sulfites, iron, and copper, are a part of the: oxidation system of wines, Small amounts of several metals in wines affect their clarity, and occasionally enough of a mineral component may be present to influence the flavor. Many, of course, are of significance in human nutrition. There are also legal limits for several. Legal limits for metals (as milligrams per liter) are reported in Table I. (Anonymous, 1955). </p><p>TABLE I Legal Limits for Metals (mg./l.) in Wines a </p><p>~~~ ~ ~ ~ </p><p>Country Arsenic Copper Lead </p><p>France 0.4 Germany 2.0 Great Britain 1.4 Switzerland b </p><p>5 </p><p>30 10 </p><p>- 1.6 0.35 1.0 3.5 </p><p>~~~ </p><p>a Anonymous, 1955; Westhuyzen, 1955. b200 ml. should not show detectable arsenic. </p><p>In this review an attempt has been made to give a fairly complete summary of the methods employed at present for the analyses of the various inorganic constituents of wines. The use of the flame photometer greatly simplifies the determination of potassium, sodium, and calcium. The polarograph appears to be useful in a number of cases, particularly for oxygen. The colorimetric methods for copper and iron are now sufficiently accurate for. routine winery analyses. The procedures for total and free sulfur dioxide could be improved, both as to specificity and accuracy. Better methods for other constituents, especially for small amounts, need to be developed, but there does not appear to be any real lack of available procedures. </p><p>Data on the source and fate of inorganic constituents have not been conducted systematically enough, though Gartel's ( 1955) recent work on the effect of cellar operations is in the right direction. In order to be able to control the level of any constituent in the final product, it is highly desirable to know what may be the range in composition of the fruit of different varieties from various localities during ripening. We also need more information on the influence of equipment and fermenta- </p></li><li><p>136 MAYNARD A. AMERINE </p><p>tion conditions on the fate of the inorganic constituents. As more and more of the inorganic components of wine are found to be important to stability, and possibly quality, the greater will be our need of this type of data. </p><p>Finally, the biochemical aspects of the inorganic constituents have been too little studied. The obvious relationship of iron to the oxidation- reduction system has been investigated by several, but not completely clarified. Some of this delay is due to our ignorance of the condition of these constituents in wines. Using iron again as an example, we are almost completely in the dark as to the ionic species actually present in wine. The case with respect to carbon dioxide in sparkling wines is similar. It may very well be that we cannot fully explain the effect of iron on wine stability until we know the electronic structural formulas and amounts of each of the forms of iron present in wines. </p><p>There is, however, too little information on the interrelationships of the various constituents. Iron content has been studied apart from the effect of copper, phosphate, or other components. The same is true of tartrate stability; except for a few investigators, the influence of potas- sium, sodium, and other constituents has been neglected. In enology, as in food technology, we need accurate, rapid methods, quantitative data, and better biochemical interpretation of the data. </p><p>The present review, like its predecessor ( Amerine, 1954), is limited to pubIications since 1930. References to some 1957 papers are included. For general publications see Advances in Food Research 5, pp. 354 to 359. Admittedly, some of the compounds included in this review are not strictly inorganic, i.e., mercaptans, organic iron, and carbonate esters. However, they have been included here where they were not covered in the previous review. </p><p>II. GENERAL METHODS OF ANALYSIS Several texts on general wine analyses have been published, Those </p><p>of Amerine ( 1955), Jaulmes ( 1951 ), and RibBreau-Gayon and Peynaud ( 1947b) include procedures for the inorganic constituents. Details for wet ashing have been given by Gartel (1956), who used a 10:1:0.5 mixture of hydrochloric, perchloric, and sulfuric acids, using octyl alco- hol to prevent foaming, and by Deibner and Bouzigues (1953b) who preferred hydrogen peroxide as the oxidizing agent. </p><p>Among the newer procedures, the flame photometer is particularly important. Stone et al. (1951) found it possible to use beer directly for caIcium, potassium, and sodium. However, a beer background solution was needed for preparing the calibration curves. Amerine and Kishaba (1952) and Amerine et al. (1953) ashed the wine or diluted it several </p></li><li><p>WINES: INORGANIC CONSTITUENTS 137 </p><p>times. Pro and Mathers (1954) made a systematic study of the inter- ference of organic and inorganic constituents in the determination of calcium, magnesium, potassium, and sodium. They reported alcohol and sucrose interference not to be of critical importance in normal wines. Cation effects on each other were likewise not significant. Phosphates and sulfates did interfere, but their interference was reduced by adding 5% dextrose. Compared with gravimetric procedures, good checks were obtained. They