T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y
Jan., 1913
The results are shown in Table 11. The treatment with calcium hypochlorite has entirely eliminated the gas formers from the 0.1 cc. samples, from 86 per cent. of the I cc. samples and from 50 per cent. of the 19 cc. samples. The filtration has improved conditions by increasing the removal to 91 per cent. of the I cc. samples and to 73 per cent. of the I O cc. samples. From these observations we q a y conclude that the calcium hypochlorite acts most efficiently in the removal of free bacteria, that the filters still further reduce the numbers by removing aggregates of bacteria which are surrounded by or enclosed in sediment. TABLEII
FORMATION O F GAS
DEXTROSEBROTHAT 37'/a0 C. 10 cc. 11411 cc. 20+ 3e0 . 1 cc. 18+ After sedimentation.. . . . . . . . . 10 cc. 10+ 01 cc. 18+ 20 . 1 cc. 14+ 7After hypochlorite ............ 10 cc. 6461 cc. 3 c 18o+ 220 . 1 cc. Filter effluent 10 cc. 3 f 81 cc. Zf 20o+ 220 . 1 cc. IN
R a w . . ......................
................
I n the second example of the efficiency of calcium hypochlorite none of the chemical was used for six days, owing to the failure to receive a shipment. I n the treatment plant lime and iron sulfate were used TABLE111 CALCIUM HYPOCHLORITE^ Bacteria Gas formation P 7 Partsper million Filter TurbidFilter e0luent chlorine Date, 1912 ity Raw effluent Raw 0.51 Mar. 13 . . . . . . . . . . . 25 1600 3 + 0.51 Mar. 14 . . . . . . . . . . . 25 3900 10 0.55 Mar. 15 . . . . . . . . . . . 210 90000 200 0.45 Mar. 16 ........... 230 400000 275 0.53 Mar. 17 ........... 500 27000 50 0.48 Mar. 18 . . . . . . . . . . . 800 125000 20 Average six days preceding period without hypo- 298 107917 93 loo%+ None 0.50 OPERATING RESULTSWITH
i
AND WITHOUT
+ + + + +
I
li
-
+
chlorite.. . . . . . . . j Mar.20 ............ 300 112000 8400 Mar. 21 . . . . . . . . . . . 400 110000 7500 Mar. 22 60000 2000 150 Mar. 23 . . . . . . . . . . . 825 44000 1700 . Mar. 24 . . . . . . . . . . . 400 56000 2000 Mar. 25 . . . . . . . . . . . 320 20000 3000 Average during period without hypo- 399 67000 4100 All+ chlorite. . . . . . . . . Mar. 26 . . . . . . . . . . . 200 20000 30 Mar. 27 ........... 220 160000 120 Mar. 28 . . . . . . . . . . . 450 75000 80 Mar. 29 . . . . . . . . . . . 4000 300000 120 Mar. 30 ........... 4000 300000 550 Mar. 31 . . . . . . . . . . . 350 250000 200 Average six d a y s ) following period 11537 184170 183 All+ without hypochlorite. ........ 1 Analyses by H. M. Ely, Danville, Illinois.
...........
-
+ + + + + +
+ + + + + +
+ .
+ + + +
83.3%
-
00 00 00
+
None
00 00 00
+
None 0.48 0.57 0.55 0.60 0.47 0.47 0.52
as coagulants. The amounts used were varied in such a way as to furnish a clear water. The calcium hypochlorite was used as an adjunct. There is approximately one hour's sedimentation after the lime and iron sulfate are added. The calcium hypochlorite
I9
is added not more than five minutes before the water reaches the filters. The water during the three six-day periods, before, during and after the failure to receive the calcium hypochlorite, was especially bad (see Table 111) as was shown by the high turbidity and the large number of colonies that developed from the raw water during forty-eight hours on gelatine a t z o o C. After the first two days of the first period the number of bacteria in the raw water were never lower than 2 0 . 0 0 0 . Only once was the turbidity below z o o , reaching a maximum of 4,000 during the latter part of the period. As shown in Table 111, the bacterial removal during the six days preceding the period without calcium hypochlorite was 99.9 per cent. and gas formers were entirely absent in the general effluent from the filters. During the period without calcium hypochlorite the bacterial removal was only 93.9 per cent. and gas formers were present in the effluent with the exception of the test made on the first day without calcium hypochlorite. During the six days following the period without calcium hypochlorite the bacterial removal was again 99.9 per cent. and gas formers were absent in all of the samples tested. These results show very decidedly the advisability of using calcium hypochlorite under conditions similar to those existing in the plants in question. UNIVERSITY O F ILLINOIS
URBANA
COMPOSITION OF THE SALINES OF THE UNITED STATES' 111. Brines from the Ocean and Salt Lakes with analyses by W. H. Ross, A. R . MERZ AND B y J. W. TURRENTINE, R . F. GARDNER Received October 9, 1912
I n the search for deposits of potassium salts in the United States two sorts of deposits have been considered, namely, continental and marine. The former, continental, are those which have resulted from the desiccation of inland seas or lakes; while the latter, marine, are the product of the evaporation of arms of the ocean which have become isolated from the main body of the ocean through the formation of bar reefs. The latter method would be analogous to that generally proposed to account for the formation of the Stassfurt deposits. Among the saline deposits in the United States, theoretically, are deposits of both kinds. These have been (or are being) subjected to scrutiny to discover if there may be potassium salts therein, as well as sodium. The search for continental deposits has confined itself to those regions which i t is known were once covered by inland seas. This statement connotes the fact that such lakes were of sufficiently recent occurrence for their marks to have remained extant on the face of the country where they existed. It is not sufficient that those areas were submerged by lakes, but for deposits of salt t o have formed, i t is necessary that the lakes shall have disappeared through desiccation rather than through drainage. Continental deposits have been sought in the undrained basins of the western part of the United 1
Published by permission of the Secretary of Agriculture.
