T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING 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' by the salimeter, i t is pumped into the so-called lime ponds, and when it approaches saturation (100' by the salimeter), thence into the "salt-making'' ponds. Here it is allowed to 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 to increase the concentration of brines which have not reached a high enough concentration to 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.
BUREAUO F S O I M DEPARTMENT O F 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 that 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, but 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, but 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 that had ceased to flow and the increase in the volume of those that were already flowing. In 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 to find a spring water suitable for bottling and use as a table water. The results will be given in another paper. Whenever i t was possible to 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,, but the writer has re-calculated them to 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 to 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 that 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
Jan., 1 9 1 3
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 .
25
n I
,’
CONSTITUENTS
ACTUALLY DFTERMINED
AS
EMPEROR SPRING ,
c
DATE O F ANALYSIS
After retubing PUTXAMSPRING PATTERSON SPRING 7 -
7
3 4 5 6 7 RESULTSIN MILLIGRAMS PER LITER Nov. 7 Aug. 12 Jan. 22 Dec. 7 Aug. 12 Feb. 7 Feb. 26 1912 1887 1905 1912 1886 1905 1912 2
1
8
9
June 19 -1891 1912
7
10
11
12
.4pril 10 April 1888 May-21 1912
1912
IONS, RADICLES,AND OXIDESDETERXINED
Formula SiOa ........................
16.95 11.71 2892.97 a
.................
so4
Before retubing
MAGNETIC SPRING
PEERLESSSPRING
HCOs. . . . . . . . . . . . . . . . . . . . . . . Nos. ........................ NO2 ......................... PO&.
a
....
trace a trace 2046.51 16.08 0.06 7.40 8.76 2.52 a 500.86 156.40 a a 104.04 1398.27 2.26 3.17 1.18
As04. . . . . . . . . . . . . . . . . . . . . . . . BO2 .........................
c1. . . . . . . . . . . . . . . . . . . . . . . . . .
Br.. . . . . . .......... I ...........................
......................
Fe and AI . . . . . . . . . h . ........
.........................
Ca. .........................
........
........
..............
K ..........................
...................
Na. Li . . . . . . . .............. NH ........................ Oxygen t o form Alz03.. dkfketl to form Fez03.. Oxygen t o form MqO,.
....... ....... ....... F ........................... Organic m a t t e r . . .............
14.80 4.00 2634.40 none trace none none trace 1773.10 16.80 1.00 a 5.60 a none 530.40 90.90 2.10 none 94.70 1298.50 0.44 5.88
6.27 trace 1822.23 a a a a a ’
781.28 0.78 a 0.16 2.61 4.63 a 366.22 98.80 trace a 72.02 539.83 0.36 a 2.18
NH,Cl. ....................... 9.40 17.46 11.22 a LiC1 . . . . . . . . . . . . . . . . . . . . . . . . . 13.70 2.64 5.20 2.19 KC1.......................... . 183.24 164.50 206.33 1 3 6 . 6 3 NaCl. ........................ ,3199.91 2771.60 2495.83 1177.35 K B r . . ...................... 24.02 25.00 14.00 1.15 K I . . .... .............. 0.07 1.30 1.12 a 5.90 Na@04.. . . . . . . . . . . . . . . 17.33 31.67 trace NaNO3.. .................... a none none a NaNOz.. . . . . . . . . . . . . . . a trace trace a NaBOz.. . . . . . . . . . . . . . trace trace trace a NaHC03.. . . . . . . . . . . . . . . . . . . . 490.67 280.87 752.30 585.31 Ba(HC03)z. & 3.90 5.56 trace Sr(HC03)z.. . . . . . . . . . . . a none trace a 949.33 547.30 984.13 599.73 Mg(HC03)s. ............ 6 a ( H C 0 & . . . . . . . . . . . . . . . . . . . 2228.49 2148.10 2141.96 1483.25 Fe(HC03)z. . . . . . . . . . . . . . . . . . . 23.60 17.80 36.47 0.51 Mn3Ol. ....... 0 a trace a Alz03. ....................... 2.52 a 10.61 4.63 Fez03 ...................... a a ..... 10.57 Si02 ........................ 16.95 14.80 11.80 6.28 Total solids in solution (computed). 7159.23 6472.60 6541.21 3692.58 Residue on evaporation d a a 4880.00 a a a a 9.5‘C.
.
............
...
...............
