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Swaine, D. J., and R. L. Mitc:heU. 1960. Trace element distribution in soil prordes. J. Soil Sci. 11(2):34 7-368. Toepfer, E. W., W. Mertz, E. E. Roginski, and M. M. Polansky. 1973. Chromium in food in relation to biological activity. J . Agric. Food Chem. 21:69-73. Tureldan, K. K., and M. Cur. 1960. The geochemistries of chromium, cobalt, and nickel: Pt. 1. Geochemical cycles. Section 1, Proceed- inp of the Twenty-First international Geological Congress, Copenflaaen. Tureldan, K. K., and K. H. Wedepohl. 1961. Distribution of the ele- Chromium 35 menta in some major units of the earth's crust. Geol. Soc. Am. BuU. 72:175-191. Voelcker, J. A. 1924. Pot-culture experiments-1921. J. R. Agric. Soc. (England) 82:286-297. Walker, R. B. 1954. Facton affecting plant growth in serpentine soils: Part 2, The ecology of serpentine soils. Ecology 35:259- 267. Whittaker, R. H. 1954. The ve,etational response to serpentine soils: Part 4, The ecology of serpentine soils. Ecology 35:275- 288.
v Lithium WALTER MERTZ, Chairman Ernest E. Angino, Helen L. Cannon, K. Michael Hambidge, A. Wouter Voors Although the effects of lithium on human health are little understood, lithium is applied in selected cases of mental disorder with apparent beneficial effect. In Texas, a strong negative correlation has been shown to exist between lith- ium intake, as indexed by water levels, and admission rates to state mental institutions (Dawson et aL, 1970). In other places, the prevalence of mental disorders correlates in some instances with location of residence, although no data on lithium intakes in these areas is currently available. Lith· ium intake has also been inversely related to a form of heart disease. The highly publicized inverse correlation between hardness of drinking water and cardiovascular mortality (Crawford et al., 1971) can be explained statistically (at least for white populations in the larger urban areas of the United States) by water lithium levels concomitant with water hardness (V oors, 1971 ). However, the biological evi- dence for protection against cardiovascular mortality from ingestion of lithium is lacking. At present, the equilibrium state between cadmium and zinc, also paralleled by the hardness of drinking water, may offer a more promising biological explanation (Perry, 1971). No requirement for lithium has been established for higher species. CHARACTERISTIC GEOCHEMISTRY AND SOURCES lithium, a light metal, has atomic number 3, an atomic weight of 6.939, and is widely distributed throughout the 36 earth's crust. It is concentrated in the silicates and alumino- silicates of acidic igneous rocks where it replaces magnesium (Mg), ferrous iron (Fe:z+), or aluminum (AI); and in pegma- tite dikes where it forms the main ores of the element, in· dependent lithium minerals [such as spodumene (LiA1Si20 6)], and the lithium micas (such as lepidolite). There is positive correlation between the lithium and fluorine contents of igneous rocks. Published averages for lithium in igneous rocks range from 22 to 65 ppm (Parker, 1967). Averages for sediments have been reported as 17 ppm in sandstones, 46 ppm in shales, and 26 ppm in limestones (Rankama and Sahama, 1950; Strock, 1936); contents of more than 100 ppm are reported for iron ores. Lithium also occurs in evaporites and lake clays of volcanic origin (Swaine and Mitchell, 1960). A Russian study (Ronov et al., 1970) of the geochem- istry of lithium in the sedimentary cycle suggests that lith· ium in the weathering zone is not dependent on the mineralogy of the original rock, its initial lithium content, or its geologic age, but is determined by the sequence of stages, or the physicochemical conditions, of weathering. It is usually concentrated in the end product, kaolinite. lithium entering clay minerals differs from most cations in being firmly bound during the alteration of the clay min· erals, and being released only during the breakdown of the clay structure during laterization. Gutkin ( 1971) has made a study of lithium in bauxites (Al2 0 3 ⢠3H2 0) and reports from 6 to 293 ppm lithium in a series of samples.