20
T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y
States. As the basins are unfilled by sedimentary or detrital material it was hoped that the saline residues would be found on the floor of the basins. Such has been the case in some instances, while in others there are indications that sufficient detrital matter has been carried into the lowest depressions of the basins to cover any saline matter once deposited there. The undrained basins of the west may be classified as follows: (I) The Lahontan Basin; (11) the Lake Bonneville Basin; (111) the group of small basins found in southern and central California and southern Nevada; and (IV) other basins of slight importance, such as the Salton Basin, formerly of great interest, but now resubmerged; the lake basins of northeastern California and southeastern Oregon and arid basins of New Mexico and small basins bordering the arid area. I. T H E L A H O N T A N B A S I N
The core of the basin in the northwestern and central part of Nevada, during the quaternary period of greatest lake expansion, was a single great lake. I t s history has been studied by Russell,' who gave it the name Lake Lahontan. The basin is nearly a unit, the divides now evident being low or discontinuous. The old lake at present is represented by a few remnants, such as the Pyramid, Winnemucca and Walker Lakes and a number of sinks, playas and saline marshes. The salts now present on its surface, in the form of crusts or brines, are certainly far less than the salts which one reasonably can assume to have been present in the larger lake. Russell accordingly has assumed that the saline material has been buried by alluvial coperings, and subsequent investigation has tended to uphold this conclusion. It is reasonably certain that the original saline konstituents of the Lake Lahontan water underlie the floor of the parent basin, either as crystalline deposits or as saltimpregnated strata of alluvial material. The rocks of the basin and its drainage area are largely igneous, though for the most part non-potassic. Consequently it is to be concluded that the salts in the early lake were largely sodium salts and alkaline in character. From a n examination of surface conditions, it is impossible to say whether, in the'deposition of these salts, the potassium was crystallized a t all or, if so, whether in segregated strata or as a crystalline mixture; or whether the mother liquor from the sodium salts deposition, containing the potassium salts, was or was not disseminated through the saline and alluvial strata. These questions can be settled only by boring, a work which the U. S. Geological Survey is now undertaking. Already a boring to the depth of several hundred feet has been sunk in the Humboldt Basin, a depression of the Lahontan, where the surface conditions indicate that the bottom of the basin may be reached. So far, only alluvial matter has been encountered, and the water obtained from the boring, instead of being a brine, is surprisingly fresh. 11. B O N N E V I L L E B A S I N
I n northwestern Utah and extending across the Monograph XI, U. S. Geological Survey.