42.70 2.30 1816.80 trace trace none none trace 1313.40 11.80 0.30 a 97.80 a none 326.40 122.80 4.40 trace 56.90 849.70 3.20 3.42
50.75 10.09 1491.93 trace trace none none trace 669.93 4.91 0.31 16.00 16.60 1.10 none 269.10 84.50 3.50 trace 34.55 487.98 1.73 2.79 0.50
30.15 13.15 39.84 20.75 17.44 35.23 3.30 7.07 96.50 4.15 1419.21 2431.21 2612.20 1394.80 3285.28 a trace 0.09 a trace 0.04 trace trace trace a a none a none none none none a none a trace trace a trace trace 725.88 1594.74 2204.28 6 1 9 . 4 6 2896.70 4.43 11.59 17.25 8.87 8.93 0.31 0.38 1.20 0.15 2.18 10.91 4.28 5.81 10.29 6.49 12.71 10.00 6.81 10.45 6.91 3.40 10.79 1.88 0.30 0.80 none trace 7.34 trace 2.56 296.90 511.01 461.91 421.57 546.44 83.20 145.73 177.79 89.04 251.32 1.30 1.29 10.22 0.47 trace 0.20 trace a 0.19 trace 39.68 110.25 26.38. 64.08 110.17 482.73 1005.04 1519.01 474.97 1906.77 1.27 4.12 2.44 1.10 4.09 2.75 3.97 a 2.36 7.80 1.60 5.07 0.88 0.10 0.38
13.50 92.80 1211.70 1.77 trace none none trace 438.10 4.09 0.31 6.19 7.57 2.61 none 231.57 63.75 trace trace 48.24 356.33 2.28 1.40 1.23
..... ..... . . . . . 24.00 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................ 2.84 ..... 0.99 ..... trace ............... . . . . . . . . . . . . . . . . . . . . . trace ............... .....................
. .
.....
11.80 21.42 2887.65 none trace none none trace 1624.43 9.55 0.85 11.47 17.09 10.61 trace 528.88 162.13 2.94 trace 112.93 1152.00 0.80 3.78 4.99
8.17 11.77 10.16 8.27 a 19.40 10.63 7.67 24.94 14.79 97.50 61.31, 71.55 198.70 34.00 2051.30 1032.31 1120.69 2429.03 3585.65 17.50 , 7.20 6.50 17.00 25.29 0.40 0.40 0.40 0.50 1.71 . 3.40 14.95 52.15 4.88 10.45 trace trace trace 0.12 trace trace trace 0.06 trace a trace trace trace trace a 151.20 281.85 91.76 169.83 385.95 8.30 , 6.62 2.50 2.44 19.32 trace trace 0.50 trace a 739.30 512.90 505.00 884.58 1079.18 1321.90 1090.00 1202.40 2069.59, 1870.74 132.90 50.88 34.70 13.61 18.47 a none none trace 10.18 1.10 3.40 10.79 1.88
{80,00t
. . . . . . . . . . . . . . .
6.99 23.02 7.10 24.76 114.22 200.11 913.83 4545.67 13.00 13,49 0.20 2.85 142.85 6.13 trace a a trace trace trace 252.95 455.37 0.89 trace 0.45 trace 5 4 0 . 2 3 1525.15 978.36 2213.08 32.72 20.69 trace 3.55 0.30 0.80
. . . . . .
4.15 13.82 88.18 629.32 6.00 0.40 137.37 2.42 trace trace 232.36 trace trace 386.69 937.87 19.68 none 2.61
.....
42.70
50.75
30.15
13.95
39.84
.20.75
17.44
13.50
4675.96
3129.17
3137.60
5851.73
7097.46
3024.84
9052.11
2474.64
a 2288.00 a 11.1OC.
2398.00 9.6OC.
4696.00 a 2188.00 10.O°C. 1 0 . 5 5 ° C . 1 1 . 1 ” C .
a a
1768.00 10.3’C.
1, 11. Chandler & Pellew-Hydrotherapy a t Saratoga b y J. A. Irwin, 1892. 2, 5. Mineral Waters of t h e U. S. U. S. Dept. of Agriculture, Aug. 12, 1905. 3, 6, 7. 8, 10, 12. Fdes N. Y.S t a t e Dept. of Health, 1912. 4. Samuel Duffield Hydrotherapy at Saratoga b y J. A. Irwin, 1892. 9. Maunce Perkins
bicarbonates. This spring has a wide reputation for bathing for the cure of rheumatism, gout and skin diseases. There has been nothing found in analyzing the water from this spring which would account for its name, “Magnetic.” The spring is an artesian well with an iron casing driven into the earth. The phenomenon of magnetism is exhibited principally in at-
a, Not given. Other References: Advertised analyses in various circulars. Therapeutic Saratoga-Amencbn Medical Association, June, 1902. “Mineral Waters of the U. S. and their Therapeutic Uses,” J. K. Crook, 1899.
