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Volume 10, 1877
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Art. LXV.—On certain of the Mineral Waters of New Zealand.

[Read before the Wellington Philosophical Society, 12th January, 1878.]

At the instance of Dr. Hector I take up the subject of this paper, but all I think necessary to do at present in this matter is to collate from our several museum and laboratory reports statements of all the analytical results which I have obtained upon these waters, and to compare them with those of the celebrated European waters which ours resemble, stating at the same time their therapeutic properties, either as deduced from their composition, or such as to my knowledge have actually been discovered by direct observation.

The arrangement of these waters here will necessarily be a geographical one, for I find that to present them in anything like a chemical order, that is, classified according to their composition, would entail upon me a far greater expenditure of labour and time than I can well spare, as several compendious tables would in such case have to be re-cast, — in fact, completely broken up, owing to their arrangement being geographical, dominantly so at least. The task of presenting our mineral waters in chemical order I therefore leave for some future time, when the whole or the greater number of them shall have been analyzed.

There is this to be said in favour of the geographical arrangement I propose, viz., that it will enable anyone to gather at a glance the nature of all the waters of any particular district which have been reported on by the Geological Survey Department.

It will be observed that several of the analytical results I shall describe are very meagre, but I have decided to enter all that has been accomplished in the Colonial Laboratory upon these mineral waters, as a little information even regarding any water may be valuable, and suffice for one's wants until opportunities occur for making it fuller.

The following is a list of the localities whence the mineral waters described in this paper were obtained:—

Lab. No.
1. Onetapu Desert, Auckland 151
2. Mahurangi, Auckland 156
3. Bay of Islands, Auckland 520
– 424 –
Lab. No.
4. Puriri, Auckland 1404
5a and b. Waiwera, Auckland 1322, 1820
6. Aorangi, Auckland 1660
7. Rangitaika River, Bay of Plenty 187
8. White Island 232
9. Waimangeao, Bay of Plenty 1524
10. Rotorua, Auckland 1859(1/15)
11 and 11a. Taupo, Auckland 1406(1/12), 1500
12. Spring near lake on west side of Waikato River 252
13. Wallingford, Wellington 56
14. Pahua, Wellington 1211, 1907
15. Northern boundary of Wellington 1567
16. Akitio, Wellington 1758
17. Hanmer Plains, Nelson 500
18. Lake Sumner, Canterbury 1495
19. Gibson Station, Southland 1668

1. Aluminous Water.

The first specimen is from Wangaehu River, Onetapu Desert, in the Auckland provincial district, and was contributed by Mr. Mair on 13th January, 1868. It is persistently turbid, and has a very sour taste. The quantity of fixed matters present in one gallon of it are 456 grains, and their composition is mainly that of common alum. A large quantity of magnesium and ferrous chloride is also present.

2. Mahurangi Water.

From the springs near Mahurangi, Auckland provincial district, three samples were collected by Mr. Justice Gillies in January, 1868:—

  • a. Cold spring, contains 74.0 grains of solid matter per gallon.

  • b. Hot spring, " " 140.4 " "

  • c. Hottest spring, " " 141.6 " "

The solid residues of a and b when analyzed proved to consist mainly of sodic and magnesium chlorides. None, however, of these samples were fully analyzed for want of material.

Mr. Justice Gillies has stated that the coolest of the springs had a temperature of 110° Fahr. at the time he obtained these samples; and that he “believed that many of our Auckland residents had derived much good from bathing in these springs for the purpose of curing rheumatism.”*

3. Acidulous Water.

An acidulous mineral water from the hot springs at the Bay of Islands,

[Footnote] * Trans. N.Z. Inst., I., p. 71.

– 425 –

contributed by Mr. Hugh Carleton on the 8th June, 1869, has a weakly acid reaction. It has a strong odour of sulphuretted hydrogen, and is slightly turbid from the presence of liberated sulphur. A slight sediment had formed in it, which was separated from the portion analyzed.

The following is the amount and composition of the soluble matters contained in one gallon of it:—

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Protoxide of iron 2.23
Lime 5.97
Magnesia 1.15
Silica 3.10
Sulphuric acid 13.60
Hydrochloric acid 66.91
Sulphuretted hydrogen traces
Fixed alkalies 41.66
Ammonia traces
Organic matter "
134.62

This water is evidently an acidulous one, and is a moderately strong chalybeate. I have not heard of its being medically tested, but it certainly should possess some therapeutic virtue.

A deposit formed by these springs has been also examined; it is a chocolate-coloured substance possessed of moderate coherence, and is spangled throughout with minute crystals of sulphur; reaction strongly acid.

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Approximate Analysis.
Sulphur 83.37
Siliceous matter 16.33
Soluble salts and acids .30
100.00

The soluble part when analyzed proved to be composed as follows:—

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Sulphate of alumina 52.43
" iron traces
Sulphate of lime with a little sulphate of magnesia 27.60
Free hydrochloric acid traces
" sulphuric acid 11.32
Alkaline sulphates and loss 8.65
100.00

4. Alkaline Water.

We now arrive at a water of a different kind from any of the preceding. It is an alkaline mineral water, and great interest in it was

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taken by the local press at the time of its collection. It is from a spring at Hikutaia, Puriri, provincial district of Auckland; collected and contributed by Mr. Robert Kelly, on whose property it is situated, and was received at the laboratory on January 5, 1873. Waters of this kind are chemically distinguished by their more or less caustic taste, which they owe to the large quantity of fixed carbonated alkalies (principally of soda) that they contain.

They are used medically for the cure of gravel, kidney diseases, gout, acidity of stomach, etc.

The value of this water medicinally, as alleged by the Maoris, is no doubt due to the large amount of carbonate of soda which it contains, as iodine only exists in very small quantity, and I have not succeeded in determining the presence of any other substance known to possess (as a component of mineral waters) specially medical qualities.

