THORPE’S ANALYSIS OF THE WATER OF THE HOLY WELL. 19 TI.-Analysis of the Water of the Holy Well,a Medicinal Spring at Humphrey Head North Lancashire. Bg THOS.ED. THORPE,Dalton Scholar in the Laboratory of Owearj College Manchester. HUMPHREY Head is a fine promontory of limestone situated on the northern shore of Morecambe Bay and the spiing issues through a fissure of the rock within a few feet from its base. The well formerly belonged to the Priors of Cartmel and its waker has long been reputed to possess medicinal virtues. Camden in the “Britt,annia,” states that so far back as in his c2 THORPE'S ANALYSIS OF THE time it was much used as an antarthritic and for cutaneous disorders. The water is perfectly clear and colourless and possesses a distinctly saline taste.It effervesces slightly on agitation indicating the presence of free carbonic acid and it exhibits a feebly alkaline reaction. On free exposure to the air it deposits a crystalline sediment consisting principally of calcium carbonate. Frequent thermometric observations made during the last two years show that its temperature is very uniform ; it rarely varies even one degree from the mean point 11.5 C. (52.7 F.) The quantity discharged through the fissure amounts to about a gallon per minute and this rate of flow is constant during the different seasons of the year. Moreover although the spring rises within ten yards of the sea at high water this amount is uninfluenced by the tide. The specific gravity of tlie water at its ordinary temperature is 1005.83 as the mean of concordant determinations made OIL samples collected on different occasions and during opposite seasons of the year.A careful qualitative analysis indicated the presence of the following bodies in estimable quantity :-BWS. Acids or Elements replacing them. Potash. Chlorine. Soda. Bromine. Lithia. Sulphuric acid. Lime. Phosphoric acid. Magnesia. Carbonic acid. Baryta. Silicic acid. Strontia. Ferrous oxide. Manganous oxide. Ammonia. In addition to the above were found traces of alumina iodine fluorine volatile and non-volatile organic matter. A special examination by means of the spectroscope was made for the recently-discovered alkaline metals in the residue obtained by the evaporation of 21 litres of the water but the search was unsuccessful.The method of quantitative analysis employed differed in no important particular from that usually adopted. It was essen- tially that detailed by Fr esenius under the head of ''Analysis WATER OF THE HOLY WELL AT HUMPHREY HEAD. of Mineral Waters,” in the last edition of his Manual. To in-sure accuracy at least two in some cases three determinations of each principal constituent were made and the amount of water taken for the several estimations was whenever prac- ticable ascertained by weight. The following synopsis shows the direct results of the de- terminations the numbers expi-ess the means of the experi- ments and give the amounts in grammes of the substances contained in 1000 grarnmes of water.1. Chlorine.. ............................... 3*31800 2. Bromine. ................................ 0*00034 3. Sulphuric acid ............................ 1.22749 4. Carbonic acid (total) ...................... 0.17259 5. Silicic acid.. .............................. 0.01753 6. Ferrous oxide ............................ 0.00193 7. Manganous oxide.. ........................ 0*00015 8. Lime and strontia together expressed as car- bonates.. ............................. 1’-057 7 7 9. Magnesia (total) .......................... 0-24602 10. Lime and strontia retained in solution’ after boiling the water expressed as carbonates.. 0.92668 11.Lime precipitated on boiling :- Total lime and strontia expressed as car-bonates.. .......................... 1.05777 Lime and strontia retained in solution after boiling expressed as carbonates*. ..... 0.92668 The remainder. ............. 0.13109 Gives in form of carbonate the amount of lime precipitated on boiling. This corresponds to lime .... 0.07341 12. Lime retained in solution after boiling :-Sum of the lime and strontia retained in solution expressed as carbonates. ..... 0.92668 Deduct the strontia (13) calculated as car- bonate ............................ 0.00333 This remainder ............ 0.92335 Corresponds to lime ........ 0.51708 * All the Btrontia was assumed to remain in solution on boiling the water. THORPE'S ANALYSIS OF THE 13.Baryta and strontia :- (a) Baryta ...".. ................ .. .. 0.00031 (b) Strontia .....,.... . . . . . ... . .. 0.00234 14. Phosphoric acid . . . .. . . ...... . ... . . .. . .,. . 0.00017 15. Lithia.. ................................ 0*00066 b. Corresponding to lithium chloride . 0-00187 16. Sodium chloride and potassium chloride and lithium chloride .. .... . . . . . ... . . .... . . 5.11537 17. Potash .. . . . ...,..."... ..... .... . . ... .... 0.06387 Corresponding to potassium chloride 0*10116 18. Soda:-Sum of the alkaline chlorides .. .. .. ... . 