HOW ON A DENSE BRINE X.-On a Dense Brine from Saltsprings Nova Scotia. By Prof. How D.C.L. University of King’s College Windsor N.S. THE analysis of mineral waters is a subject full of interest. Chemists see in every instance means of comparison respecting the accumulation of ingredients in the solvent and matter for argu- ment concerniiig the chemical changes capable of producing the associatioris observed. The s:gnificance of water analyses when properly executed and reasoned on is shown by the amount of criticism which has appeared* of late years on the want of uniformity in the modes of arranging the results both BY regards the standard of quantity and the principles upon which allotment of the constituents ehould be made. Geologists consider the nature and quantity of the contents of waters in connection with the sources of the elements and find in waters at once the proofs and the agents of important changes in the composition of the earth.Every one mill remember what use was made of such el-idence in the Presidential address of Sir C. Lyell at the late meeting of the British Associatioil at Bath. The importance of the researches of Forchhammer on the constitution of sea-water has been still more recently declared in the annual address of the President of the Royal Society. Physicians and invalids need only be reminded that curative properties may be at once justly assigned to a water in consequence of its analysis having been minutely made. 3t is curious that among the analyses recorded of late years few or none are of waters of brine-springs excepting the very it See for esamples R.Ha in es M.B. in Chemical News iv 29 and Editorials in the kame Journal iii 285 315. Also Miller ii 1088 flst ed.). FROM SALTSPRINGS NOVA SCOTIA. valuable series by Hunt in the ‘‘Geology of Canada.” Several most interesting waters have been examined in which chloride of sodium is a chief constituent but its amount is so nearly approached by that of some other salt that such waters are properly called strongly saline in contradistinction to true brines in which com- mon salt is by very much the prepmderating ingredient. I hope the following account of a true brine will be acceptable. The water is remarkably dense and presents some interesting features in its composition :-Nova Scotia affords a considerable number of waters rather strongly charged with mineral matters springing up in rocks of different geological age.Of these I have described several and one,* arising at Bras d’Or in Cape Breton in rwks probably of Silurian age has so far as the relative arnoiints of chlorides and sulphatea are concerned a decided resemblance to that of Wheal Clifford analysedt by Pro. W. A. Miller and described by Sir C. Lyell at Bath. (Wheu I analysed the Bras d’Or water czsium and rubidium had not been discovered and I had only material to determine the leading ingredients.) In both these and in some similar waters described hy Hunt,$ srilphates are very small in amount ;in most of tliese Canadian waters indeed they are absent while chloride of calcium chiefly abounds with chloride of sodium.Other waters of this province have a large amount of eulphate of lime,§ and exceedingly little chlorine. The water now to be described contains an unusually large quantity of both common salt and sulphate of lime. The water rises in the carboniferous system and most. probably in the beds called here the gypsiferous limestones. Tliis system is known to furnish brine.springs in various parts of the province and salt has been made from a few of them including the subject of this paper. The particular locality of this water has its name from the number of its “salt-springs,” for as I am informed by the Rev. Mr. M‘Kay who occupies the manse at the spot and who kindly collected the water for my experiments there are several small salt-springs found liere along a low bank over the length of 150 yards along which course the salt water oozes out at many intervals depositing salt at some places.Besides tliese there are the principal spring from which the water was not * Chemical News ix 97. + Chemical News x 181. Geology