also got good recovery of added calcium, magnesium, potassium, and sodium. For a further discussion of the factors influ- encing the applicability of flame photometry see Bauserman and Cerney ( 1953). Bauserman and Olson ( 1955) used ethylenediaminotetraacetic acid (EDTA) to separate calcium so as to avoid ashing. </p><p>The polarograph has been employed for a variety of purposes by Almeida (1942), Rentschler and Tanner (1953), and Tanner and Rent- schler ( 1955). Methods for determining arsenic, phosphate, copper, zinc, iron, and manganese in musts and wines were outlined by Heide and Hennig (1933a). Dean (1951) used a spectrograph to determine 16 elements in the ash. In addition to those discussed herein he found barium, cobalt, lithium, and nickel, but in very small quantities. Bonastre and Pointeau (1957) used the polarograph for copper, lead, manganese and zinc determination. </p><p>1. EFFECT OF MINERALS Frolov-Bagreev ( 1949) and Frolov-Bagreev and Andreevskaia ( 1950, </p><p>1955) believed their data indicated that high manganese, molybdenum, vanadium, titanium, and boron contents had a favorable effect on the organoleptic quality of wines. They suggested this might be due to their poisoning of enzyme systems. Deibner ( 1952) favorably reviewed this research, but inspection of the data shows such large variations in the amounts of the elements that it is difficult to evaluate the claim. Wines with high manganese and molybdenum did receive high organo- leptic scores, but wines low in these elements had scores nearly as high. Lomkatsi (1956) added small amounts of copper, zirconium, nickel, cobalt, and thallium to fermenting musts. There was general stimulation and improvement in organoleptic quality, but again the effects are small and variable. Thallium (10 mg. per liter), copper (0.02 mg. ), and cobalt ( 10 mg.) seemed to be the most effective. </p><p>The effect of magnesium, sulfur, iron, copper, manganese, titanium, tungsten, and boron on vine growth was studied by Engles (1949), who considered these minerals favorable to growth. The sources of copper, iron, zinc, arsenic, and lead in musts and wines have been reviewed by Kieffer (1948). </p></li><li><p>138 MAYNARD A. AMERINE </p><p>Excessive or unusual mineral contents in the wine can arise from a variety of sources. The composition of the soil may lead to high mineral contents in the musts and in the resulting wines, In some cases, soil fungicides or insecticides on the grapes get into the crushed grapes and result in high metal content. Then there are the additions from equip- ment: metal crushers, filters, pumps, etc. Recently antiseptics and clari- fication agents have posed a problem, though some of these materials are of ancient origin (calcium sulfate, sodium chloride, various sulfites, fluorides, etc. ) , Even the metal content of quite dissimilar chemicals may pose a problem. The lead content of impure citric acid, for exam- ple, has been found to be high enough to create difficulties. The action of various metals on alcoholic beverages was studied by Walter (1951). The effect of metals on wines was also studied by Mrak et al. (1937), who reported a tolerance of 2 mg. per liter for aluminum, chromium, copper, and iron; 5 mg. for tin and zinc; and 50 mg. for nickel under the conditions of their experiment. The oxidation-reduction potential of the wine and other factors will influence this tolerance. Dougnac (1935) gives some data on minerals in wines in relation to their health values, mainly from pre-1930 papers. </p><p>2. BALANCE OF IONS </p><p>The principles of physical chemistry were applied by Genevois and Ribdreau-Gayon (1933) to the problems of the ions in wines and par- ticularly to the dissociation of acids and the pH. Since the ion activities are not known, their calculations can be considered only as a first approximation. Genevois ( 1934) reported that the mineral composition of wines, particularly of potassium, calcium, and magnesium, is similar to that of muscle and liver. About one liter of wine per day would furnish '/3 to $4 of the body's needs of these elements. A complete balance of the cations and inorganic and organic anions found in six Portuguese wines by Correia and JBcome (1942b) showed that the usual analytical procedures are accurate enough to account for the total mineral content. Berner (1952) has made a balance of cations and anions for eight Swiss wines. A summary of much of the data on this subject may be found in Ribhreau-Gayon and Peynaud (1947a). </p><p>3. ASH </p><p>a. Methods </p><p>Eckert (1950) reported work by Bohringer showing that the ashing should be done at a temperature not exceeding 600OC. (1112OF.). While no new principles for the determination of the ash or of the alkalinity </p></li><li><p>WINES : INORGANIC CONSTITUENTS 139 </p><p>of the ash are involved in the procedure of Sumuleanu and Ghimicescu (1935b), their titrating in the absence of carbon dioxide is worth noting. </p><p>b. Ammounts </p><p>De Soto (1951) analyzed the minerals in the ash spectrographically; his results are reported in Table I1 for seven samples (g . per 100 g. ash). These data are somewhat variable, e.g., the 10,000-fold range in alu- minum and the 5,000-fold range in iron, suggesting that further work is desirable. Furtherm...</p></li></ul>