Soils Swaine (I9SS) reports the content of lithium in soils to be from 8 to 40 ppm. Steinkoenig (191 S) reported I 0-100 ppm in soil and 20-80 ppm in subsoil from 19 samples in 6 different areas of the United States. Recent studies by the U.S. Geological Survey (1972a) in Missouri show geo- metric means ranging from IS to 32 ppm lithium for soil in the state. Lithium values of soil proflles taken over sev· eral different types of rock in Scotland (Swaine and Mitchell, 1960) do not show a consistent concentration in any one soil horizon (Table 12). In the arid basin and range province of the western United States, lithium is concentrated in hydraulically closed basins. In these basins, there is an upward move- ment of soluble salts to the ground surface, where con- centration is effected by evaporation and plant transpira- tion. In an evaporative basin, lithium may remain in solution until a late stage in the process, when it is precipitated along with sodium, potassium, and boron in the chloride and sul- fate zones (Stewart, 1963). In several western basins, lithium and potassium are commercially produced by evaporation of the brines. Lithium is also concentrated in lake clay de- posits of volcanic origin. Surface sediments, collected from low areas in 11 closed basins, contained 30-1 ,SOO ppm lithium (median, 300 ppm) and from 30 to ISO ppm lith· ium (median, 70 ppm) in 8 open basins (Lombardi, 1963; Kelley, 1948). Water Information on lithium concentrations in water is sparse because it is not usually measured in routine water analyses. Data for treated municipal water supplies for I 00 cities (Durfor and Becker, I964) indicate a median of about 2 TABLE12 Lithium Content of Various Rocks and Derived Soils Lithium Content, ppm Soilb Horizen Rock Type Rocka Humus A Granite 40 20 80 Sandstone 3S 8 Serpentine o.s 10 Andesite so Slate and shale 90 60 Olivine gabbro 30 Gneiss 70 aTurekian and Wedepohl (1961); Bowen (1966). bswaine and Mitchell (1960). 8 17S 8 2S 80 80 3S 60 c 200 6 2S 60 100 40 so Lithium 31 ppb, a figure which is probably representative of the level of concentration in many fresh waters in the United States. Concentration data for selected streams are given by An- gino et al. (1969) and others (Anderson, I971; Dutt and McCreary, 1970; Heidel and Frenier, I96S). A study by the U.S. Geological Survey (1972a) of water in Missouri has shown somewhat higher lithium values than the median of 2 ppb for United States cities. Five samples of groundwater were collected in each of six types of geo- logic materials. The results, shown in parts per billion are as follows: Quaternary alluvium Glacial drift Cretaceous-Tertiary strata Pennsylvanian Mississippian Cambro-Ordovician, SW Missouri Cambro-Ordovician, SE Missouri geometric mean S.6 12.0 2.0 68.0 1.6 11.0 0.66 geometric deviation 3.6 2.0S 31.2 2.02 S.83 2.73 S.94 A notable example of high lithium concentrations in wa· ter consumed by a particular population is reported from the Pima Indian Reservation in Arizona, where lithium values run as high as 380 ppb (H. L. Cannon, personal communication). Maps showing the concentrations of lithium in water (Anderson, 1972) and the geographic distribution of heart disease in the United States (Sauer and Brand, I97I) are given in Figures 4 and S. Low concentrations of lithium in water appear to correlate in a general way with a high incidence of heart disease in the eastern United States. Conversely, waters of very high lithium content in several of the western states are not found in areas where the inci· dence of heart disease is lowest. Although convincing evi- dence is not available, a large intake of lithium, as well as one that is too small, may be deleterious to health. Lithium is known to be concentrated in waters from hot springs, oil-field brines, highly mineralized waters, salt la- goons, and hydrologically closed basins. As a general rule, lithium in water correlates positively with hardness. It is easily removed from rocks and sedi- ments in weathering and, because of the high solubility of the simplest and most common lithium compounds, tends to remain in solution. Thus, water may constitute a major source of lithium for man and animals. It is dominantly ionic in aqueous solutions and tends to go into solution with sodium; lithium correlates negatively with aluminum but positively with magnesium, sulfate, and chloride (Bear, I964). As a result, lithium concentrations are gen- erally higher in chloride and sulfate waters than in bicarbo- nate water. The low levels of lithium found in most waters probably reflect the scarcity of the element in source rocks (Hem, 1959).