of Canada p. 647. $ Chemical News x 98 and Trans. N. S. Inst. ii. HOW ON A DENSE BRINE taken for some reason connected with the state of the neighbour- irig river and also a spring rising at about 9 yards distance from tliis in a hole dug by a company who made salt from the water about twenty pears ago. From this last spring the water analysed was taken in September 1864.Mr. M'Kay tells me the water is applied externally for the cure of rheumatism and he believes it to be effective. I imagine the spring to be thermal for my attention was first drawn to it by a gentleman mentioning as ZL singular circumstance tliat the rocks forming the basin of the water in which he bathed were sensibly warm to his feet. The water as received contaiiied floating organic matter in small amount arid on standing it smelt very decidedly of sulphuretted hydrogen due of course to the reduction of asulphate. To ohtain ail idea of the amount of change occurring under these circum- stances I determined the sulphuric acid twice at an interval of a full month The first experiment gave 92.799 grains SO per gallon. , second , , 91.020 , 99 >) It appears then that the waters alter considerably from this cause which is often observed in operation.On this account the total lime magnesia and sulphuric acid given below are as found in portions of the water taken for analysis on the same day; the chlorine was determined four days after. The first alkali deter- mination proving unsuccessful I could only take that made about a month later than the experiments mentioned and I found the chloride of potassium to be very small in amount. Phosphoric acid was found in decided quite determinable quantity and I believe the precipitate formed on bJ- boiling contained a portion of this acid for in an analogous water I proved it to be present in the peroxide of iron obtained from the carbonates thrown down Boracic acid was also clearly indicated after evsporatiug about 22,000 grains of water and testing with turmeric paper the liquid which drail;ed from the nearly dry residue rendered acid by hy- drochloric acid especially by dipping and drying the paper several times in succession.Bromine was detected without difficulty in about 8,000 grains bnt iodine could not be found in the same quantity. Nitric acid could not be found in the residue of 22,COO gratins. The following are t,he results of the quantitative analysis so far as it was attempted the substances actually found bcing these :- FROM SALTSPKINGSJ NOVA SCOTIA. Grains Grains. Grains. in a gallon. 14,000 water gave by boiling *755CaO.CO = CaO.CO 3.775 J> >, J> *775ZMgO.PO,= MgO.CO 2*93;L JJ >J >> 0025Fe,O = FeO.CO 0 181 J> 2>500 )J *O20 SiO = SiO 0-560 JJ >J ;J 9.475 BaO.SO = SO 91.020 >, JJ ) 5.870 Ca0.C02 = CaO* 89.920 J Y> 1) 1.2802MgO.PO,= MgOt 12.910 300 ¶J 44.400 AgCl = C1 2561*a06 ,J 800 >> 47.240NaCl = NaCl 4133.500 JJ By calculating on the pim of Fresenius we obtain as existing in the water these constituents :-Per cent.Grains per galIon. 0. Carbonate of Lime .. .. -00539 3.775 Carbonate of Magnesia .. .. *00418 2.932 Carbonate of Iron .. .. .. *00025 -181 Silica .. .* .. .. .. -00080 -560 Sulphate of Lime .. .. .. -22104 154.730 Chloride of Calcium.. .* .. -07415 51.910 Chloride of Magnesium .. .. -03904 27-330 Chloride of Sodium (+ a little KCl) 5.90500 4133.500 Phosphoric Acid Boracic Acid Undetermined.Bromine i Organic Matter --6.24985 4374.918 Specific gravity at 53" Fah. . 1046.69. The total weight of solids contained is very large. The follow- ing list shows the contents of some waters selected from the very limited number of those holding more than 1,000 grains in the gallon :-* After deducting CaO = CaO.CO thrown down by boiling. + After deducting MgO = MgO.COn thrown down by boiling. VOL. XVIII. E HOW ON A DENSE BRINE Gains in a gallon. ‘I’he most strongly saline water of Cheltenham contains .. .. .. .. .. 1033*600* The strongest brine of Canada contains .. 1469-909t Sea-water (mean quantity) contains .... 2401280Q The second strongest saline water of Canada contains .. .. .. .. .. 3242.260f‘ The water of saltsprings Nova Scotia contains 4374,918 The strongest saline water of Canada contains. . 