Jan., 1913
state borders into eastern Nevada is a somewhat larger basin recorded by Gilbert' as Lake Bonneville. This basin is also a topographic unit and was once occupied by a great quaternary lake. The last remnant of this lake is found in the present Great Salt Lake of Utah. The Bonneville Basin differs from the Lahontan in that i t is set in Paleozoic sediments inste9.d of rocks of igneous origin. It is to be expected, therefore, that its salines are largely neutral salts, rather than alkaline, consisting mostly of the chlorides and sulfates of sodium and magnesium. That such is actually the case is seen from the analyses of the water of Great Salt Lake.' I t is to be expected that potassium salts would have been present in Lake Bonneville only in small amounts, and such seems to be the case from the analysis of the Great Salt Lake water. It is possible that, a t some previous time, the lake may have gone completely t o dryness, when the saline accumulation of the preceding age was deposited, and that the salts of the present lake represent the accumulation of more recent age. There is no evidence a t hand, however, by which to substantiate such a supposition. Desiccation has taken place in the Great Salt Lake to the point of saturation with respect to sodium sulfate and of high concentration in sodium chloride. Crystallization is now taking place in the lake to the extent, a t least, that sodium sulfate precipitates during cold weather, forming a crystalline crust on the surface. The crystals doubtless fall to the bottom of the lake, though it has not been established that there is a n accumulation of saline material on the bottom. Neither the probable geological history of the Bonneville Basin nor the character of the rocks in which i t lies offers any indication of the presence of segregations of potash, and a negative conclusion may be considered warrantable. 111. T H E G R O U P O F S M A L L B A S I N S F O U N D I N C E N T R A L
AND
SOUTHERN
CALIFORNIA
AND
SOUTHERN
NEVADA
The region south and southwest of the Lahontan Basin is similarly lacking in seaward drainage. This area likewise was occupied by lakes during a n earlier period: The topography of the country is such that i t is divided by high qnd continuous mountains into a number of small basins, each with its individual characteristics. I n this area'are included the Mojave Desert and Searles, Saline, Amargosa and Death Valleys. The rimmocks of these basins are varied and have been but little studied. It is known, however, that surrounding them lie rocks of both igneous and sedimentary origin. The basement granites of the Sierra Nevada are exposed in places in the western part of the area, especially toward the south. Searles Luke.-Of particular interest among t,he basins of this group is the Searles Marsh, or Lake, in San Bernardino County, CaliEornia, which has been found in the last stages of desiccation. At pr5sent the lake, or dried-up remnant of a lake, covers an area of 11 square miles and is of unknown depth. -It is covered by a crust of saline material, beneath which 1 2
Monograph I, U. S. Geological Survey. "Data of Geochemistry," Clarke, U.S. Geologual Surv. Bulletm, 491.
Jan., 1913
T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y
lies a mixture of saline and clayey material. The saline crust has a thickness of 7 5 to I O O feet and is composed principally of sodium chloride, sulfate, carbonate and borate. Considerable segregation has taken place in the crust, though the stratification is not a t all well defined. And there is no strict demarcation between the saline and clayey strata, but rather a gradual transition from the one to the other. Various crystalline, saline minerals are found intermixed with the loosely-defined strata. Among these are halite (NaCl), thenardite (Na,SO,), gypsum (CaSO,.zH,O), gaylussite (Na,Ca(C0,),.5H20), borax, hanksite (Na,,K (SO,) o(COJ)IC1),etc.1 Both the saline and clayey strata are impregnated with brine. The analyses of the Searles brines, reported below in Table I , were made by Mr. A. R. Merz, of the Cooperative Laboratory, Mackay School of Mines, Reno, Nevada, and were duplicated by Mr. j . G. Smith, of the Bureau of Soils. TAELE I-ANALYSES O F BRINESFROM SEARLES LAKE. POTASSIUM OXIDE RECORDED A S PER CENT. OF TOTAL SOLIDS Sample number . . . . . . . . . . . . . . . 198 199 200 201 202 203 Total solids, grams per 100 cc., 44.29 4 4 . 6 9 4 3 . 6 6 4 2 . 8 6 4 3 . 9 6 4 3 . 4 5 Potassium oxide.. . . . . . . . . . . . . . 7 . 6 3 6 . 2 3 6 . 8 9 6 . 0 6 7 . 2 7 6 . 5 7
...
The system which is represented by the Searles Lake brines-one containing chlorides, sulfates, carbonates and borates of sodium and potassium-is extremely complex. I t cannot be accurately foretold, therefore, what the conditions controlling the separation of potassium salts therefrom will prove to be, or with what ease or difficulty the separation may be made. Since the carbonate and borate are among the more valuable of the various possible products of the lake, the potassium salts may be produced as a by-product. A study of the system, sodium chloride, sodium sulfate, sodium carbonate, sodium borate, potassium chloride, potassium sulfate, potassium carbonate, potassium borate, and water, or, in short, the system represented by the water of alkaline lakes and typified by,the brine of Searles Lake, is being studied in the laboratories of the Bureau of Soils, with a view to the separation of potassium salts from such brines.’ The following complete analysis of the brine from the Searles Marsh is by Dr. W. H. Ross, of the Bureau of Soils. BRINE ,FROM SEARLESLAKE. EXPRESSED IN PERCENTAGES O F THE ANHYDROUS SOLIDS Ca Si02 none COS 6.70 0.023 Cl Mg trace POI 0.30 37.02 Mn none Br NO3 none 0.094 Cu none I As202 0.083 0.004 Alp08 0 . 0 1 2 SO1 12.96 P,O, 3.00 Fez03 0 . 0 0 3
TABLE 11-ANALYSIS
Na K Li Rb Ba NH4
33.57 6.06 0.01
none none none
OF
1 This statement is made on the basis of recent observations. The Searles Marsh has been described by Wm. Irelan, Mineralogist, in the 10th Ann. Rpt. State Mineralogist, Cal. State Mining Bureau, pp. 534-9, 1890. The chemico-engineering problems involved in the extraction of potassium salts from the Searles brine have been investigated during the past summer by Mr. John W. Hornsey, Consulting Engineer, 49 WalL Street, iYew York City. As a result of the successful outcome of these investigations, we are informed by M r , Hornsey, under date of December 27th, t h a t the operating company has begun the erection of the first of four units of an extracting plant with a capacity of about 125 tons of potassium chloride per day. I t is intended to increase this to a production of about 500 tons per day. In addition to potassium chloride the plant will produce soda ash and borax, with the probability of adding other products later.