38 THE RELATION OF SELECTED TRACE ELEMENTS TO HEALTH AND DISEASE ---,....,.... __ _ : : if·-... o;> f \ -···-----. ; \ ·r-···------.:,-· -.1'\....,_.... ' . . ,. . . II 6-··-··-·-- .j \ I A ..i. "'-~· .. 1 o 6 : aA I / <,, II ! \ -a..;r' I : L ⢠, 6 ) ··- II ) '··-··--r.·· -··~ ·· -.. ~ - ··-··-··-··-"( 6 1 . il' t:. ---~ 8 ) ⢠64 ·- I I .. ⢠⢠· " ·-~ .. ··-··-.f_t:._ i ⢠: ⢠... ⢠i ⢠. ..... t:. ·-. : a9 ⢠,.~ !-··-··-··-"'"') . I!Q ~ r··- ··t. :~ r-··-··:·-----~- ~ .. , .. ~. ⢠8 i ,.;· -r-··----~--L .. , ~ ⢠~ \ i 111 j 6 d' 6 : ⢠o;l \- ··-·£··~/ o;l \ i f 0 tO ,r-··- ·· --A- --- ··:·~ ⢠\. . ⢠⢠. ... oibl ⢠\ "' j_ ! 0 ⢠~ i â¢â¢ \ _I ·f. r. o;l. ⢠⢠I ~. ⢠r-··-· --~ Q . ! ⢠i ⢠i ... ~ ; i ··--(~ ⢠⢠i⢠⢠at i ⢠-...... ..... . : ⢠........ 8 .. ! r---4{"" '"- ··- -~ '·· ., __ \ EXPLANATION \... r·-..... Ground- Surface Unknown Lithium in m1croorams '' \ water water source per liter \ 0 6 0 ~.5 ·."\ o;> ⢠11 >0.5 to ~10 · ⢠⢠⢠>10 to ~100 '---.. .. a 100 200 300 â¢oo Ml LES ⢠8 >100 ~piled br Barbaro M. Andorolft FIGURE 4 Map showing concentrations of lithium in surface and groundwaters of the conterminous United States (Anderson, 1971). Plants Uthium is not known to be an essential plant nutrient; however, it can affect plant growth and development. Uthium has been shown to exert a stimulating effect on the growth of plants, particularly of the Solanaceae family, but it retards the growth of citrus. According to Evans and Sorger ( 1966), at least one enzyme from a halophile is ac- tivated by sodium and lithium and not by potassium, am- monium, or rubidium. Those enzymes that are activated by potassium are not activated by lithium. Bertrand ana- lyzed 680 plants from 68 families and reported an average of 0.85 ppm (dry wt) in monocotyledons and 1.3 ppm (dry wt) in dicotyledons (Bertrand, 1952, 1959). Robin- son et al. (1971) found an average of 0.3-0.42 ppm (dry wt) in various classes of vegetation. Borovik-Romanova (1965) analyzed 138 plants from 8 soil types by emission spectrography, using potassium chloride as a buffer. She found that plants generally have an average content of from 0.15-0.3 ppm, but plants rooted in saline soils may contain 2- to 10-times that level. A comparison oflevels in foods and forage is shown in Table 13. Kent (1941) showed that lithium accumulates first in the root and then in older leaves, where it becomes im· mobilized. Bradford ( 1966) reported high lithium values (dry wt) in crops irrigated with water containing 0.1-0.2 ppm lithium. He found more lithium in leaves than in roots. Vlasiuk and Okhrimenko (1967) experimented with various levels of lithium to determine effects on growth, development, and productivity of tomatoes and potatoes. The lithium was introduced as lithium sulfate in amounts of0.1, 1, 2, 5, 10, and 30 ppm in soil, and the experiments were repeated six times. Curves plotted using doses com- pared to weight are bimodal with two optional values. For tomatoes, these were 0.1 and 2 ppm; for potatoes they were 0.1 and S ppm: The reason for these double optima is un- known. In 1969, the same authors reported that lithium has a positive effect on the photochemical activity of chloroplasts and the chlorophyll content of tomato and pepper leaves, with a consequent increase in the yield (Vlasiuk and Okhrimenko, 1969). Borovik-Romanova (1965) reports that lithium forms part of the protein frac- tion of the leaf and that lithium ions subsequently affect the metabolism of protein and carbohydrate in the plant. Addition of lithium salts can either stimulate plant