4762,960t The water of the Dead Sea (largest amount found) cont aim .. .. .. .. I8550*000~ If we compare the Saltsprings-brine and some other waters rich in chlorides with sea water as regards the relation of chlorine to sulphuric acid we observe great dissimilarity ;thus :-c1. so,. In the strongest Cheltenham water the relation is as 100 32-10 In Sea-water (interior of Baltic) ) , 100 14.9711 , (open ocean mean) , , I00 1‘1*89[1 7, In Saltsprings water , 100 3.55 In VC%eal Clifford 9 , 100 1-83 In Dead Sea 9 , 100 0.35 On the other hand out of 21 Canadian waters abounding in chlo-rides sulphuric acid is found in five only and in these in quite small proportion ; and the same is the case in the Bras d’Or water before mentioned as resembling these and the water of Wheal Clifford.Although the relative amount of sulphuric acid is low in the Saltsprings water as compared with that in sea-water the quantity of sulyhate of lime it forms is larger than is found in most waters. In looking over numerous analyses I have met with few waters which resemble closely or exceed the Saltsprings and some other Nova Scotia waters in this respect. The following * Scudamore quoted in Abel and Rowney on Cheltenham WatersJ Chern. SOC.Qu. J. 1848 vol. i. p. 193. -f Hunt Geology of Canada pp.547 548. 5 Forchhammer Proc. Roy. SOC in Chemical News x 293. Booth and Muckle Jahreabericht 1849 p. 613. II Fo r c h h a m m e r Eoc. cit. the other calcillations are mine from published analyses before referred to except in the case of the Dead Sea ; the analgsis of thia taken is by Mar c h a n d Jahresbericht 1840 p. 613. FROM SALTSPRTNGS NOVA SCOTIA. 51 list shows in round numbers the amount of sulphate of lime contained in some of the waters be€ore adverted to and in some others :-Grains in aga:lon. Bras d’Or water Cape Breton contains Sulphate of Lime 1 Wheal Clifford water Cornwall >9 J? 12 Dead Sea water ,3 9 61 I?ath water YY >> 96 Sea water (British Channel) >9 ,? 98 Che1 tenham water (strongest) St.Catharine’s water Canada > 9) , > 116 153 Spa Spring water Nova Scotia >I ,I 106 Wilrnot water 9 >J > 12 4 Saltsprings water 9 >¶ > 158 Wilmot water ¶Y I> ,> I61 Ivandn water The Banat ,9 9) 195 I As according to Fresenius 70,000 grains of pure water can dissolve only 163 grains of sulphabe of lime it appears that two of the Nova Scotia waters are very nearly saturated while that of Ivanda in the Banat is considerably supersaturated. Hence we have in the latter case an illustration of the way in which the solubility oi salts is modified by the presence of others. l’lie analysis of Iranda water is contained in an account of some mineral waters published at the London Eshibition of 1862; it is by Ragsky. It will perhaps be agreeable to some to see what other salts are present in the water to account for the pre- sence of so much sulphate of lime ;the leading constituents are in round numbers :-Grains in agallon.Sulphate of Lime .. .. .. 195 Sulphate of Soda .. .. .. 881 Chloride of Magnesium.. .. .. 109 Nitrate of Magnesia . . .. .. 21 -Amount of ingredients being . . 1238 ahd sulphate of sods is one of the salts mentioned by Fr eseniu s as increasing the solubility of sulphate of lime. I may meiition that in the Spa Spririg and Wilmot waters in the list above EfL HOW ON A DEXSE BRINE given the total contents per gallon are respectively in round tiurnhers 138 and 141 grains so that the sulphate of lime is by much the leading ingredient.While upon the subject of the solubility of salts I venture to touch upon two other cases in hopes of exciting useful discussion in an assemblage of chemists. One of‘ these is the solubility of carbonate of lime in water. According to Fresenius (Quantitative Analysis 3rd ed. p. 496) “the simple carbonates of lime and magnesia are not altogether insoluble in water and to be as nearly accurate as possible proper correction must accordingly be made for this in the calculation.” On consulting p. 634 at experiment 25 we find that 10,601 parts cold water dissolve 1 part of carbonate of lime; hence a gallon= 70,000 grains of