Plpril, 1932
INDUSTRIAL AND ENGINEERING CHEMISTRY
LITERATURE CITED Adeney, Fifth Rept. Royal Commission on Sewage Disposal, App VI, 13-23 (1908). Adeney and Dawson, Sci. Proc. Roy. Dublin SOC.,18, 199-202 (1926). Cooper and Nicholas, J. SOC.Chem. Ind., 47, 320-2T (1928). Cooper and Read, Ibid., 46, 154-6T (1927). Cooper and Read, Ibid., 46, 156-7T (1927). Cooper and Read, Ihid., 46, 413-81‘ (1927). Elder, IND.ENG.CHEM.,21, 560 (1929). Foreman, N. J. State Dept. Health, Public Health News, 13, 132-6 (1928). Greenfield, Elder, and McMurray, IND.ENG. CHEM., 18, 1276-9 (1926). Horowita-Wlassowa, Goldberg, and Goldberg, Brch. Hyg., 98 2 3 3 4 0 (1927). Illinois State Water Survey. Bull. 5 (1907). International Critical Tables. Vol. V. D. 446. McGraw-Hill, 1926. Krafft and Wiglow. Be?., 29, 1329 (i896)
463
(14) Levine, Sopperland, and Burke, Iowa State College, Eng. Expt. Sta., Bull. 68 (1923). (15) Lewkowitsch, “Oils, Fats and Waxes,” 5th ed., vol. 1, p. 133, Macmillan, 1913. (16) McBain, Trans. Faraday SOC.,9, 99 (1913). (17) MoBain, J. SOC.Chem. Ind., 37, 249-521‘ (1918). (18) Mohlman, Edwards, and Swope, 1x0. ENG. CHEM.,20, 242-6 (1928). (19) Standard Methods for m’ater Analysis, 6th ed., A. P. H. A.. 1925. (20) Symons and Buswell, IND. ENQ.CHEM.,Anal. Ed., 1, 161 (1929;. (21) Symons and Buswell, Ibid., 1,214 (1929). (22) Theriault, U.S. Pub. Health Bull. 151 (1925).
RECEIVED Auguat 10, 1931. Presented before the Division of Water, Sewage, and Sanitation at the 81st Meeting of the American Chemical Society, Indianapolis. Ind., March 30 to April 3, 1931. This paper ia a n abatrsct of a thesis submitted in partial fulfilment of the requirement8 for the degree of master of science in chemistry in the Graduate School of the University of Illinois.
Zinc in. Water Supplies EDWARD BARTOW AND OTIS MELVIN WEIGLE,State t-niversity of Iowa, Iowa City, Iowa disappearance of all but one of The limits of permissible zinc in drinking the m a n y s p r i n g s a t B a x t e r n a t u r a l w a t e r s . Zinc water have been questioned, and this ineestiSprings, Kans. sometimes occurs in tap gation was undertaken to secure data concerning Water coming in contact with water, having bpen dissolved these limits. Methods of analysis were checked, zinc in g a l v a n i z e d iron pipes from the zinc coating of galand a method was adapted to test samples in the a n d cisterns f r e q u e n t l y disvanized iron pipes and storage solves considerable zinc. Weintanks. field. The more accurate standard method of the land (24) found 5 p. p. m. of Underground waters occurA. 0. A. C . was used in the laboratory. zinc in the water supply of the ring in zinc-mining regions freA survey was made of natural waters of the chemical l a b o r a t o r y of t h e quently c o n t a i n considerable Missouri-Kansas-Oklahoma zinc district. Waters University of Tubingen. This zinc. The alternate exposure containing as high as 50 p . p . m. of zinc were contamination was traced to the of the zinc ore to air and moisgalvanized pipes leading into the ture favors its s o l u t i o n . The found. Animals and humans were drinking buildings. same principle a p p l i e s t o the waters known to contain zinc. A water which was d r a w n leaching effect of the s u r f a c e Water containing varying amounts of zinc from a well through a galvanized water on the e x t e n s i v e piles sulfate was fed to rats. The rats drank 50 of waste rock m a t e r i a l from iron pipe, several hundred yards p . p . m. of zinc as zinc sulfate over a period of which most of the zinc ore has in l e n g t h , was r e p o r t e d by been removed. Schwarz (18) to c o n t a i n 32.4 several weeks with apparently no