In the annexed analysis the composition of the fixed matters present in one gallon of this water is stated in grains:—

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Soda 199.010
Potash 2.587
Lime 11.088
Magnesia 8.008
Iron traces
Silicic acid 2.772
Sulphuric acid 2.903
Carbonic acid 300.438
Phosphoric acid a little
Chlorine with iodine traces 13.313
540.119

These constituents permit of being arranged as follows:—

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Chloride of sodium 21.938
Iodide of magnesium traces
Sulphate of soda .940
"potash 4.938
Carbonate of iron traces
Bi-carbonate of lime 28.506
"magnesia 25.625
" soda 452.393
" lithia traces
Silica 2.772
Phosphoric acid not determined
537.112
– 427 –

It should be stated here that the amount of carbonic acid given in the above analysis is merely computed, sufficient of it being taken to make up all the substances in union with it to bi-carbonates. Besides the acid necessary for this, there is a considerable quantity present in a free state: indeed, the water is, I believe, described as effervescing strongly when escaping from the spring.

This water is clear and sparkling, caustic as before observed, and has a specific gravity of 1006.46 at 60° Fahr.

Exposed to the atmosphere a crystalline precipitate formed, consisting principally of carbonate of lime, the following being its approximate composition:—

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Carbonate of lime 81.21
"magnesia 18.79
Iron oxide traces
100.00

I append an excellent and very elaborate description which has been published of this mineral spring:—

“About a mile and a-half from Say's, there may be seen an interesting mineral spring, which will well repay a visit. As we are not aware that it has ever been described, we devoted some time to its examination. On approaching the spring from Say's, a white, somewhat elevated patch strikes the eye. At a distance of half a mile it is very conspicuous in the surrounding fern and swampy land, and looks not unlike a deposit of guano as seen sometimes on the coast. Turning aside to inspect, a few yards through the fern on the left-hand side of the track, we found ourselves on a hard, whitish, oval-shaped mound of calcareous matter, about fifty feet in length and thirty-five feet wide, and of generally level surface. The western end of the ellipse slopes gently away to some low, boggy land, green with raupo, toetoe, and convolvulus. The other end is level with the harder and higher ferny surface of a low, flat spur from the neighbouring ranges, and at this end is an oval-shaped hole, about six feet by five, and three-and-a-half feet deep, but contracting regularly downwards like a funnel. The bottom is a mere tube of about three inches in diameter, down which a stick was thrust to a depth of eight feet from the surface. This hole is full of cold, clear, bubbling water, which overflows by a gutter about two inches deep and three inches wide, sunk in the hard crust of the mound and coursing outwards to its western extremity, where the small rill of water loses itself in the swamp below. Bubbles of gas continuously ascend in three or four columns from the bottom of the hole, and burst on the surface in rapid succession. The water has the pleasant, brisk, and

– 428 –

alkaline taste of soda-water, and has evidently built up, by its continuous depositions of the calcareous matter which it holds in solution, the whole of the white-crusted mound which surrounds the pool.

“It may assist the imagination of the reader if he fancy a painter's palette, magnified to a diameter of fifty feet and placed on a low piece of New Zealand swamp and fern. The palette will represent the white mound formed by the calcareous incrustation, the thumb-hole, the bubbling spring. A wavy line drawn from the thumb-hole to the further extremity of the palette is the gutter by which the overflow escapes.

“The deposit from the water is of two distinct kinds—the principal calcareous, and forming the bulk of the surrounding incrustation; the other is soluble in water, has a caustic taste, and is found only during dry weather as a recent white efflorescence caused by exposure to the air, or as little starry groups of crystals in the water of the gutter (soda?). The water is highly charged with carbonic acid gas—as much as five ounces by measure of this gas having been obtained from a soda-water bottle full of the water. That both water and carbonic acid gas (otherwise ‘foul air’ or ‘choke-damp’) exist deep in the earth's crust, is a fact well-known to every miner on the Thames. Deeper still than our mines have penetrated, what water there is must be under a great pressure, and thus rendered capable of absorbing a very large quantity of the gas. When thus supercharged with gas, it has the faculty of dissolving carbonate of lime in considerable quantity, and if it comes in contact with that substance underground will rapidly take it into solution. Suppose now the water, charged to excess with carbonic acid gas, and thereby holding carbonate of lime in solution, to force its way to the surface of the ground: The pressure is taken off; the gas escapes bubbling at the spring; and since the lime can no longer be held dissolved, it deposits itself wherever the decarbonized water runs from its fountain. Such a deposit is formed in New Zealand around many a less fascinating spring than that of Puriri, and we have found at such places mossy and other incrustations which rival the similarly grown travertine of Europe. Three other little bubbling springs were found in the immediate vicinity, all very small, and not one having any zone of incrustation.

“Until a proper chemical analysis shall have been made, it is impossible to form an opinion of the value of this spring as a medicinal agent. That its mineral, gaseous, and other constituents possess some valuable properties, I should think there can be little doubt; and when these are better known it is possible that the medical men of the Thames and elsewhere may be not unwilling to recommend its use to their patients in certain diseases for which it may be found beneficial.”

– 429 –

5. The Waiwera Hot Springs.

These springs, now deservedly in such repute, were sampled for the Laboratory here so far back as January 26th, 1873, by Mr. Hardy; and this sample (a) was about that time analyzed, that is partially so, the result being as follows, stated in grains per gallon:—

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Organic matter 1.70
Chloride of sodium 112.32
"potassium 1.46
Carbonate of lime .82
" magnesia .41
Sulphate of lime .73
Silica 2.70
120.14

This water as received was clear, and with a slight alkaline reaction.

Since this analysis was made quite a large supply of this water has been presented by His Excellency the Marquis of Normanby, and upon this (b) a full analysis has been made. It is considerably more saline, as will be seen, than the former sample, so much so that it manifests a distinctly saline taste when applied to the palate. In other respects, however, it possesses similar characters.