5.11537 Deduct potassium chloride . . 0*10116 , lithium chloride.. . . .. 0*00187 0*10303 ICI-Remainder sodium chloride ..5.00234 Corresponding to soda ...... 2.65224 19. Ammonia ... . ..,.... . . . ,... . . . . . ... . . .... 0.00016 20. Total of fixed constituents. .. . .,.... . ... . . .. 7019260 In order to facilitate reference and comparison with other mineral waters the acids and bases art! here associated after the method adopted by Fresenius founded on the assumption that the strongest acid is combined with the strongest base &c. due consideration being of coume given to the fact that the greater or less degree of the solubility of the salts considerably modifies the manifestations of the affinities. Comparison of the total amount of fixed constituents found directly with the sum of the several constituents associated in the above manner.(The manganese and iron are calculated to the degree of oxidation in which they occur in the residue dried at 180" C.) WATER OF THE HOLY WELL AT HUMPHREY HEAD. 23 Barium sulphate .............. Strontium sulphate ............ Calcium sulphate .............. Potassium sulphate ............ Sodium sulphate .............. Magnesium bromide .......... Lithium chloride .............. Sodium chloride .............. Ammonium chloride .......... Magnesium chloride .......... Calcium phosphate ............ Calcium carbonate ............ Ferric oxide .................. Mangano-manganic oxide ...... Silicic acid .................. The residue dried at 180" .. 0*00047 0*00414 1.25677 0°13031 0.34651 0.00042 0.00201 4.71189 0*00033 0.61767 0*00038 0-13071 0.002 14 0~00016 091753 -.-7.22144 7.19260 Amount of the several constituentB in one litre and in one gallon of the water :-Barium sulphate ........Strontium sulphate ...... Calcium sulphate ........ Potaasium sulphate ...... Sodium sulphate ........ Magnesium bromide. .... Magnesium iodide ...... Lithium chloride ........ Sodium chloride ........ Ammonium chloride ...... Magnesium chloride ...... Calcium phosphate ...... Calcium fluoride ........ Calcium carbonate ...... Ferroua carbonate ...... Manganous carbonate .... Silicic acid .............. Organic matter .......... Grm.per litre. 0-00047 0-00416 1.26414 0*13107 0.34353 0*00042 traces.0*00202 4.739 32 0.00033 0.62126 0*00038 traces. 0.13147 000313 0-00024 001673 traces. 7.26367 Grainsper gallon . 0-0329 0.2912 88.4898 9.1749 24.3971 0.0294 traces. 0.1414 331.7524 0.0231 43.4382 0.0266 traces. 9.8029 0-2191 0.0168 1.2341 traces. 508-5199 24 THORPE'S ANALYSIS OF' THE WATER 01. THE HOLY WELL. Cb. c. Cb. in. Gas dissolved in the water and expelled by ebullition in vacuo measured at 11**3C. and 760 rnm. barometer. . . .... . The above composition is perfectly uniform at the different seasons of the year as will be seen from a comparison of the numbers obtained &om the following determinations of the total amount of solid residue sulphuric acid and chlorine con- tained in water collected on (A) August 30th 1865 and on (B) January 1st 1867.1. Estimation of the total amount of fixed constituents. The weighed quantity of water was evaporated with a known weight of pure sodium carbonate in a platinum dish and the residue dried at 180"C. until its weight appeared constant :-Water employed. Residue obtained. Amount in 1000 grm. A. 50.1645 0.3607 7.1947 €3. 66*0903 0.4755 7.1905 2. Determination of sulphwic acid. Barium chloride producing an immediat,e precipitation in the water acidified with hydrochloric wid the estimation of the sulphuric acid was effected without previous evaporation :-Water employed. BaSOI obtained S04H2in 1000 grma.A. 135.390 0.3953 1.2281 B. 96.816 0-2824 1.2269 3. Determination of chlorine (together with traces of bromine and iodine). By Mohr's volumekric method ie. with standard ailver solution and potassium ohromate :-Water employed. Silver required. Chlorine Btc. in 1000 gms. A. 39.2872 0-3969 3-3183 B. 22.7887 0.23025 3.3181 The constant compo&ion and temperature together with the uniform rate of flow of this spring seem to indicate that it originates in a reservoir of considerable extent situated pro- bably in some extensive cavern or fissure at the junction of the slate and limestone formations. Its uniformity of composition &c. cannot be attributed to the influence uf the neighbouring ACTIO?; OF PERMANOANATE OE' POTASH ETC.tide. That such is not the case is well seen fi-om a comparison of the ratios of the amounts of sulphuric acid and cldoiine con- tained in sea-water with the amounts of these bodies deter- mined as above in the water of the Holy Well. In the former case the ratios are as 1to 8 in the latter as 1to 3. Lastly the absence of nitiic acid and the minute quantity of ammonia and organic matter preseiit in the water indicate the comparative freedom from putrescible organic remains of the strata through which the spring rises. My best thanks are due to Dr. Roscoe for the use of his laboratory in the above analysis.