harmful results. Parker and Bailey (16)report p. p. m. of zinc oxide. Many Zinc in many drinking waters comes f r o m w a t e r s f r o m zinc m i n e s and families using this water comgalvanized iron pipes. If a pure zinc were used concentration mills with a zinc plained of intestinal troubles. in the galvanizing, there should be less zinc content as high as 1862 p. p. m. Abbott ( 1 ) reports that the dissolved by the water. Mine waters analyzed b y water of Devil’s Lake, N. D., W a r i n g (23) s h o w as high as which seemed more toxic to fish It seems advisable that, until further informa6500 p. p. m. of zinc. Such than its composition indicated, tion is obtained, 5 p . p . m. or less of zinc should waters have a taste so astringent showed after careful analysis 15 remain the standard for drinking water. that they are not likely to be p. p. m. zinc. used bv men or animals. Jackson (10) saw: . Two- springs in Newton County, Mo., on the road from I have on numerous occasions examined water for zinc which Joplin to Seneca, about a quarter of a mile north of Shoal Creek, known as East Spring and West Spring, were notable has had very marked physiological action with 5 or 6 p. p. m. of zinc present. Notably in Falmouth Foreside, a summer place for their large content of zinc (4)-120.5 and 132.4 p. p. m., near Portland, Me., where they put in new water-supply mains respectively. These analyses were made by Hillebrand (5) of galvanized piping and started to drink it early in the spring in 1891. He says those waters were supposed to have a without flushing, the entire town was badly affected by it. I peculiar composition, owing to the strong metallic astringent ordered the pipes thoroughly flushed two or three times, using well water as drinking supply in the meantime, after which no taste left in the mouth after swallowing. further trouble occurred. One of the authors (Weigle) spent considerable time in The same difficulty arose with the new annex to our Natural April, 1931, in an unsuccessful effort to locate these springs. Science building where many of the fish and smaller animals were I t seems probable that the extensive underground excava- killed by the water which was used, and where a number of the instructors and professors were made very ill. This water tions in the zinc-ore bearing vicinity have intercepted the contained about 8 p. p. m. of zinc. In this case also, after flushing flow of these waters. The same explanation is given for the thoroughly several times, no further trouble occurred.
I S C o c c u r s in a fen.
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464
I N D US T R I A L A N D E N G I S E E R I N G C H E MI S T R Y
Stacks (19) in his report on “The Effect of Artesian Water upon Galvanized Steel Pipe,” which describes an investigation a t Moline, Ill., says, “About 30 days after the water system had been completed and in operation, complaints were heard regarding the quality of the water as it came from the fountains, and many of the employees were taken ill with cramps, fainting spells, and nausea, soon after drinking the water.” Conditions became rapidly worse and it was necessary to remove the zinc coating from the entire system of pipes.
FIGURE 1. MAP OF ZINC DISTRICT SHOWING LOCATIONS OF WATERSSAMPLEDCONTAINING ZIXC Hazen (6) reports that no harmful results were observed from the common use by the city of Brisbane, Australia, of rain water containing 17.1 p. p. rn.of zinc. The water had been stored in galvanized iron tanks. The water supply of West Berlin, Mass., drawn through 4000 feet of galvanized iron pipe, contained 18.46 p. p. m. of zinc, but appears to have produced no unpleasant results
(14).