Lithium 39 â¢â¢ Q,~ RATE PER 100,000 POPULATION FIGURE 5 Map showing U.S. coronary heart disease (International Classification of Diseases, Cause 420) death rates, white males, age 45~. 1959-1961 (Sauer and Brand, 1971). HAWAII ⢠CS3 Lowest octile 278 - 462 ⢠Highest octile 666-915 - growth or cause toxicity symptoms to appear. The amount of lithium that is helpful depends on the tolerance of the particular species and the form of salt administered. Puc- cini (1957) reported that several lithium salts improved the growth ofcarnations, but that lithium carbonate was toxic. Voelcker (1912) found any lithium salt to be stimu- lating to wheat in amounts of less than 20 ppm but toxic at soil levels greater than 30 ppm. He reported lithium ni- trate to be the most toxic salt, yet at the same time the most stimulating to growth when not more than 10 ppm of it is present in soil. There is a considerable difference in the tolerance of vari- ous species to lithium concentrations. Citrus is sensitive to lithium, and toxicity symptoms develop in citrus trees grow- ing in California, where the lithium content of the soil is only 12 ppm (Bradford, 1966), but where lithium content in plants reaches 40 ppm (dry wt) or as much as 400 ppm in the ash. Toxicity in avocado seedlings was produced by the addition of 16 ppm lithium to the soil. Symptoms in- clude necrotic spots in the interveinalleaf tissue and even- tual browning and curling of the leaf margins. Edwards (1941) reported meristem damage in root tips of corn grown in high-lithium soils. Some plants, on the other hand, are tolerant of lithium, and their growth is stimulated when the soil contains con- siderable amounts. The best known of these is tobacco, a member of Solanaceae. In plot experiments, Headden (1921) found 230 ppm lithium in the ash [or about 25 ppm (dry wt)] of Nicotillna afrmis and SO ppm lithium in the ash of Nicotillna tobacum, but only a trace in alfalfa grown in the same soil. A maximum value of 4,400 ppm in ash [or about 750 (dry wt)] was reported by Strock (1936). Borovik-Romanova (1965) found species of Thalic- trum, Adonis, Cirsium, Nicotillna, Sa/sola, Solanum, Ranun- culus, and Lycium and Atropa belladonna and Datura stra- monium to accumulate lithium to an unusually large degree. It was noted that the lithium content is highest in samples with high alkaloid contents, which also vary with locality and growing season. In recent years, lithium compounds have often been used in organic synthesis and may participate in the biosynthesis of alkaloids. Bertrand ( 1959) reports that poppies are very tolerant of lithium. Vinogradov (1952) describes a lithium flora that includes Thalictrum (Ranunculaceae) and denotes a change in flora of alum lakes in volcanic areas. Linstow ( 1929) reported Lycium barbarum of Solanaceae to be a lithium indicator. The absorption of lithium by plants in arid basins of the basin and range province in the western United States is much greater than that observed by Bertrand (1952, 1959) in France, or by Robinson et al. ( 1971) in the eastern United States. The median content for 67 angiosperms in the basin and range region is I SO ppm in the ash, or 22.8 ppm (dry wt) lithium, as compared to an average of 1.3 ppm (dry wt) in angiosperms collected by Bertrand. Samples collected on the Pima Reservation in Arizona contained an average of 0.09 ppm lithium in well water, 58 ppm in soils, and 77 ppm (dry wt) in produce. The highest content in edible produce was 4.6 ppm in onions; 160 ppm (dry wt) was found inLycium, the fruit of which is used for jelly. Pickleweed containing 3,000 }>pm in the ash, or 840 ppm (dry wt), grows without apparent damage