The quantity of fixed matter present in a gallon of it is 219.495 grains, divisible as follows:—

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Chloride of sodium 116.715
" "potassium .091
" "lithium traces
Iodide of magnesium traces
Sulphate of soda .383
Bi-carbonate of soda 87.513
" "lime 10.692
" "magnesia .954
" "iron .683
Alumina traces
Silica 2.464
219.495

This water is of the same kind as that from Puriri, in the same provincial district, but is only of about half its strength. It compares most nearly with the famous continental waters of Vichy in France and Fachingen in Nassau, both of which are largely used medicinally.

I find that Dr. J. Carey has given a testimonial to Mr. R. Graham, of Auckland, in favour of this water, which is to the following effect:— “Having

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observed during my stay at Waiwera the good effects produced by the use of the water, both by drinking and bathing, I am convinced of its efficacy in many disorders, more especially in rheumatism, scrofula, and gout.”

6. A sample of Water from Aorangi.

This water was despatched here by the late Sir Donald McLean, for the purpose, I believe, of having an opinion as to whether it is a mineral water in the popular sense of the term. The characters of it are—colour, pale yellow; tasteless; odourless; weakly saline.

The following is the composition of the solid matters therein, calculated in grains per gallon:—

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Chloride of sodium 1.87
Sulphate of soda 1.08
Carbonate of soda 1.81
"lime 1.76
"magnesia .81
"iron .94
Silica 1.56
Organic matter 3.92
13.75

The carbonates are calculated as neutral or mono-carbonates, but there is a considerable quantity of carbonic acid present in the water beyond what is required for this.

From this it appears that the water can hardly be a mineral one, and if it has therapeutic qualities at all, they must be of a very feeble kind. Date of receipt, December 12, 1874.

7. Water averred to be of a poisonous nature.

Taken from a spring near Rangitaiki River, Bay of Plenty, and contributed by A. P. Seymour, Esq., 14th April, 1868, was found to be slightly turbid and of a faintly sour and styptic taste, with the odour of sulphuretted hydrogen. The quantity was too small to admit of a complete analysis being performed upon it. The total quantity of fixed matters found to be present in the water was 8.19 grains per gallon. They chiefly consisted of alkaline and earthy silicates.

The water was especially examined for mineral substances of a poisonous nature, and the only one partaking of this quality is the gas instanced—sulphuretted hydrogen. Assuming this to be the substance producing the symptoms of poisoning stated, the fact of the water becoming innocuous on exposure to the air can be explained by the circumstance that this gas would soon remove itself or oxidize to an innocuous compound.

8. Acidic Mineral Water from White Island.

Was collected by the Survey in 1868. As received it was colourless and

– 431 –

transparent. A slight sediment had formed which mainly consisted of gypsum in crystalline forms. Its specific gravity is 1.088 at 60° Fah., and the total amount of dissolved matter present to the gallon is 13,638 grains, which is made up as follows:—

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Sulphate of iron (proto) 1059
"soda 658
"potash 275
"lime 235
"magnesia 60
"alumina 80
Chloride of alumina (sesqui) 1703
Siliceous matter 21
Hydrochloric acid, free 9547
13,638

This is therefore shown to be a highly saline water, and charged with free acid to such an extent as in all probability will render it useless for medical purposes.

A full description of the mode of occurrence of this water and the geological structure of White Island have been given by Dr. Hector.*

9. Acidulous Mineral Water.

The water of a small lake—Waimangeao—near Patauki, Mount Edgecombe, is considered to be of a poisonous nature, owing to the fact that birds frequently fall into it when attempting to fly across.

The sample of it which I had was not sufficient to allow of its complete analysis; it was forwarded by Mr. J. C. Young on the 31st of °ecember, 1873.

Characters as follows—Clear and tasteless and of a weak acid reaction. A red deposit had formed consisting of iron oxides, combined with organic matter. The water separated from this deposit yielded 11.084 grains of solid matter per gallon, and it contained a large quantity of carbonic acid besides to which its acidity is due. These solid matters had the following composition approximately:—

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Organic matter 2.956
Alkaline chlorides with carbonates and traces of sulphates 4.928
Sulphate of lime and magnesia .246
Silica 2.954
Iron oxides traces
11.084

[Footnote] * Trans. N.Z. Inst., III., 278.

– 432 –

From this analysis, etc., it appears the water itself is innocuous as a beverage, but is heavily charged with a gas which is poisonous when inhaled, and which, as it escapes, poisons the air above, hence the effect of this air on birds immersed in it.

10. Mineral Waters of the Rotorua District.

A very interesting series of waters has now to be described. They were obtained from the famous geysers and hot water springs of Rotorua by Captain Mair, at the suggestion of His Excellency the Marquis of Normanby, and are reported on in the “New Zealand Gazette” of the 3rd May last.

These waters are fifteen in number, and, as will be seen, while they are generally characterized by the highly siliceous nature of their saline matter, they divide as to their medicinal qualities into two classes.

In the following account of the results obtained, I copy the temperature of the several springs to which they refer, as also the physical description of these springs, from the notes of Major Mair, which were attached to the schedule forwarded with the water.

The quantitative results are stated in grains per gallon.

No. (1)—Is the water from Te Tarata, or the spring which forms the great white terrace of Rotomahana. This is a true geyser, having a large crater-shaped basin 90 feet in diameter, the lip of which is about 70 feet above the level of the lake.

This basin is emptied by an explosive effort, which throws the water to a height of 40 feet, emptying the basin, which again fills up rapidly. The water trickles over the ledges of the terrace, depositing fresh layers of siliceous sinter as it cools in its progress to the lake. The water in the basin has a deep azure blue colour, and a temperature of 210° Fah.

As received at the laboratory, it was faintly turbid, but without any deposit, colourless, and having an alkaline reaction.

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Analysis.
Silicate of soda 68.48
Mono-silicate of lime 1.62
" magnesia .53
" iron .51
Sulphate of potash
" soda 7.84
Chloride of potassium 2.87
"sodium 62.61
Phosphate of alumina traces
Lithia "
144.46

All but soda are mono-silicates, the little excess of silica, 7.66, is included in the soda-silicate.