21
The sample was collected by Mr. E. E. Free, of the same Bureau, from a well on the marsh designated as -47. Additional results, in the following table, are expressed in percentages of the original brine, by weight, The weight of the total solids was taken after drying a t 110’ C., and includes some water of hydration, and organic matter. This is expressed by the value recorded as loss on ignition. TABLEI11 Sodium carbonate in solution3.04 Total solids, a t 110’ C.. . . . 3 0 . 3 4 Loss on ignition. .......... 0 . 6 9 Sodium bicarbonate in s o h . 0 . 7 5 Anhydrous solid. . . . . . . . . . 2 9 . 6 5 Potash, KzO.. . . . . . . . . . . . . . 2 . 1 7
.
Railroad Valley.-It has been long known that the brines of Railroad Valley, Nevada, contain a remarkably high percentage of potassium salts. The recent analyses of various samples of these brines, performed by A. R. Merz, are given in the subjoined table. The potassic brines of this valley, however, are found impregnating the detrital material on the floor of the depression and, as are the brines of many such basins, are confined to the upper portion of this material. The composition of these brines in the various parts of the flat are extremely variable, not only in concentration but in the relative proportion of the various salts. The exploration of the valley is being continued by the Railroad Valley Saline Company. This company has sunk a well which a t present has reached a depth of 1 2 0 0 feet and has not yet reached the bottom of the original lake which submerged this valley. Large’ volumes of fresh water, artesian in character of flow, are now obtainable from this boring.‘ Following is given the log of the well as recorded in a report on “Potash,” by E. E. Free and published by the exploitation company. LOG Feet 1- 32 32-103 103-132 132-136 136-178 178-2 14 214-285
O F RAILROAD
VALLEY HOLE
Sand with occasional clay layers Quicksand Alternations of quicksand and clay White clay with small seams of fine gravel or coarse quicksand Heavy clay Quicksand Alternations of clay and sand, layers 1 f t ’ t o 10 ft. thick
Artesian water, especially a t 128 f t .
Artesian water Artesian water in most of the sands, especially a t 220 and 250 it.
Sand, coarser in upper part. Pebbles 3 4 in. in diameter a t 285 f t . Artesian water Tough clay 305-336 Quicksand with some clay and some small 3 3 6-340 gravel Artesian water Clay, with occasional streaks of quicksand 340-365 Quicksand with very small streaks of clay Artesian water 365-375 Tough, gray clay 375-390 Quicksand Small artesian flow 390-391 3 9 1 4 1 8 Tough, gray clay 4 1 8 4 1 9 Quicksand Small artesian flow 4 1 9 4 2 9 Brown clay Quicksand 429430 Small artesian flow 4 3 0 4 6 0 Clay, gray in lower part, changing t o brown in upper 4 6 0 4 6 1 Quicksand Artesian water 4 6 2 4 7 0 Blue-green clay, with a white layer on top 1 WeI are advised by Mr. Hoyt S. Gale, of the U. S. Geological Survey, that similar fresh water is being met a t about the same depth in the boring he is supervising near Fallon, Nevada, in the Lahontan Basin. It may, perhaps, be regarded as a sign of great promise indicating t h a t there is no great dissemination of salines in the detrital fill of these basins, and per contra, that there are segregated salt layers somewhere below the surface, though a t what depth cannot be predicted as yet. 285-305
22
T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y Loo OF RAILROAD VALLEYHOLE( C o n t i m d )
Feet 470471 471-478 478479 479-500 500-504 504-519 519-520
Quicksand Lead-colored clay Very fine sand White and blue-green clays Blue-green clay with some coarse sand White and blue-green clays Quicksand
520-529
Gray clay with occasional sand streaks
Gray clay Very fine quicksand Blue-green clay Quicksand with some light colored clay and some coarse gravel 541-560 Yellowish, white and blue-green clays 560-561 Quicksand 561-586 Blue-green and white clays 586-587 Quicksand 587-596 Clay 596-609 Alternations of sand and clay, the proportion of sand increasing downward 609-637 Clay, whiter in upper part 637-638 Quicksand 638-676 Tough clay, white and greenish in color 676-677 Quicksand 677-680 Alternations of clay and sand 680-691 White clay 691-700 Alternations of clay and sand 700-719 Clay, brownish on t o p 719-720 Sand 720-738 Brownish clay 738-746 Clay and quicksand mixed. Some coarse gravel 746-759 Tough, brownish clay 759-771 Sand alternating with very tough, brownish clay 771-785 Tough, brownish clay 785-786 Quicksand 786-790 Clay 790-791 Sandy streak in clay 791-798 Brownish clay 798-805 Alternations of clay and sand 805-8 16 Clay, hard and brown in lower part 816-822 Quicksand and gravel 822-824 Hard white clay 824-846 Clay and sand alternating every 2 to 6 in. Proportion of clay increases with depth 846-850 Brownish clay 850-855 Sand and gravel 855-865 Rapid alternations of clay and sand 865-876 Gray clay 908-924 Sand and gravel 924-934 Light and gray clay 934-941 Fine sand 941-945 Gray clay 945-947 Sand 947-967 Clay, yellow on top, gray below 967-968 Sand and gravel 968-1088 Hard, dry clay 1088-1089 Dry sand 1089-1 175 Hard, dry clay
29-533 533-534 534-539 539-541
Artesian water
Artesian flow smelling of sulfuretted hydrogen Small artesian flow in sands. All smell of sulfuretted hydrogen
Strong artesian flow
Artesian water Small artesian flow Small artesian flow, a t 605 f t .