tracting small objects to the iron casing, the clinging of a steel tape t o the tubing when measuring the depth of the well and the deflection of the magnetic needle in the vicinity. The belief is that the phenomena are induced by earth magnetism, aided by the rise and fall of the drill inside of the iron casing, producing sharp vibrations which tend to facilitate the
26
T H A J O U k N A L O F I N D U S T R I A L A N D ENGINEERING C H E M I S T R Y
Jan.,
I913
readjustment of the polarized particles of iron and waters. The Patterson used to appear on the market theiiorientation to the direction of earth magnetism as a bottled water, but the spring is not being exa t that point.’ ploited now. When, after the drill is magnetized, i t is repeatedly SANITARY ANALYSES passed (in the process of drilling) up and down through In order to insure the wholesomeness and purity of the easing in the same position and direction of move- the waters, sanitary and bacteriological analyses of ment, i t gradually imparts its magnetism to the casing. the springs have been made from time to time. The Sometimes in driving the casing, by means of a heavy sanitary analyses have shown small amounts of free weight, vibrations are set up much the same as those and albuminoid ammonia, low nitrates, and nitrites. in the drill and induce more or less magnetism. The bacteriological examinations showed a very low Opposite the Peerless and Magnetic Springs and count and absence of B . Coli, which indicates high about one hundred (100)feet south of the celebrated sanitary purity. High Rock, is situated the Emperor Spring. This STATEHYGIENIC LABORATORY spring was cleaned and retubed to a depth of I I 7 feet STATE DEPARTMENT O F HEALTH ALBANY, NEWYORK in April and gives a water twice as strongly mineralized as the water showed before retubing. It is just back THE QUANTITATIVE SEPARATION OF MIXTURES OF of this spring where the escarpment of the geological CERTAIN ACID COAL TAR DYES’ fault, which gave birth to the mineral springs, is best By W. E. MATHEWSON displayed. Received January 22, 1912 This rocky cliff in now exposed as the buildings with INTRODUCTION their attendant refuse and rubbish heaps, which forThe use of immiscible solvents for separating mixmerly concealed it, have been removed. The water tures of acid coal tar colors is discussed in most standof the Emperor Spring flows freely a t the surface of ard works on the subject. Loomis’ gives data conthe ground and resembles very closely that‘ of the cerning the solubility of a large number of common Peerless. It has a good supply of gas and is suitably dyes, and Seekers has published qualitative separamineralized. The water is drunk a t the spring, free tions of Orange I and Naphthol Yellow S from certain service being maintained. The excess or overflow other dyes depending on the use of amyl alcohol. from the bowl is piped across the road to the Magnetic In such procedures any variation made in the acidity bath house, where i t is used for bathing. has been attained by using acids of different degrees The Putnam Spring was discovered in 1890 and is of dissociation, as acetic acid and a mineral acid, about 2 0 0 feet deep. This was known as the Leving- and not by adding varying amounts of the same acid. ston Spring and is north of the Patterson Spring and Chiefly with the object o making a quantitative separated from it by Phila Street. This Spring is sit- separation of the colors permitted in foods (Naphthol uated in the Congress Park group and belongs to the Yellow S, Ponceau 3 R, Orange I, Amaranth, Light milder class. The Putnam has not been exploited Green SF Yellowish, Erythrosin and Indigo Carmin) , 4 commercially, except in connection with the mineral their ratios of distribution between dilute hydrochloric water baths at the Levingston bath house, which acid of different concentrations and certain immiscistands upon the same lot and under which the waters ble solvents were determined.5 The data indicated of the spring emerge. This spring does not flow a t the a method that gives good results in practice and is of surface of the ground, so the sample for analysis was quite general applicability. Some figures have also obtained by pumping. The analysis is given for its been obtained for other similar colors that will show scientific interest and completeness of the series. The where separations can be made and can also be apwater is high in sulfates. It is not used a t the bath plied for qualitative differentiations. house at present, as an arrangement has been made DATA OBTAINED whereby the surplus water from the Hathorn Spring In the accompanying table the figures given show No. I is pumped to the baths and used for bathing. the percentage of color remaining in the aqueous A few feet south of the Putnam Spring is the Pat- layer after shaking with an equal volume of the imterson Spring. This Spring was discovered in 1888 miscible solvent. A solution containing a quantity and is 2 5 0 feet deep, 190 feet being through solid rock. of dye equivalent to 0.1000gram of pure color was This spring is in the Congress Park area on property diluted to 50 cc. with water and standardized hydronorth of and adjoining the Hathorn Spring No. I . Its chloric acid, sufficient of the latter being taken t o relations to the latter spring are intimate, as have give the solution exactly the acid normality desired. been shown in recent experimental work on the pump- I t was then shaken out with 50 cc. of the solvent. ing of this spring and noting the effect on the mineral (This shaking was continued for five minutes with content, flow, and other physical conditions of the dichlorhydrin, two minutes with the ot’her solvents.) Hathorn No. I , This water is also high in sulfates 1 Published by permission of the Secretary of Agriculture. and is very similar to the Putnam. 2 U. S. Dept. Am., Bureau of Chemistry, C h c . 63. The waters of the Patterson have been deemed val3 “Allen’s Commercial Organic Analysis,” 4th Ed., Vol. V. 1 U.S. Dept. Agr., Office of the Secretary, Food Inspection Decision ‘76. uable for certain disorders of the human body, but 5 Distribution ratios of the permitted dyes betweeq dilute hydrothey have not had the reputation of some of the other chloric acid and amyl alcohol were sent out by the writer in April, 1911, 1 Underground-Water Papers 1910. Supply Paper 258.
U. S . Geological Survey Water-
in a circular letter in connection with the cooperative work of the Association of Official Agricultural Chemists.