– 433 –

No. (2)—From Ta-pui Te Koutu, three-quarters of a mile from Ohinemutu, a large pool, 60 to 80 feet deep. The usual temperature of the water in this pool is from 90° to 100°, with westerly or southerly winds; but if the wind changes to N. or E., the water rises four feet in level, and the temperature increases to 180°, with a strong outflow. Thick masses of slimy Confervoid plants line the bottom of the pool. As received, the water was clear and colourless, with an alkaline reaction.

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Analysis.
Silicate of soda 32.12
Mono-silicate of lime 1.62
"magnesia .40
"iron .67
Sulphate of soda 7.06
Chloride of potassium .97
"sodium 29.94
Phosphate of alumina traces
72.78

Excess of silica over what is required to pass these bases as mono-silicates is 5.55.

No. (3)—From Turi-kore or Whakarewarewa, 2(¾) miles from Ohinemutu. The sample was taken from a waterfall which drains from a large pond 300 yards long, the reservoir of a number of boiling springs that are in continual activity. The temperature of this fall is from 96° to 120°. The water is of a dirty brown colour, and is in great repute among the Maoris for the cure of all cutaneous diseases. As received, it was clear and colourless, with a faintly acid reaction, which changes to alkaline on boiling the water.

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Analysis.
Silicate of soda 16.32
"lime 1.61
"magnesia 1.14
"iron .39
Sulphate of soda 13.47
Chloride of potassium 1.24
"sodium 53.61
Phosphate of alumina traces
87.78

No. (4)—From Kuirua, in the native village of Ohinemutu, on the shore of Rotorua Lake, where a strong stream flows from a number of hot springs which cover an extent of about 30 acres. This has a temperature of from 136° to 156°, and is so soft that clothes can be washed in it without the use

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of soap. It deposited a white flocculent sediment in the bottles, leaving the water clear, with a faint yellow tint, and an alkaline reaction.

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Analysis.
Mono-silicate of soda 2.57
"lime .34
"magnesia .12
"iron .31
Sulphate of soda 10.31
Chloride of potassium 2.08
"sodium 45.70
Phosphate of alumina traces
Silica, free 18.42
79.85

No. (5.)—From Koroteoteo, or the “Oil Bath,” at Whakarewarewa.— This is a strong boiling stream, the recorded temperature being 214° from two springs, one of which, surrounded by beautiful sulphur incrustations, throws a powerful jet to a height of 20 feet. The water is distinctly alkaline, or slightly caustic, which is probably the reason for it being termed an “oil bath.”

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Analysis.
Mono-silicate of soda 2.08
"lime 3.16
"magnesia .76
"iron .85
Sulphate of soda 7.49
Chloride of potassium 1.46
"sodium 66.34
"lithium traces
Silica, free 22.40
Phosphate of alumina traces
104.54

No. (6).—Otukapuarangi, the “pink terrace” of Rotomahana. This terrace has been built up round a great circular pool 180 feet in diameter, from which there is a strong outflow of clear bright water, having a temperature of 204° to 208°, and depositing siliceous sinter of a delicate pink tint in large quantities. As received, the water was faintly acid, changing to alkaline when boiled.

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Analysis.
Silicate of lime 1.91
"magnesia 1.16
Chloride of potassium 1.05
– 435 –

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Chloride of sodium 93.55
Sulphate of lime 10.96
"soda 1.01
Alumina as phosphate .54
Silica, free 43.95
Iron oxides traces
154.13

No. (7.) Manupirua, on the S.E. shore of Rotoiti, a beautifully clear pool 20 feet in diameter, having a temperature of 107° to 110°, at the foot of a high pumice cliff on the shore of the lake. The water is clear, with a bluish tinge, harsh to the touch, and deposits sulphur. This pool has a strong outflow of 40 to 50 gallons per minute, and is reported to have great curative properties.

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Analysis.
Mono-silicate of lime 1.51
"magnesia .77
"iron .99
Sulphate of soda 11.50
"lime 2.43
Chloride of potassium .47
"sodium 6.25
Silica, uncombined 8.53
32.45

No. (8.)—From Te Kauwhanga, 1(¼) miles from Ohinemutu, a powerful sulphur bath, having a temperature of 204°. The water as received was clear and colourless, with a distinct acid reaction, and evolving an offensive odour; it deposited a brownish sediment on being boiled. This bath is reputed to have great curative properties, and is known to tourists as the “Pain-killer.”

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Analysis.
Sulphate of potash 2.96
" soda 34.37
Chloride of sodium 59.16
"calcium 3.33
"magnesium 1.27
"iron .25
Phosphate of alumina traces
Silica 16.09
Hydrochloric acid 7.60
Sulphuretted hydrogen 2.01
127.04
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– 435 –
– 436 –

No. (9).—Cameron's Bath, situated in the same locality as No. 6. It is a muddy pool, 20 feet in diameter, having a temperature of 109° to 115°, but kept in a state of ebullition by a powerful escape of gas, which causes faintness when inhaled. The pool has no outflow, and the water is a dirty chocolate colour. As received, the water had a persistent acid reaction and offensive odour; it had deposited a siliceous sediment in large quantities.

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Analysis.
Sulphate of potash .94
"soda 33.47
"alumina traces
"lime 2.11
"magnesia 1.14
"iron 1.20
Phosphate of alumina traces
Sulphuric acid, free 76.79
Hydrochloric acid, free 7.28
Sulphuretted hydrogen .41
Silica 7.01
130.35

No. (10).—From Perekari, 1(½) miles from Ohinemutu. Temperature of water 130° to 150°. A boiling pool in a sand-spit near the lake, in which the water is discoloured, and has a very offensive smell. As received, it was clear and colourless, with a strong acid reaction; it had deposited a great deal of sediment, which consists of nearly pure silica.

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Analysis.
Sulphate of soda 26.75
"alumina traces
"lime 2.45
"magnesia 1.86
"iron .76
Chloride of potassium .63
Phosphate of alumina traces
Hydrochloric acid, free 5.38
Silica 18.17
56.00

No. (11).—From Te Kauwhanga mud bath, 1(¼) miles from Ohinemutu. A thick, brown, muddy water, covered with an oily slime, and having a temperature of 80° to 100°. When received, it had deposited a heavy muddy sediment, and had a persistent acid reaction, and an offensive odour.