Small artesian flow
Very small artesian flow Very small artesian flow in the sands Artesian flow Small artesian flow
Jan., 1913
TABLE IV-ANALYSES OF BRINES AND SALINE CRUSTS FROM RAILROAD VALLEY, NEVADA. A. R. MERZ. ANALYST. TOTALSOLIDS AS GRAMS PER 100 cc. POTASSIUM OXIDE AS PERCENTAGE OF TOTALSOLIDS PerPerPerSample Total centage Sample Total centage Sample Total centage no. solids K20 no. solids KaO no. solids KZO 1 3.68 33.86 6.97 127 76.40 9.06 91 70.97 2 6.65 9.87 92 74.72 44.08 8.46 128 62 .08 2.73 3 93 56.37 55.20 12.19 7.54 129 55.22 4 8.54 94 16.68 49.10 10.02 3.98 130 20.87 4.53 5 58.32 7.39 131 83.40 7.18 95 53 .OO 2.06 6 48.32 11.03 9.20 132 40.42 96 71.64 7 6.14 8.46 97 69.12 42.62 7.72 133 12.63 6.23 26 2.07 9.22 134 13.04 5.25 98 55.16 3.39 28 8.52 135 68.64 13.16 4.25 99 64.96 1.81 6.22 30 5.76 137 14.18 6.52 100 66.62 1.16 0.97 43 2.22 138 4.55 5.29 101 34.48 1.30 45 8.96 139 47.18 27.36 5.03 102 55.18 15.74 48 5,94 33.98 3.10 103 43.24 3.90 143 82.46 54 2.66 25.24 0.89 104 53.96 3.78 144 2.83 55 6.38 145 41.34 22.74 3.28 105 72.64 2.26 72.06 6.73 146 56 53.80 1.22 106 46.38 57 9.26 5.00 148 7.58 58.22 1.65 107 76.38 3.41 149 44.22 6.58 58 33 .OO 5.87 108 60.02 4.83 2.38 152 29.80 27.56 59 4.10 109 58.72 11.62 11.92 3.90 153 24.48 62 4.68 110 28.54 6.11 154 1.05 111 59.62 64 12.09 11.78 27 3 6 5.45 155 69.00 10.17 12.10 66 1.65 112 59.16 7.86 11.46 6.20 156 71 4.35, 113 56.48 59.92 5.03 12.82 76 4.23 158 4.55 8.53 114 72.22 3.79 1.53 159 67.92 58.22 80 6.85 115 41.24 1.48 81 6.02 162 48.92 56.63 2.98 116 10.56 13.99 5.49 82 6.16 163 55.72 3.67 120 5.36 13.97 5.82 164 84 14.09 4.06 122 79.56 12.10 3.26 1.90 165 64.62 87 30.46 4.53 124 68.74 3.42 76.58 2.94 166 88 2.33 125 45.42 24.03 1.53 5.04 168 41.10 5.71 126 56.90 89 25.58 90 49.48 7.91
Death Valley.-In Table V are given the analyses of a number of brines from Death Valley. TABLE V-ANALYSES OF BRINES FROM DEATH VALLEY. A. R . MERZ, ANALYST. TOTAL SOLIDS RECORDED AS GRAMSPER 100 cc. POTASH AS PERCENT. OF TOTALSOLIDS Sample Total KaO nugber Location solids per cent. 306 Surface pond about middle of valley. 36.5 1 3.42 307 Shallow hole dug about mile north of sink 20.36 1 .08 326 Water standing in slough about middle of valley ................................ 1.50 10.42 327 Water from ten-foot hole about middle of 3.31 valley ................................ 36.81 331 Water from six,-foot hole dug near Geol. Sur. bench mark in middle of valley. About 1 mile east of No. 327.. 33 .80 0.96 338 Water from three-foot hole dug in north 3.08 flat. (Cf. Table VI). . . . . . . . . . . . . . . . . . . 33.28 339 Water from three-foot hole dug near west side of valley west of Furnace Creek Ranch.. ... 2.77 1.75 341 Water from four-foot hole dug about middle of valley due west of Furnace Creek Ranch 15.12 2.38 342 Water from three-foot hole dug near east side of valley, due west of Furnace Creek Ranch 34.18 2.98 343 Water from slough a t old bridge, west of 2.25 Furnace Creek Ranch. . . . . . . . . . . . . . . . . . 32 .05
.......