Mason ( I S ) says he “has been unable to trace any evil effects due to the presence of zinc in drinking water, even when the quantity rose as high as 23 p. p. m. in a water which is in constant use. It might be well to add that, in the particular case just cited, the zinc was derived from a long stretch of galvanized iron pipes, and the ainount of the metal present was subject to great and frequent fluctuations for reasons that were not apparent.” Krohnke (11) and Wittus (25) recommend solid zinc pipes as a substitute for lead water conduits. Rinck (17) finds that the amount of zinc dissolved from solid zinc tubing in ordinary tap water is about 2 to 5 mg. per liter, and recommends the use of massive zinc pipes for conveying water. The literature gives such conflicting reports concerning the harmful effects of zinc that it is not surprising that the standards for zinc in drinking water have been questioned. They are as follows: Standards adopted by the Treasury Department, June 20, 1925, for drinking and culinary water supplied by common carriers in interstate commerce (22) (quoted and discussed by
Olds, 16) include the following concerning zinc in water: Zinc shall not exceed 5.0 p. p. m. I n the explanation of the drinking-water standards referred to above, the statement is made that “for the chemical determinations referred to in this report, the methods of analysis recommended by the Association of Official Agricultural Chemists (8) are satisfactory and may be substituted for those recommended by the American Public Health &socistion (&).’,
J’ol. 24, No. 4
Before adopting the method of the Association of Official dgricultural Chemists for the analysis of zinc in water, a11 effort was made t’o adapt the urobilin method developed by Lutz (12) or the method of Fairhall and Richardson ( 5 ) , both used for the determination of zinc in foods. The accurate determination of zinc in drinking waters by the regular gravimetric, titrimetric, or electrometric methods is impracticable for small amounts. For example, 10 liters of water containing 1 p. p. m. of zinc yields only 10 mg. of zinc on evaporation. It would be necessary to evaporate too large a volume of water to secure a sufficient quantity of zinc. Methods suitable for the determination of small quantities of zinc in small volumes of water must be used. For concentrations of zinc in water from 1 to 50 p. p. m., the ferrocyanide turbidimetric method gave very satisfactory results. The method developed by Lutz (12) in 1925 had such difficultiesthat it seemed preferable to use a less sensitive method using a larger amount of water. The ferrocyanide turbidimetric or nephelometric method, as developed by Fairhall and Richardson (5) was compared with the method of analysis of the Association of Official iigricultura1 Chemists. The latter method was more rapid and sufficiently accurate for present purposes, and was adopted for these tests. A method of testing samples a t their source was needed. After experiments with the methods of Thresh @ I ) , of Howard (Q), and of the Association of Official Agriwltural Chemists, a field test was adopted: FIELDTESTFOR Z I N IS WATER A 20 X 150 mm. Pyrex tube containing 1 cc. sulfuric acid (1:l) was filled two-thirds full of the water sample. Then about 1 cc. of a 10 per cent potassium ferrocyanide solution was added and the tube shaken. Since mater containing 1 p. p. m. zinc thus treated will show a slight opalescence within a few minutes, and since a sample of water containing 5 p. p. m. or more of zinc will produce a strong opalescence almost immediately, it became very simple t o select those Tvaters apparently containing zinc. J ~ A T E R SO F ,\IISSOURI-KA~SAS-OKL*Hoara
Z I s C DIsTRIC‘r
Since it was probable that the large zinc-producing area of Missouri, Kansas, and Oklahoma would have ground and surface water supplies containing zinc, plans were made for a survey of this territory. Out of the numerous samples tested by the field test, eleven sources of water supply were selected, and representative samples secured for laboratory analysis. The results of the final analyses of these selected samples are shown in Table I. TABLEI. . h A L Y S E S O F S.4MPLES FROM ELEVEN SOURCES O F RATER SUPPLY IS MISSOURI-KANSAS-OKLAHOXA ZINC DISTRICT Zrsc SOLIDS IN SOLGTICJY SAMPLE .iprilc‘ .\laya AprilG Maya REMA R K R P,n.n. P,o,m. P.o.m. P.V.~. Blank 0 0 0 1 . . . .b ..ti 737 5 2 .... 1883 ll.5 1636 50 3 2343 .... a151 13.7 11 i 4 .... 993 2 629 3.9 5 .... 46 1 366 10 11.2 6 .... 23.7 270 427 15 7 .... 57s 3 . 4 554 2 8 8 .... 287 279 1.5 2.2 9 .... 201 193 5 5 10 as9 317 39 40 11 413 406 12 10 10.6 Check ‘1 R. p . m. 1 0.9 13 Check 10 p. p. rn. .. .. 10 10 14 a 1931. b Paxson mine pumps shut down.
0
..
LOCATIOX AND USE
OF
..