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Analysis.
Sulphate of potash .77
" soda 23.71
" alumina 1.46
" lime 2.04
" magnesia 1.62
" iron 1.47
Phosphate of alumina traces
Sulphuric acid, free 7.60
Hydrochloric acid, free 7.66
Sulphuretted hydrogen 3.19
Silica 13.86
63.38

No. (12).—From Ariki-kapakapa, 2 miles from Ohinemutu, a small pool with a strong outflow, having a temperature of 160°. It deposits sulphur, and is surrounded by a great number of other baths and mud volcanoes. It is reported to have powerful curative properties. It was colourless as received, with a heavy deposit of silica, and an acid reaction, which was permanent at its boiling point.

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Analysis.
Sulphate of potash .38
" soda 12.51
" alumina .68
" lime 2.21
" magnesia 1.29
" iron 3.15
Phosphate of alumina traces
Sulphuric acid, free 13.96
Hydrochloric acid, free 2.62
Silica 18.15
54.94

No. (13).—Sulphur Bay Spring, on the edge of Lake Rotorua, formed by innumerable small jets forced up through sand, having a disagreeable odour, and a temperature from 90° to 100°. This bath is reported to have a powerful action on the skin, owing no doubt to the large quantity of sulphuric acid it contains. As received, it was colourless, with a slight flaky sediment.

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Analysis.
Sulphate of potash .07
" soda 8.37
" lime 2.50
" magnesia .93
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Sulphate of alumina traces
" iron 2.68
Phosphate of alumina traces
Sulphuric acid, free 18.02
Hydrochloric acid, free .86
Silica 10.08
Sulphuretted hydrogen 1.01
44.52

No. (14).—From Ti Kute, the “Great Spring,” 10(½) miles from Ohinemutu, a pool three-quarters of an acre in extent, having a temperature varying from 100° to 212° in various parts. It boils furiously, and dense volumes of steam are continually rising from it. The water is of a muddy brown colour, and contains a large proportion of sulphuretted hydrogen, and is reported to be wonderfully efficacious in cases of rheumatism and cutaneous disease.

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Analysis.
Sulphate of potash .59
" soda 12.66
" alumina 11.22
" lime 1.01
" magnesia .69
" iron 1.73
Phosphoric acid traces
Sulphuric acid, free .77
Hydrochloric acid, free 1.63
Sulphuretted hydrogen 5.74
Silica 12.40
48.44

No. (15).—From Te Mimi, Okakahi, a waterfall having a temperature of 90° to 112°. It drains from the preceding (No. 14), and only differs from it in being more dilute, and having a larger proportion of sulphuric acid, and less sulphuretted hydrogen.

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Analysis.
Sulphate of potash .13
" soda 4.78
" alumina traces
" lime 2.04
" magnesia .93
" iron .23
Phosphate of alumina traces
Sulphuric acid, free 12.48
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Hydrochloric acid, free 3.82
Sulphuretted hydrogen .98
Silica 4.12
29.51

I give below in a tabular form the respective quantities of the several substances found to be present in a gallon of each of these waters:—

No. Temperature. Silica. Iron Oxide. Alumina. Lime. Magnesia. Soda. Potash. Lithia. Sulphuric Acid. Chlorine. Sulphuretted Hydrogen. Total Contents.
Deg. Fah.
1 210-214 39.31 .30 .02 .77 .21 67.10 1.81 * 4.42 39.36 153.30
2 90-180 20.18 .30 .01 .77 .12 32.37 .61 3.98 18.63 76.97
3 96-120 13.63 .20 .01 .77 .45 39.84 .81 7.59 33.18 * 96.48
4 136-156 20.09 .10 .07 .16 .07 30.01 1.31 5.81 28.72 86.34
5 214 25.72 .46 * 1.24 .30 39.47 .91 * 4.22 40.96 113.28
6 204-208 45.66 * .54 5.54 .46 50.01 .66 6.33 57.27 166.47
7 107-110 10.31 .40 .06 1.41 .31 8.33 .30 7.91 4.01 * 33.04
8 204 16.09 .14 * 1.68 .62 46.36 1.60 * 20.72 46.72 2.01 135.94
9 109-115 7.01 .54 * .81 .38 14.61 .51 98.72 7.08 .41 130.07
10 130-150 18.17 .30 .04 1.01 .62 12.59 .39 18.16 6.21 57.49
11 80-100 13.86 .70 .38 .84 .54 10.35 .42 25.44 7.45 3.19 63.17
12 160 18.15 1.49 .20 .91 .43 5.46 .16 25.44 2.53 54.77
13 100-212 10.08 1.27 * 1.03 .31 3.94 .04 26.04 .84 1.01 44.56
14 90-100 12.40 .82 4.91 .83 .23 5.53 .32 19.49 1.59 5.74 51.86
15 90-112 4.12 .10 .05 .84 .31 2.09 .07 17.22 3.72 .98 29.50

Note.—The phosphoric acid present is omitted from this table, but appears in the detailed account of these waters.

None of them in their natural state gave any indication of the presence of either iodine or bromine, nor were any such indications observed for those waters which, for more rigorous testing, I evaporated to a small bulk. The waters I thus treated especially for these elements are Nos. 1–6 and 10–14, and as they represent all the kinds of waters of this series, I think it may be safely concluded that these substances are either absent, or, if present, are in quantities so small that they will not exercise any appreciable effect upon any one using these waters.

The metal lithium was found in waters Nos. 2, 7, and 9, but only in such small quantity as not to be readily detected, except spectroscopically.

As this is a substance having active medical properties, even when administered in small quantities, if continuously, it is often an important matter that its presence in any mineral water should be known to those who use it.

A perusal of these analytical results will show that the waters in question belong to two distinct classes—the alkaline and acidulous.

[Footnote] * Traces.