40 THE RELATION OF SELECTED TRACE ELEMENTS TO HEALTH AND DISEASE TABLE 13 Lithium Content of Forage and Produce by Sample Area Lithium Content, ppm (dry wt'f Crop Type, by Family Eastern United Statesb Gramineae Timothy 0.069-0.28 (4) Wheat Sorghum Suprcane Com (kernels) Leguminosae Alfalfa 0.014-0.14 (3) Beans (fruit) 0.14 (1) a over 0.023-0.23 (7) Peas (fruit) 0.19 (1) Mesquite beans Solanaceae Potatoes 0.014 (l) Other species of Solimum Tomato Tobacco 0.37 (l) Wolfberry (Lycium) Other families Beets 0.023 (1) Cabbage 0.093 (l) Carrots 0.014 (1) Onions 0.23 (1) Radishes Capers Apples 0.023 (l) Tea Cotton 0.23 (l) TOTAL (range) 0.014-0.37 aNumben in parentheses indicate number of samples. bRobinson t!t al. (1971). cH. L. Cannon (unpubl.) . dBorovik·Romanova (1965). in salt soils containing 500 ppm of lithium. All species in the basin studies that contained 400 ppm or more lithium in ash are sodium chloride accumulators. It has been re- ported that sodium protects against lithium toxicity in human beings; the possibility of a similar protection in vegetation should be investigated. The lithium content of native plants in the Southwest correlates well with the lithium content of the soils in which the plants are rooted, except for certain species that accumulate the element. The same relationship has been reported in Russia by Borovik-Romanova (1965). Areas in which plants are deficient in lithium are un- known in the United States, and a requirement for lithium has not been established. Lithium is being used to increase the yield of sugar beet crops (and probably is used on po- tatoes and tobacco) in the Ukraine (Vinogradov, 1952). Crops grown in closed basins in California, Nevada, and Arizona are exposed to toxic levels of lithium. Pima Indian Reservationc Soviet Uniond < 0.4 (1) 0.85 (1) < 1.2 -2.2 (2) 4.4 (1) l.S (1) 0.56-3.1 (2) 0.4 -1.4 (2) 0.26~50 (5) 0.4 (1) 31 (l) 160 (l) 3.4 -58 (2) 1.4 (1) 4.6 (l) 2.7 (1) 3.6 (l) 1.2 (l) 2.3 (l) < 0.4 -160 0.26~50 Mammals lithium is concentrated to a limited extent in the endocrine organs; i.e., the thyroid, uterus, placenta-probably the pan- creas-the midbrain, adrenals, and ovaries (Gmelin, 1960; Wittrig, Anthony, and Lucarno, 1970). Limitations of assessment techniques of the past impose restrictions on the possible interpretations of data in the older literature. Average total daily human intake was pre- viously estimated to be 2 mg (Bowen, 1966), but a more recent estimate of daily intestinal absorption is 20 1-tg (Wittrig, Anthony, and Lucarno, 1970). This discrepancy probably reflects the fact that not all lithium in foods is absorbed by the intestine (Kent and McCance, 1941). How- ever, medicinal lithium salts in drinking water are believed to be completely absorbed. The absorbed lithium is largely excreted within 24 h (Ljungberg and Paalzow, 1969), except for a portion prob-
ably retained intracellularly. It is excreted mainly by way of the kidney (Ljungberg and Paalzow, 1969; Schou, 1957; Trautner et al., 1955; Foulks et al., 1952), and, under equi- librium conditions, daily urinary excretion of lithium is held to be a valid index of daily intestinal absorption. Geographical differences in lithium contents of human urine have been reported by Wittrig, Woods, and Anthony (1970) and E. B. Dawson (personal communication, 1971). High levels of lithium in neuroendocrine tissues have been reported from autopsy data on both wild animals and hu- man beings (Wittrig, Anthony, and Lucarno, 1970; Wittrig, Woods, and Anthony, 1970) not known to have been either treated with lithium or excessively exposed to it. These high levels in the necropsy material approximate those of lithium- treated patients (Francis and Trail, 1970) and suggest the influence of geographical differences in the lithium levels of local foods and water. EFFECTS ON HEALTH lithium administered in a dosage of 3 mg ionic lithium (or more) per kilogram of body weight per day decreases ag- gressive behavior in humans and other vertebrates (Levy, 1968; Weischer, 1969). This is 10,000-times the assumed natural daily intake of lithium. The action of such large doses is currently explained by the intracellular presence of lithium in the adrenergic sympathetic central neurons (Kopin, 1969), where it probably inhibits sodium ionic action through competition. Toxic symptoms have been reported at the pharmaco- logical dose level in humans. Lithium intake induces goiter through its effect on the thyroid