INDUSTRIAL A N D EAiGINEERING CHEMIISTRY
May, 1927
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Natural Sodium Bicarbonate Waters in the United States’” By W. D. Collins and C. S. Howard UNITEDS ~ A T EGEOLOGICAL S SURVEY, WASHINGTON, D. C
T
HE type of natural water most generally used in the
United States is characterized by its content of alkaline earth bicarbonates. Diagram 1 is typical of waters that contain only small quantities of dissolved mineral matter. No. 2 may be taken to represent all the Great Lakes, which furnish public supplies for many large cities. Mississippi River, represented by S o . 3, is used for the public water supplies of cities from Rlinneapolis to New Orleans. The general character of waters from its eastern tributaries is much the same as that of the main river, but they are usually lower in sulfate. Over large areas in the Middle West the well waters are similar to that a t Dayton, Ohio, represented by diagram 4. Practically all the typical calcium bicarbonate waters contain sulfate and chloride. I n areas where gypsum is abundant the sulfate may exceed the bicarbonate and the waters may be characterized as calcium sulfate rather than calcium bicarbonate wat’ers. Many waters carry so much sodium sulfate or sodium chloride that the calcium and 1 Received March 25, 1927. Presented before t h e Division of Water, Sewage, a n d Sanitation a t t h e 73rd Meeting of the American Chemical Society, Richmond, Va., April 11 t o 16, 1927. Published by permission of t h e Director, United States Geological Survey. f
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magnesium are minor basic constituents. Brines from salt springs or from deep wells are likely to contain only comparatively small proportions of constituents other than sodium chloride. These may all be regarded as special classes, not affecting the statement that the calcium bicarbonate waters constitute the common type of natural water. Sodium bicarbonate waters have long been recognized at mineral-water resorts and a t numerous “soda” springs. Their widespread occurrence in ordinary wells throughout the United States has not been so generally known, probably because they are not so common in areas in which the most attention has been given to the composition of natural waters. Some waters contain little dissolved mineral matter except sodium bicarbonate, as illustrated by diagrams 5, 6, and 7 . These are undoubtedly to be classed as sodium bicarbonate waters. Many other waters may be said to contain sodium bicarbonate, although neither sodium nor bicarbonate is a predominating radical. The presence of sodium bicarbonate is indicated in diagrams such as Nos. 8, 9, and 10, which show the bicarbonate as more than equivalent to the sum of the calcium and magnesium. I n this paper the term “sodium bicarbonate water” will be reserved for waters in which sodium
I
A n a l y s e s of Natural W a t e r s (from Published R e p o r t s ) I--Catskill supply, New York C i t y , 1921 2---Lake Michigan, Chicago, Ill., 1921 8-Mississippi River, St. Louis, Mo., 1906 ?-Well a t Dayton, Ohio. 60 feet deep, 1922 a-Well a t Commerce, Miss., 1650 feet deep, 1919
6-Well a t Long Beach, Calif., 1153 feet deep, 1921 7-Well a t Smithfield, Va., 330 feet deep, 1918 8-Wells a t Montgomery, Ala., 200 t o 700 feet deep, 1021 9-Well a t Canton, Ohio, 180 feet deep, 1915 10-Wells a t Urbana-Champaign, Ill., 16: feet deep
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and bicarbonate are the predomiiiating radicals. The term “waters containing sodium bicarbonate” is applied to the true sodium bicarbonate waters as well as to some that have only small excesses of bicarbonat’e over the calcium and magnesium (diagrams 8 and 10). I n order to learn the distribution of sodium bicarbonate waters in the United States an examination was made of publications cited in a bibliography of reports that contain considerable numbers of analyses3 In addition examination was made of analyses in recent reports for Ohio4 and Arkansas5 and of about 2000 unpublished analyses made by the United States Geological Survey. I n all about 8800 analyses were reviewed. Many large groups were so uniformly in one class or another that they were not considered in detail. Of 5050 analyses noted individually as showing or not showing t’he presence of sodium bicarbonate, about 1250 show ab least a small quantity. Many are distinctly sodium bicarbonate waters. This proportion is probably high, because some of the areas for which the analyses were considered individually are those in which sodium bicarbonate waters are known to occur. It is not possible to prepare a map showing the areas of occurrence of sodium bicarbonate waters. The available analyses are too few, and for many large areas there is no reliable information. For certain states and larger areas, however, fairly definite statements can be made. The Atlantic Coastal Plain is perhaps the best defined area in which sodium bicarbonate waters are found. Hundreds of analyses show only 1 or 2 parts per million, or even less, of calcium or magnesium with several hundred parts of sodium and almost negligible quantities of sulfate and chloride. I n this area hard water is found in many shallow wells, but the sodium bicarbonate water is extensively used. Out of 321 