WATERSANALYZED
Sample 2 . Blank. Sample 2. Paxson Mine, west of Baxter Springs, Kans.
Pumps deliver 1500 gallons per minute. The water is cold and
I N D U ST R I A L A N D E N G I
April, 1932
has no objectionable taste. Cattle like it. The fish pond, containing fine bass, perch, and catfish, has been supplied by this water for 4 years. One man says he frequently drinks this water, sometimes for 3-week periods, with apparently no bad results. In May, 1931, the mine pumps shut down. Sample 3. Tar River at Cardin, Okla., near bridge on Highway 7, had cattle tracks t o the water’s edge, indicating its use. Local people report that cattle drink this water with no apparent harm. Carp and catfish were caught in this water; also frogs and turtles were seen in the river. Sample 4. Creek south of Picher, Okla., has clear goodlooking water. Cattle use it with no apparent harm. Sample 5. Creek in Oklahoma contains fish and supplies water for a large farming district. Sample 6. Short Creek, Empire, Kans., furnishes drinking water to a number of cattle ranging the pastures along its banks. Sample 7. Creek west of Galena, Kans., is used by cattle. The sample was taken south of the bridge on Highway 166. Sample 8. Mine cave-in, 5 miles west of Joplin, Mo., 50 yards from location of sample 12, furnished drinking water for cattle. I t is a good fishing pond. Sample 9 . Old mine shaft used as a well, 5 miles west of Joplin, Mo., was used by families nearby until recently. As it shows signs of caving in, they fear t o go close t o the shaft. Sample 10. Cave-in (old mine shaft), 5 miles west of Joplin, Mo., is a favorite swimming hole. Hogs raised on this water look fine. Sample 11. Creek or mine drainage near Pickett cave-in, 5 miles west of Joplin, Mo., has clear cold water. Cattle and sometimes men drink this water. Sample 19. Short Creek, 5 miles west of Joplin, Mo., a halfmile south of Highway 66, has a chats road built through it t o make a watering place. A man has watered his horse in this creek two or three times a day for 3 years with no bad results. Carp, bass, and perch have been caught here. From the best evidence obtainable, the water containing zinc was used by man and animals without harmful results. To confirm or disprove evidence obtained from the analyses of the water in the Missouri-Kansas-Oklahoma district, tests were made with rats. TEST WITH RATS
No systematic effort had apparently been made by others to determine the effect of inorganic zinc salts administered to animals in drinking water. Heller and Burke ( 7 ) , after feeding rats food containing zinc salts, and Thompson, Marsh, and Drinker (SO), after feeding rats solutions of organic zinc salts, report that no evil effects were noticeable. A preliminary experiment was made here to study the effect of zinc upon rats, using pure zinc sulfate m drinking n-ater. Rats refused to drink a solution containing 5000 p. p. m. of zinc, possibly on account of the astringent metallic taste. The amount of solution drunk by the rats decreased as the amount of zinc increased. After the preliminary experiment, an extended series of tests was made. Twenty-four male rats, 33 days old a t the beginning of the experiment, were used for 40 days. Groups of four rats in individual cages mere given during the entire period one of the six solutions: (1) distilled water, (2) tap water, and water containing (3) 50, (4) 100, (5) 500, and (6) 1000 p. p. m. of zinc, respectively, as shown in Table 11. TABLE11. EXPERIMENT WITH TWENTY-FOUR M.4LE RATS (Summary of averages for 40 days. four rats on each solution and in individudl cages) WEIGHT AMOUNTOF WATER GAINED SOLX. FOOD ZINC Distilled Tap Zinc: 50 p. p. 100 p. p. 500 p. p. 1000 p. p.
m. m. m. m.
Grams
CC.
Grams
Mo .