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The alkaline ones differ from those of this class which have been already described in being silicated instead of carbonated. They are, in fact, eminently siliceous waters comparing with the hot spring water of Iceland; any carbonic acid which may have been present in the water when situated at a great depth, being eliminated therefrom as it reached the surface, in consequence of the superior affinity of silicic acid for alkaline bases at elevated temperature and low pressure.

This substitution of silicic for carbonic acid will only affect the waters for therapeutic purposes where they depend in part or wholly for their desired effect upon the presence of carbonic acid. When the alkaline character of the water, however, is alone to be regarded, I do not see why these silicated waters of ours should not (when of about the same strength) be quite as useful as those alkaline waters of the European spas in which the alkalies are combined with carbonic acid, and when neither iodine nor lithium are present to any notable extent. The waters of this kind are Nos. 1–6.

The waters of the other class—the acidulous—are also remarkable as being those from which carbonic acid has been wholly eliminated; but in this case a so-called mineral acid, hydrochloric or sulphuric acid, is the substituting one in place of silicic acid as in the waters of the former class. Silicic acid is, however, generally present, but in a free state as a hydrate, all the silica which is entered in the analytical results of these waters being of the kind known as soluble silica. The waters of this class are Nos. 8–15. Certain of these are hepatic, some strongly so, that is, they contain sulphuretted hydrogen in quantity, and it is only the waters of this kind which it would be safe as yet to look upon as having useful medicinal qualities to a remarkable degree.

These waters are Nos. 8, 9, 11, and 13–15, or those of Kauwhanga, Cameron's Bath, Te Kauwhanga, Sulphur Bay Spring, Ti kute, and Te mimi, Okakahi, respectively.

These waters should prove efficacious in cases of rheumatism and skin diseases. The more palatable ones will of course be those which are the least acidic.

I cannot find that these waters strictly compare with any of those afforded by the European spas; the free hydrochloric or sulphuric acid present in them clearly separating them therefrom.

11.—Taupo Mineral Waters.

I now have to describe a series of twelve waters from various hot springs in the provincial district of Napier, which were presented to this department in June, 1873, by Dr. W. I. Spencer.

– 441 –

Only two of these interesting waters have as yet been fully analyzed, they are Nos. (11) and (12); the former, from the Hot Springs of Tarawera, contains a considerable quantity of free hydrochloric acid, its principal constituent being sodic-chloride.

The other water (No. 12) is from Parkes' Spring, Taupo, and is the most saline water of this series; it contains, besides, much silica.

Both waters are rich in iodine.

Subjoined are the results of these analyses, stated in grains per gallon.

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Tarawera, No. 11. Parkes' Spring, No. 12.
Chlorine, with bromine traces 40.497 56.076
Iodine .714 1.012
Sulphuric acid 2.150 2.156
Silica 2.221 16.752
Carbonic acid traces *35.751
Alumina .621
Iron 1.049
Lime 2.036 1.994
Magnesia .492 .613
Potash 3.681 5.675
Soda 46.495 80.710
Lithia traces traces
Phosphoric acid
99.956 200.739

It will be gathered from these results that the Tarawera water is distinctly an aluminous one, that is, it contains alum in some quantity, and is fairly rich in iodine. It has but few representatives in Europe. One of these is the Labassère (Hautes Pyrénées) which is drunk for bronchial and laryngeal catarrh. The strength of this water, however, is only about one third that of ours.

The other water, that from Parkes' Spring, Taupo, is of very much the same character as that from the Waiwera Hot Springs, but is far richer in iodine; it bears a great resemblance to the mineral water of Luhatschowitz, in Moravia, which is useful in chronic bronchial catarrh, especially if combined with scrofulous complaints, and in congested liver and hemorrhoids arising from sedentary habits.

The samples from the other springs have been examined so far that their general character has been ascertained. The results will be found in the table given on the next page, computed in grains per gallon.

It should be stated that all these samples of mineral waters gave evidence of the presence of sulphuretted hydrogen, but as they were enclosed in corked bottles, the quantity of this gas naturally existing in them could not be ascertained, organic matters, such as cork, being able

[Footnote] * The carbonic acid in No. 12 is that which is in a combined form; there is, besides, a quantity of this acid in a free state.

– 442 –

to generate sulphuretted hydrogen from aqueous solutions of the sulphates when in contact with them—a circumstance I note here especially for the guidance of collectors of mineral waters for analysis.

No Salts soluble in water. Principally alkali chlorides. Salts soluble in acids. Principally sulphate of lime. Silica. Total of Salts. Loss by ignition. Physical character. Reaction.
1 5.28 .74 7.86 13.88 3.47 paleeyellow, clear faintly acid.
2 13.88 4.31 9.25 27.44 3.08 colourless, clear " "
3 3.85 1.69 2.94 8.48 1.54 " " " "
4 138.07 4.21 10.03 152.31 3.09 " " " "
5 64.72 1.63 18.51 84.86 12.97 yellow, turbid " "
6 8.13 9.24 15.75 33.12 1.52 colourless, clear slightly acid.
7 24.12 3.84 28.51 56.47 3.24 " " " "
8 127.62 9.62 6.25 143.49 4.61 " " neutral.
9 6.16 3.08 12.33 21.57 4.65 pale yellow slightly acid.
10 3.09 4.62 6.10 13.81 3.08 colourless, turbid " "
11 2.22 99.95 " " clear very acid.
12 16.75 200.73 " " faintly acid.

In the following schedule the localities of these waters are stated, together with certain interesting particulars respecting them which have been furnished by Dr. Spencer. The general character of each, as deduced from the foregoing table, is also given:—

No. (1).—Otumuheka Spring; collected 1st March, 1873; a siliceous water, more than half its solid matter being silica; the remaining portion is principally chloride of sodium with a notable quantity of iodides.

No. (2).—From same locality; collected same time as above, and is also a siliceous water, but although it contains a larger proportion of alkaline chlorides than this water, it gives but slight indications of iodine.