Artesian water Strong artesian flow in all sand strata
................
Strong artesian flow
Small artesian flow
This log has been interpreted favorably. On the basis of this interpretation i t appears reasonable t o believe t h a t the potassic brines of previous ages may have undergone evaporation in this basin, possibly t o the point of deposition of potassium compounds, and t h a t such deposits lie buried beneath the accumulations of detrital material now being explored. I n the following table of analyses of brines and saline crusts from Railroad Valley the numbers lacking from the series are those of samples whose total saline content was so low as t o make them of slight interest:
I n Table VI are given results of fuller analyses of certain typical brines of this general region. The actual determinations are of potassium chloride and sulfuric acid. The sodium is calculated from the weights of chlorine and sulfuric acid in excess over t h a t required t o saturate the potassium. These brines are free from carbonates and contain, if any, a t most only traces of calcium and magnesium. Owens Lake, occupying a depression on the extreme western border of this area, is of interest in view of the fact t h a t its brine has been shown t o contain 4.54 per cent. of potassium.’ 1
Loew. Ann. Rept. Geol. Sum., W.100 Mer., 1878, P. 190.
Jan.,
1913
T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y
TABLE VI-ANALYSES OF CERTAIN BRINES FROM RAILROAD,DEATH, AS GRAMS PANAMINT AND DIXIE VALLEYS. RESULTSARE RECORDED PER 100 cc. A. R. MERZ, ANALYST Total Total solids solids by by addi- detenniNo. Locality KC1 NaCl Na@OI tion nation 12A143 Railroad Valley auger hole bored in north end of f l a t . . . . . . . . . 1 . 4 7 1 2 . 1 8 1.28 14.93 15.74 12A154 ditto, hole dug by R. V. Co., north end. offlat 2.24 8.89 0.86 11.99 12.09 338 North end Death Valley, sample mentioned above.. ..... 1 . 6 1 2 5 . 2 1 6.56 33.38 33.28 Coop. Panamint Valley. ColLabSot lected by S. W. 142-1 Austen. ........... 0 . 3 9 6.44 0.74 7.57 7.80 Coop. Death Valley, dug hole Lab. near center of vallot ley. Collected by W. 161-1 G. Luckhardt ....... 3 . 0 6 2 5 . 9 7 9.71 38.74 40.02 coop. Lab. lot Water from Dixie Val214-2 ley, Nev.. 4 . 1 4 23.38 12.06 39.58 43.47
.
.............
.........
IV. O T H E R BASINS O F SLIGHT IMPORTANCE
I n Table VI1 are recorded analyses of brines from certain undrained lakes of southeastern Oregon.
a commercial possibility due to the ingenious method of Balard, as elaborated by Merle and Pechiney.1 This reached its maximum development a t Geraud en Camarque, a t the mouth of the Rhone, where it was operated in conjunction with an extensive solar evaporator of ocean brine. The mother liquors from the “salt gardens” were subjected to further treatment by the Balard process for the extraction of potassium chloride. A product of about 80 per cent. purity was obtained. I t is estimated that the annual output in potassium chloride from this process was a t one time 400 tons per annum. The exploitation of the potassic compounds encountered in the socalled Stassfurt deposits of salts was partially instrumental in bringing about the decline of the kelp industry in Europe and successfully impeded the further development of the industries based on the extraction of potassium chloride from sea water. The value of and ready market for the low-grade potassium compounds, or mixtures, as manure salts for fertilizer purposes should prove an advantage to the latter industry to-day not enjoyed by that industry in its incipiency. The Solar refineries of the Pacific Coast are situated a t San Mateo, M t . Eden and Alvarado, California. Technology.-The sea water is pumped a t high tide into one end of a long series of shallow ponds. These are connected with each other, and as the evaporation proceeds, the brine flows through the series of ponds,
TABLEVII-ANALYSES OF BRINESFROM SALINE LAKES OF OREGON.POTASH RECORDED AS P E R CENT. O F TOTALSOLIDS. A. R. MERZ,ANALYST Total solids KzO Grams per No. Location 100 cc. Per cent 11B9 Water from Summer Lake. .......... 2.04 1.54 Alkali Lake, water from middle “lake” llB49 or pond on playa. . . . . . . . . . . . . . . . . 11 . 5 6 4.08 Alkalilake. Water fromsouth “Lake” 17.52 3.59 llB64 TABLEVIII-ANALSSES O F BITTERNSF R O M Water from Albert Lake., 4.50 1.79 llB70 AXALYST Serial 11B 11B 11B The brines of the remnant lakes and the salt crusts No. 198 199 200 of the playas of other basins in the northwest and K . . . . . . . . . . . . . . . . 8 . 2 1 3 . 4 1 3 . 2 southwest have been examined and, in brief, their Na . . . . . . . . . . . . . . . 7 2 . 6 6 2 . 7 6 0 . 9 2.2 0.6 Ca . . . . . . . . . . . . . . . 1.2 salts have been found to be largely non-potassic in Mg ............... 2 4 . 0 2 3 . 4 5 0 . 6 composition. In no other instances to date have C1. . . . . . . . . . . . . . . . 1 7 9 . 2 1 7 6 . 6 1 7 9 . 4
...........