172.5 167.7
1266 1146
530.7 489.7
0 0
167 162.7 153.2 143.7
1030 981 844.7 748.5
497 506.2 469.2 443
51.5 98.1 422.3 748.5
K E E 13. I N G C H E 11.1 I S T R Y
465
,4 greater amount of distilled than tap water mas drunk; the gain in weight was greater and the amount of food eaten was greater. The amount of water drunk by rats on tap mater, 50 p. p. m. of zinc, and 100 p. p. m. of zinc decreased with the increase in zinc content. However, there is no appreciable variation in the gain in weight and the amount of food eaten. The rats on solutions containing 500 p. p. m. and 1000 p. p. m. of zinc solution drank considerably less, ate less, and gained less. These results might be due to the astringent metallic taste of the solutions containing a high percentage of zinc sulfate. All the rats were apparently healthy a t the close of the experiments. Those on 1000 p. p. m. of zinc solution were noticeably irritable and easily startled on hot days but on cool days were apparently normal. I n reporting the harmful effects of zinc in water supplies in contact with galvanized pipes or containers, the possible effect of other impurities has not been considered-for example, cadmium and arsenic which are sometimes present in zinc used for galvanizing. The indications that pure zinc salts in reasonable amounts in drinking water are not harmful, and the facts that pure zinc can now be made cheaply and that pure zinc is difficultly soluble, suggest the possibility that the solvent action of waters on galvanized iron pipes could be reduced by galvanizing them with pure zinc. NOTE: Since presenting this paper, 6. W.Sheel has made tests for arsenic in zinc from galvanized iron pipe and in various samples of commercial zinc. The amount found, a few parts per million, is 80 small t h a t arsenic is eliminated as a possible cause of trouble in galvanized iron pipe of the present day.
LITERATURE CITED Abbott, G . A., Proc. I n d i a n a Acad. Sci., 34, 181 (1924). Am. Pub. Health Assoc., “Standard Methods of Water Analysis,” 6th ed., p. 54, 1925. Assoc. Official Agr. Chem., “Official and Tentative Methods of Analysis,” 2nd ed., p. 92, 1925. Clarke, F. W., U. S. Geol. Survey, Water S u p p l y Paper 364, 14 (1914). Fairhall, L. T., and Richardson, J. R., .I. A m . Chem. Soc., 52, 9 3 8 4 4 (1930). Hasen, Eng. N e w s , 57, 387 (1907). Heller, V. G., and Burke, -4.D., J . Biol. Chem., 74, 85-93 (1927). Hillebrand, W.F., U. S.Geol. Survey, Bull. 113, 49 (1893). Howard, C. D., J . A m . Vater W o r k s Assoc., 10, 411 (1923). Jackson, D. D., private correspondence, H. M. Palmer and Edward Bartow. Krohnke, O., J . Gasbel., 55, 421 (1912). Lutz, R. E., J . I n d . Hug., 7 , 273 (1925). Mason, W.P., ”Water Supply,” 4th ed., p. 465, Wiley, 1917. Massachusetts Board of Health Report, p. 495, 1900. Olds. H. N..Water W o r k s Ena.. _ . 82.. 366 (1929). . . Parker, H. N., U. S. Geol. Survey, Water S u p p l y Paper 273, 335 (1911). Rinck, A , 2. .Vahr. Genussm., 28, 99-103 (1914). Schwarz, F., Ibid., 14, 482 (1907). Stacks, D. H., Proc. Illinois Water S u p p l y Assoc., 5, 123 (1913). Thompson, P. K., Marsh, M., and Drinker, K. R., Am. J. Physiol., 80, G5 (1927). Thresh, J. C., “The Examination of Water Supplies and Waters,” 2nd ed., p. 317, Churchill, London, 1913. U. 5. Pub. Health Service, Drinking Water Standards, Reprint No. 1020, 40, 693-721 (1925). Waring, W.G., U. S. Geol. Survey, r a t e r S i ~ p p l lPaper ~ 273, 356 (1911). Weinland, R. F., Z. Nahr. Gejiussm., 19, 362 (1910). Wittus, J . Gasbel., 56, 936-7 (1913); J . SOC.Chem. Zrid., 32, 957-8 (1913). RECEIVED November 23, 1931. Presented before the Division of Water, Sewage, and Sanitation a t the 82nd Meeting of the American Chemical Society, Buffalo, N. Y., Sugust 31 to September 4, 1931. This paper is an abstract from a dissertation submitted in partial fulfilment of the requirements for the degree of doctor of philosophy in the Department of Chemistry, State University of Iowa, by 0. M. Weigle.