analyses for the Coastal Plain of Virginia 206 show sodium bicarbonate, and in most of these the other constituents are present in insignificant quantities. I n the Coastal Plain of South Carolina 73 analyses out of 102 show sodium bicarbonate. The Coastal Plain province extends from southern New Jersey in a strip of varying width along the Atlantic and Gulf coasts to Mexico. Its inner boundary is about at Richmond, Va., Columbia, S. C., Augusta, Ga., Montgomery, Ala., the junction of Mississippi, Alabama, and Tennessee, Cairo, Ill., Little Rock, Ark., and Dallas and San Antonio, Tex. Florida is different from the rest of the Coastal Plain in not having many waters that contain sodium bicarbonate. None was found in 425 analyses made for a report on the chemical character of the natural waters of Florida. A number of very soft waters are found in this state, but they contain only small quantities of dissolved mineral matter. I n southern California, in Nevada, and in southern Arizona a good many well waters contain sodium bicarbonate. I n North Dakota sodium bicarbonate waters are common; in Montana they have been reported in counties for which analyses are available. Many waters containing sodium bicarbonate are found in Illinois, especially in the northern and central parts. Some are reported for Indiana. In southern Minnesota some waters contain sodium bicarbonate. I n a group of several counties in the southwestern part of Pennsylvania 37 waters out of 96 contain sodium bicarbonate; in 13 counties in the southeast,ern part only 3 out of 143 analyses show sodium bicarbonate. Out of 538 analyses of ground water in Ohio4only 22 showed the presence of sodium bicarbonate. Published reports :Collins a n d Howard, U. S. Geol. Survey. Waler-Supflly Pager 660 (1926). 4 Foulk, Ohio Geol. S u r v e y , 4th S e r . , Bull. 19 (1925). 5 Hale, Arkansas Univ. Eng. Expt. Sta., Bull. 2 (1926):
J-oL 19. S o . 5
for Iowa and Kansas show almost no waters that contain sodium bicarbonate. Very few have been reported for Wisconsin. S o analyses of such waters have been found for northern California or for S e w England. For the rest of the country the information at hand is not sufficient to justify any general statements in reference to large areas. Even the statements given above may be modified when more analyses are available. It has been commonly believed for a long time that many sodium bicarbonate waters are waters of ordinary composition which have been softened as they passed through rock formations that hare the properties of the exchange silicates so widely used in commercial water-softening. Reviews of literature on the subject and discussions of the occurrence of naturally softened waters in certain areas are given in two recent publications of the United States Geological Survey. Searly all the natural sodium bicarbonate waters of the Atlantic Coastal Plain are almost entirely free from calcium and magnesium and furnish valuable supplies for private and public use. I n other parts of the country more of the waters that contain sodium bicarbonate still carry enough calcium and magnesium to be decidedly hard, and in many places the quantities of sulfate and chloride are sufficient to make the waters unsuitable for general use. 8 Renick C S Geol Suvue)’, Ii’aler-Sufiply Paper 520, p 53 (1926); Riffenburg I b z d , 660,p 31 (1926)
Crystalline Substances Isolated from Lignin’ By George J. Ritter U. S. FOREST PRODUCTS LABORATORY, MADISON,Wrs.
N paper by Kurschner2 there appear description and Iurood photomicrographs crystalline substances isolated from lignin t h a t was prepared by fungus and enzyme action. a
of
I n this connection it is interesting t o recall some of the results of the microchemical study of wood now in progress a t the Forest Products Laboratory. Crystalline substances have been extracted by ether, acetone, and alcohol from chemically prepared wood lignin. The crystalline arrangement, form, and general character of these crystals are very similar to, if not identical with, those described by Kiirschner. The substances isolated in this laboratory exhibit definite optical properties with polarized light. It is believed t h a t a determination of the chemical composition and structure of these products will be an important step toward solving the composition of lignin. The preparation of quantities sufficient for that purpose are under way. Here, then, is a case in which lignin prepared a t moderate temperatures by the slow process of decay yields products similar t o those from lignin isolated by drastic chemical meansnamely, treatment with 72 per cent sulfuric acid. The latter is generally considered to be chemically different from lignin in the original wood; hence, the similarity just noted confirms the previously published findings of this laboratory that ligneous material resulting from decay differs in composition from that in the original sound wood.3 In working with ether extracts from lignin prepared by either chemical or fungus-enzyme action, the investigator must guard against any contact of cork with the solution, as the latter will become contaminated with similar crystalline substances. Received April 11, 1927. Z. angew. Chem., 40,224 (1927). a THISJOURNAL, 16, 137 (1924). 1
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