No. (3).—From the Otumuheka Stream. This stream has a temperature of 78° Fahr., and forms bathing places at Lake Taupo. It is a very similar kind of water to No. (1), and, like it, is rich in iodine.

No. (4).—From the Ruahine Hot Springs, on ground belonging to Mr. Locke. These springs have a temperature as high as 190° Fahr. They are eminently saline, the principal constituent being chloride of sodium, and appear by comparative tests to be the richest in iodine of any of this series of waters; collected 1st May, 1873.

No. (5).—From the baths of Orakeikorako. As received this was very turbid and high coloured. It did not lose its turbidity when allowed to be at rest for a long time. It is highly charged with saline matters, principally alkaline chlorides, and it gives a very distinct reaction of iodine. The organic matter is high in this water.

No. (6).—From a bath named after Mr. McMurray. Is a siliceous water, comparatively poor in chlorides, but rich in iodides.

– 443 –

No. (7).—From the alum caves at Orakeikorako, collected 1st May, 1873. Differs from any of the preceding waters in containing a large quantity of sulphate of lime. It gives evidence of possessing only traces of iodine.

No. (8).—From the Crow's Nest, collected 1st May, 1873. Temperature of spring 179° Fahr., similar to No. (4). Quantity of iodine present is very minute, but still can be detected in it as unconcentrated.

No. (9).—From Waipahahi. Forms a pool 50 by 30 yards, the native name of which is Konekeneke. It has a rocky bottom and forms a fine swimming bath. Temperature of water varies from 98° to 120°; collected 1st May, 1873. This is a siliceous water, from which iodine appears to be absent; at least this element could not be detected in it when concentrated to one-fifth of its original bulk.

No. (10).—From a hot spring on the Oranui block—Te Hukahuka. Forms a bathing place 15 by 10 feet. A cold water creek and hot springs issue from its enclosing rocks at side and bottom. This resembles the spring water of a slate country except that it is largely charged with iodine; collected 1st May, 1873.

From the above tables and schedule it will be seen that we have several kinds of mineral waters here, both hot and cold, within no great distance of each other, which is a circumstance likely to be of considerable advantage to many who may desire to use mineral waters for their health.

It is to be observed that while there is this difference in the constitution of their saline constituents they nearly all contain iodine in sufficient amount to impart to them very decided therapeutic properties. This substance, it may be stated, has been proved to be very efficacious when externally applied in cases of cutaneous eruptions.

I should state that so far back as July, in 1871, I partially analyzed a water (contributed by Mr. Murray Gibbs) from Haweraroa, Tarawera district, but whether taken from the same spring as No. (11) was, or from a hot spring at all, I have no information. However, it is essentially an acidic water like No. (11). As received it was opalescent, of a weak reddish-blue colour, and had an odour of sulphuretted hydrogen. This opalescence is due to the presence of hydrated silica, which in a minutely divided or gelatinous form is transfused throughout the liquid.

The free acid present is principally or wholly the hydrochloric.

11a. Hepatic Mineral Water.

A water collected by Dr. Hector, from Burton's Taipo, is strongly hepatic. Besides the sulphuretted hydrogen which gives it this quality, it contains the other characteristic substances—arsenic and iodine—both however, in small quantity. It is slightly acid, but acquires a strong and persistent alkaline reaction when evaporated to a small bulk.

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In obtaining these data, I unfortunately exhausted my stock of this water.

12. Water from spring on west side of Waikato River.

A water from a hot spring near a lake on the west side of Waikato River, Auckland, contributed by Mr. Justice Gillies, 23rd September, 1868, is clear, of a decided alkaline reaction, contains 47.04 grains of fixed matters to the gallon consisting principally of alkaline chlorides, the remainder being chiefly silicate and sulphate of lime with alkaline carbonates. There was not sufficient of this sample to allow of a complete analysis of these fixed matters.

The following is Captain Hutton's description of this spring—“It was about four miles from Lake Wangape in the Waikato. There were several hot springs close together, but this was the largest of them being fifteen yards long by five yards broad, and it was very deep; the water was so hot that it was impossible to bear the hand in it for more than a second, and on one occasion when he was in company with others, having caught a pig for dinner, they fastened it with flax and threw it into the spring, and on taking it out it was perfectly scalded and they had no difficulty in scraping the hair off; the temperature of the spring was from 160° to 200° Fahr. at the very least. The water itself was almost tasteless; he had drunk it himself. He thought it was the carbonate of sodium which gave it an alkaline reaction. What its effects would be as a mineral spring he could not say; but it was easy of access; was very prettily situated, and was not more than 50 miles from Auckland, and he trusted that some day it would be called into use.”*

13. Wallingford Mineral Water.

The first water which I have to notice, as coming from the provincial district of Wellington, is one from Wallingford; contributed 15th June, 1866. As only a few ounces of it were at my disposal, I have only been able to determine its character and the proportion of the saline matter contained therein. It is faintly acid; has a pure strong saline taste, and is somewhat turbid from the presence of aluminous substances. The total quantity of fixed salts present in a gallon of it is 826 grains. They are mainly composed of alkaline and earthy chlorides. There are present also traces of certain bromides and iodides.

Dr. Grace subsequently handed in a water from about the same locality as the above. The two are similar, but the former is the richer in iodine.

14. Mineral Water of Pahua.

α. This is from a spring on Mrs. Sutherland's run, and is remarkable for the quantity of iodides and the comparative paucity of sulphates therein.

[Footnote] * Trans. N.Z. Inst., I., p. 71, ed. I.