water must dissolve 6.58 grains. Is this amount allowed in all .water znalyses where the salt is met with? We have only to calculate the results given to find that it is not though it is found necessary :,ometimes when there are not sufficient acids for the bases to calculate the snperfluous bases as carbonates as is stated to be the in Abel and Rowney’s analysis of Cheltenham waters (Chem.SOC.Qu. J. I 193 1848) where in one case 22.08grains of carbonate of lime are given while only 12.36 were actually found per gallon. I observe that at the meeting of the Chemical Society held February 5th 1863 this question of the solubility of carbonate of lime was discussed and it was then stated by Dr. Paul (Chemical News vii. p. 80) “that experiments of Fresenius and Dr. E. Nicholson prove that aboiit two grains per gallon is the utmost limit of the solubility of czr-bonate of lime in water.” The President Dr.Hofmann said “in his opinion the amount of carbonic acid required to dissolve carbonate of lime was considerably less than that dciiianded to form bicarbontte of lime ; the proportion however did not appear to be always definite.” Nothing more transpired ns to the actual amount of the salt dissolved by water. The secorrd case is the solubility of carbonate of magnesia in water. To what extent is the salt soluble in pure water? As to its solubility in mineral water Dr. Sterry Hunt says (Geology of Canada p. 557) “It is well known however that an excess of carbonic acid is not necessary to retain carbonate of magnesia iu solution. Carbonate of magnesia is soluble to a considerable extent in an excess of carlionate of soda or of chloride r,f mag-nesium ; and a large quantity of magnesia may be held in solution FROM SALTSPRINBS NOVA SCOTCA.in the form of sesqiii-carbonate.” Under these circumstances what becomes of the ‘‘proper correction’’ of Fresenius “for the solubility of carbonates of lime and magnesia in wuter,” and what reference can be made to the amount of those salts dissolved even when water containing them has been boiled to the expulsion of all carbonic acid if it depends on the nature and quantity of other saltps also present. It was mentioned in a previous page that the Saltsprings water rises in the gypsiferous rocks of lower carboniferous age; it is interesting to find evidence of salt existing in these rocks as this circumstance as well as the occurrelice of gypsum makes them resemble the new red of England.As before stated numerous saltstirings are known to arise in the carboniferous system iii different parts of this province and I may add that at one plsce Antigonish 50 miles from Saltsprings is the c‘ Salt pond,” and at another Whycogomagh in Cape Breton 100 miles from Sdtsprings is the “Salt mountain,” supposed to have been so called from the presence of brine-springs. No beds of salt have been met with but I have small quantities of crystallised rock- salt from a gypsum quarry at Windsor in which several years ago,” 1 proved the existence of sulphate of soda and natro-boro-calcite and subsequeritlyt of sulphate of soda holding im- bedded a new borate which I called cryptomorphite.In this connection the detection of boracic acid in the Saltsprings water arising some 60 miles from Windsor has peculiar Interest. It is possible that there is a coustaut association of those substances which have thus already been found together in greater or smaller quantities in gypsum or in waters froin gypsiferous rocks viz. common salt sulphate of soda magnesia-salts and boracic acid with the gypsum forming the enormous deposits of this rock in Nova Scotia. The significance of these bodies occurring together will be seer. by consulting Hunt’s papers 011 the formation of gypsum and magnesian rocks (Sill. Am. J. [a] xxviii. 365 et seq.) Beds of limestone rich in magnesia are soine-times found e.g. at Walton contiguous to beds of gypsiim. Much however remains to be learned respecting the relations of these rocks; in the meantime it is well to put upon recurd such facts as are gathered concerning them. * Sill. Am. J. [Z] xxiv 230. f Ibid. xxxii 9 and Edin. New Phil. J. 1861.