potassium compounds been found in even remotely commercially interesting amounts. SOLAR REFINERIES
O F T H E PACIFIC COAST
When potassium compounds first found employment in the arts and industries, their main sources were kelp, or the ashes of sea weeds, and barilla.‘ Kelp was a sintered mass of potassium, sodium, calcium and magnesium chlorides and carbonates, with which various amounts of sand were intermixEd. Generally, during the incineration, interaction had taken place to form silicates. For the preparation of potassium salts this was leached and the lixiviate, after being allowed to settle and filtered, was evaporated for the fractional crystallization of potassium sulfate and chloride. The preparation and treatment of kelp during the early part of the 19th century constituted one of the important industries of the northern British Isles. Following the development of the market for potash, the extraction of the latter from sea water became For a complete bibliography of the literature dealing with kelp and barilla see “Reference List of Papers Concerning the Economic Uses of Algae and Concerning the Salts Derived from Ashes,” which is printed as Appen. S. of Senate Document 190, 62nd Congress, 2nd Session, being a preliminary report by the Bureau of Soils on the “Fertilizer Resources of the United States.”
23
SO4 . . . . . . . . . . . . . . . 3 0 . 0 3.0
Br . . . . . . . . . . . . . . .
31.4 2.0
53.6 2.0
SEA
WATER. R. I?. GARDNER.
11B 201
11B 202
14.6 21.5 24.5 4.7 0.5 1.0 62.7 79.4 183.3 220.1 74.2 62.0 3.0 2.0
11B 204
lln 205
35.0 11.8 9 3 . 6 551.1 0.2 1.1 8.6 43.9 180.4 190.8 29.0 55.8 2.0 2.8
CONVENTIONAL COMBINATIONS KCl. . . . . . . . . . . . . . 1 5 . 6 25.5 25.5 27.8 41.0 66.7 22.5 NaC1. . . . . . . . . . . . . 1 8 4 . 2 1 5 9 . 1 1 5 4 . 6 6 2 . 1 1 1 . 9 2 3 7 . 6 129.7 CaCI2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 . 8 132.9 MgC12. ............ 7 7 . 1 84.5 110.8 176.3 256.9 Na2S04.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.4 2.3 1.7 CaS04.. ........... 4.0 3.3 0.6 3.7 MgS04.. . . . . . . . . . . 3 3 . 9 39.8 65.0 91.5 75.3 35.8 65.4 iMgBrz.. . . . . . . . . . . 3 . 4 3.4 3.4 3.4 2.3 2.3 3.2 DESCRIPTION OF
SAMPLES
Leslie Salt Refining Works, San Mateo, Calif. Mother liquor: representative sample from near northwest corner of mother-liquor pond. 11B 199. Leslie Salt Refining Works, San Mateo, Calif. Sample from southeast corner of mother-liquor pond. 11B 200. Leslie Salt Works, San Mateo, Calif. Mother liquor from salt-making pond (solar evaporator or “salt garden”); pond has been “making salt” during the summer. 11B 201. Oliver Salt Works, M t . Eden, Calif. Mother liquor from slop pond. Represents an accumulation of 5 years. 11B 202. Oliver Salt Works, M t . Eden, Calif. Mother liquor which has been subjected to some special treatment. 11B 204. California Salt Co., Alvarado, Calif. Mother liquor from “slop” pond. Represents about 3 years’ accumulation, with the abstraction of considerable quantities for “forcing” purposes and the addition of small quantities of other waste liquors. 11B 205. Pioneer Salt Co., San Francisco, Calif. Mother liquor. One year’s accumulation. 11B 198.
1 For a description of this process, cf. Wurtz, Hoffmam’s Be?. Wienev Ausirllung, [I] 1875, 410; Lunge, Chem. Ind., 1883, 225.