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The first time that this character of the water was elicited was in May, 1872, when I had a small phial of it presented to me by Mr. Douglas McLean, and in my official report thereon I stated that it gave a good reaction of iodine to the proper tests even when unconcentrated, a proof of the richness of any water in iodine, and that by chromatic tests it was ascertained the quantity of this element present in a gallon of the water would not be less than one grain. Further, I urgently requested a sufficiency of this water, to allow of a complete analysis being made upon it, and this I was promised; but the difficulties attending the transport of bulky parcels from these springs here for several years prevented this promise being fulfilled until April 16, 1877, when a large keg of this water (b) was delivered here by Mr. Alex. Sutherland, and I was then enabled to make a very full analysis of it, and note with considerable exactitude its general properties. It proved to be a clear and strongly saline water characterized by the presence therein of a very large proportion of sodic chloride, and an amount of iodine unusual for natural water, a considerable portion of which is very singularly in a free state. It manifests very distinct alkaline reaction, even at common temperatures and when unconcentrated. Lithia appears to be absent, at least I could not detect it, even spectroscopically, in the spirituous extract of the salts contained in half a gallon of the water.

The total quantity of matter which I have determined in one gallon of it is 1474.096 grains, the constitution of which I have made out as follows:—

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Chloride of sodium 1303.329
" potassium .501
" magnesium 34.960
" calcium 120.885
Iodide of magnesium .582
Bromide of magnesium traces
Sulphate of lime 3.026
Phosphate of alumina .641
" iron traces
"lime .430
Bi-carbonate of lime 6.451
Silica 1.696
Iodine, free 1.595
1474.096

Total quantity of iodine to the gallon (free and combined) 2.127 grains.

This water appears to be therefore a strongly chlorinated one, unusually rich in iodine, and, as before stated, is remarkable, and I might almost say unique, in having a portion of the iodine in a free state. The last circumstance has induced me to request a further sample of the water, to be taken under especial precautions to avoid the introduction of anything into it

– 446 –

which would liberate this element. I may state here that I have not yet heard of the existence of free (native) iodine being authoritatively announced.

This water comes under the sub-class alkaline chlorinated water, and therefore resembles those of Wiesbaden, Kreuznach, and Aix-la-chapelle of the continental waters, and those of Cheltenham, Harrowgate, and Leamington of the English ones. It is, however, remarkable for its generally superior strength over the English water of this class, and therefore should manifest medical effects in a corresponding proportion when properly tested.

15. Mineral Water from northern boundary of Wellington.

Another water of the same class as the above, but one considerably less iodized, is that from a mineral spring occurring about the Wellington boundary of the run of Mr. Douglas McLean. Its characters are as follows:—Somewhat turbid, has a decidedly saline taste, and is feebly alkaline to test paper. Its principal constituent is chloride of sodium; it differs from sea-water, however, in containing a notable quantity of carbonate of soda; also in giving a very distinct reaction of iodine to the proper tests for this substance, even when these are applied to the water as unconcentrated. The following results of its analysis are expressed in grains per gallon:—

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Soda 219.310
Potash 2.833
Lime 2.219
Magnesia 7.158
Lithia traces
Iron oxides 1.481
Silica 6.418
Chlorine 240.362
Sulphuric acid .715
Carbonic acid 18.444
Iodine and bromine traces
498.940

These results allow of being expressed in the following manner:—

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Chloride of sodium 392.594
Chloride of potassium 4.448
Iodides and bromides not estimated
Sulphate of soda 1.269
Carbonate of soda 18.604
" magnesia 15.031
" lime 3.961
" iron 6.386
Silca 6.418
444.711
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This water, it will be observed, contains a notable quantity of carbonate of iron, a fact which confers upon it the additional character of a chalybeate, and therefore that of a tonic.

16. Akitio Acidulous Mineral Water.

This is the last water of the Wellington series I have to describe. The sample as received from Mr. Douglas McLean was very turbid, quite tasteless, and colourless when clarified. It is largely charged with free carbonic acid, and gives no reaction of iodine with the starch test when its salts are greatly concentrated.

The following are the results obtained by its analysis computed in grains per gallon:—

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Silica 4.15
Iron and alumina .93
Lime 13.14
Magnesia 2.32
Soda with a little potash* 4.68
Chlorine 1.84
Sulphuric acid 1.02
Carbonic acid, combined 9.57
37.65

This water is therefore eminently a carbonated one containing lime as the principal basic substance of its salts.

It is decidedly chalybeatic and is very much of the same character as the water of Pyrmont (Waldeck) and Recoaro (Venetia).

17. Nelson.

The Hot Springs, Hamner Plains, Nelson, were sampled by Mr. W. T. L. Travers for the Laboratory, 5th April, 1869. The water is transparent, colourless, and tasteless, but decidedly alkaline to test paper even in its normal state. A flocculent precipitate had settled, principally silica, which amounted to 2.11 grains per gallon. The total of fixed matters present was 86.4 grains per gallon. Of this 2.88 grains were silica, the remainder being principally alkaline chlorides and carbonates.

18. Canterbury.

The water of certain thermal springs at the head of Lake Summer, provincial district of Canterbury, has been partially examined, and with the following results:—Reaction faintly acid, colourless, and nearly transparent; total quantity of fixed matter present to the gallon 18.516 grains, which principally consist of alkaline chlorides. Contributor—Dr. Haast; date of receipt, 8th October, 1873.

[Footnote] * Not sufficient water to allow of its determination.

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This water, therefore, appears of such a character that we can hardly expect it to have any marked therapeutic qualities. Though from a thermal spring I question the propriety of designating it as a mineral water, that is, in any special sense of the term.

19. Southland.

A water from Mr. Edmund Gibson's home station, Southland provincial district, was collected in January, 1875, by Mr. Charles Traill, who states that it is deemed a specific for diarrhœa. It is feebly but distinctly alkaline, is quite clear, and tasteless. Submitted to a partial analysis, it afforded me a quantity of fixed salts, equal to 18.516 grains to the gallon, and 7.5 grains of volatile substances (organic matter principally), the rest being ammoniacal salts. There was not sufficient saline matter afforded me to allow of their nature being exactly ascertained, but I observed a considerable quantity of ferric salts present in it; the bulk of these matters were, however, alkaline chlorides and carbonates. It will be observed that the organic matter is very high in amount, and it is to some astringent principle of this that I am inclined to attribute its potency as a specific for the ailment above-mentioned.

The comparisons with European waters given in this paper are founded on the information afforded in Mr. P. Squire's Companion to the British Pharmacopœia.