gland, possibly by reduc- ing the blood thyroxin level (Shopsin, 1970), and has been responsible for congenital malformations because of an ad- verse effect on the function of the reproductive system (Schou et aL, 1968; Szabo, 1970). POLLUTION Currently, the status of man-made contributions of lithium to the environment is not clear. Information compiled by the U.S. Geological Survey (1972b) in connection with the Southwest Energy Study shows that coal being used in the Four Corners Power Plant has a median lithium content in the ash of 89 ppm; the fly ash in the stack has a median of 79 ppm; and wind-deposited fly ash contains 40 ppm. RECOMMENDATIONS FOR RESEARCH There is good evidence that some forms of mental illness can be alleviated by administration of large doses of lith· ium, and suggestive epidemiologic data relative to cardio- vascular disease are provocative. In view of the large num- Lithium 41 bers of people afflicted with these two disorders, the following recommendations are made: 1. Animal studies designed to determine whether lithium is an essential element should be conducted. These studies should include investigations into mechanisms of action and possible metabolic role, particularly in the endocrine system. 2. "Natural experiments," based on lifelong residents and wildlife in specific geographical areas, should be ex- ploited. _ 3. Lithium content of surface water and groundwater samples should be routinely determined as a means of cor- relating hard water with lithium content and cardiovascular disease. 4. Air, rocks, and food products in general, especially plants of the Solanaceae family (potatoes, tomatoes, green peppers, tobacco), and such things as cow's milk need to be assessed for lithium levels in relation to geographic lo- cation. REFERENCES Anderson, B. M. 197 2. Lithium in surface and ground waters of the conterminous United States. U.S. Geol. Surv. Open-File Rept. U.S. Geological Survey, Denver, Colo. 7 pp. Angino, E. E., 0. K. Galle, and T. C. Waugh. 1969. Fe, Mn, Ni, Co, Sr, Li, Zn, and Si02 in streams in the lower Kansas River Basin. Water Resour. Res. 5 :698-705. Bear, F. E. I ed I . 1964. Chemistry of soils. Am. Chern. Soc. Monogr. No. 160. Waverly Press, Baltimore, Md. Bertrand, D. 1952. The distribution of lithium in the phanerogams. C.R. (Acad. Sci., Paris) 234:2102-2104. Bertrand, D. 1959. New investigations on the distribution of lithium in the phanerogams. C.R. (Acad. Sci., Paris) 249:787-788. Borovilt·Romanova, T. F. 1965. The content of lithium in plants. In lnst. Geokem. Akad. Nauk, U.S.S.R., N. I. Khitarov 1 ed I. (Transl. Jerusalem, 1969.) Bowen, H. J. M. 1966. Trace elements in biochemistry. Academic Press, New York. 241 pp. Bradford, G. B. 1966. Uthium. In Diagnostic criteria for plants and soils, H. D. Chapman I ed I. Division of Agricultural Sciences, University of California, Riverside. pp. 218-224. Crawford, M.D., M. J. Gardner, and J . N. Morris. 1971. Cardio- vascular disease and the mineral content of drinking water. Br. Med.Bull.27:2l-24. Dawson, E. B., T. D. Moore, and W. J. McGanity. 1970. Mathe- matical relationship of drinlting water, lithium, and rainfall to mental hospital admission. Dis. Nerv. Syst. 31 :811-820. Durfor, C. N., and E. Becker. 1964. Public water supplies of the 100 largest cities in the United States, 1962. U.S. Geol. Surv. Water Supply Pap. No. 1812. U.S. Government Printing Ofnce, Wash· ington, D.C. 364 pp. Dutt, G. R., and T. W. McCreary. 1970. The quality of Arizona's domestic, agricultural, and industrial waters. Univ. Ariz. Agric. Exp. Stn. Rept. No. 256. University of Arizona, Tucson. 83 pp. Edwards, J. D. 1941. Cytological studies of toxicity in meristem cells of the roots of Zea mays. Proc. S.D. Acad. Sci. 21:65-67. Evans, H. J., and G. J. Sorger. 1966. Role of mineral elements with emphasis on the univalent cations. Ann. Rev. Plant Physiol. 17:47-76.