T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y
24
gradually increasing in concentration. Gypsum is deposited during this stage of the process. When the brine has reached a concentration of about 75" or 80' b y the salimeter, i t is pumped into the so-called lime ponds, a n d when it approaches saturation (100' by the salimeter), thence into the "salt-making'' ponds. Here it is allowed t o deposit salt during a summer. At the end of the season, the mother-liquor is run off or pumped off and the crystallized salt is scraped from the bottom of the pond. The mother liquor is either discarded or is stored in ponds. This is used a t times t o increase the concentration of brines which have not reached a high enough concentration t o deposit salt. The approach of the end of the season, rather than the concentration of the impurities in the mother liquor, is the determining factor in bringing the evaporation to a close. The mother liquors contain, in addition t o their saline constituents, a considerable amount of organic' matter consisting of bacteria, the larvae of a certain fly, and the disintegrated remains of fish. The color of the mother liquors is red.
u. s.
BUREAUOF S O I M DEPARTMENT OF AGRICULTURE WASHINGTON
RECENT ANALYSES OF THE SARATOGA MINERAL WATERS. 11. B y LESLIERUSSELL MILFORD Received October 8, 1912
I n THISJ O U R N A L , 4, 593, was published the first of the series of analyses which are being made for the Saratoga Reservation Commission by the State Department of Health. The analytical data published showed that those springs were four of the most highly mineralized in the reservation. They are strongly alkaline-saline waters having a large excess of sodium chloride and a high calcium and magnesium bicarbonate content. Since this first paper was written several more analyses of the various springs have been made. The results which are given below show t h a t these springs are less mineralized than the four previously published and are representative of the milder salinealkaline class. Many of these saline-alkaline waters of Saratoga differ from each other, for all practical purposes, merely in the degree of concentration of their mineral substances. The investigation has shown that the mineral water basin is relatively large and waters of diverse mineralization are found, b u t all have general and characteristic constituents. Some of the most valuable waters are so similar throughout, or the gradations are so finely shaded off that the choice between them becomes a personal factor. The strongest waters have a strong purgative or cathartic and diarrhetic action on the system, while the less highly mineralized become of relatively mild therapeutic effect, b u t are valuable and useful table waters. The waters of which the analyses are here given are used partly for drinking and partly for bathing. The pumping of the waters for the gas contained in them has been stopped and the springs are rapidly
Jan., ~ 9 1 3
increasing in flow, mineralization, and carbon dioxide content. Sanitary improvements have been made and the physical conditions have been altered a t many of the springs. Some have been cleaned, some retubed, some capped and some fitted with a water column to. give a hydrostatic head, thus preventing a wasteful flow of the water and exhaustion of the other springs. .The depleted mineral water basin is rapidly restoring itself and the ground water is approaching its normal level. This fact is shown by the revival of many of the springs t h a t had ceased t o flow and the increase in the volume of those t h a t were already flowing. I n the Geyser Park district the famous Geyser Spring has become active and is now throwing a stream of water seveterr and one-half (7 I / ~ ) feet above the surface of the ground, Two other " spouters" have recently been discovered which throw large streams of water accompanied by great volumes of gas nearly seventeen (17)feet into the air. Such conditions give very promising results and prove the wisdom of having unified ownership- of the springs, cessation of pumping the waters f6r gas, and the conservation of most interesting and v&luabl& group of springs in the world. Experiments and research work are now being conducted t o find a spring water suitable for bottling and use a s a table water. The results will be given in another paper. Whenever i t was possible t o obtain an advertised analysis, or analytical data from a previous published report, these have been inserted. Many of these older analyses were reported in grains per U. S. gallpn,,b u t the writer has re-calculated them t o a uniform basis of milligrams per liter and re-stated as ions. The hypothetical compounds have been calculated also from these ions t o conform t o the scheme addpted by the United States Department of Agricu1,tum '&Ad . followed by the State Health Department. The analyses which follow give the cbmparis'ons ofthe mineral content of the springs when analyzed ai' various dates by other analysts and the recent work of the writer. DESCRIPTION O F THE SPRINGS
The Peerless Spring is opposite the famous High Rock and was discovered in 1887. It is one hundred and fifty (150)feet deep and flows freely at, the surface of the ground. The water is highly charged.with carbon dioxide gas and is suitably mineralized-, making a very popular and palatable drinking water. 1t.contains the same general chemical compounds t h a t exist in all of the Saratoga waters, principally, sodium chloride, calcium, magnesium and sodium bicarbonates. Free service is maintained throughout the year, and the public have availed themselves of the opporzunity t o drink the water. The surplus water is used in the Magnetic bath house. Situated about ten (IO)feet from the Peerless is the Magnetic Spring which illustrates the fertility and diversity of Saratoga's mineral water resources. This spring was discovered in 1873and is fifty (go) feet deep. The waters of this spring are mQderately mineralized and, like the Peerless, contain the importaht constituents, sodium chloride, calcium, magnesium and sodium
