Mineral waters of Europe; including a short description of artificial mineral waters

Front matter

THE MINERAL WATERS

OF EUROPE.

-*_

Preface

Most of the objects had in view in writing the present work have been incidentally mentioned in the Introductory Chapter. It may, however, be desiderable to enumerate concisely the chief points which have actuated the authors in penning the " Mineral Waters of Europe.''

The book is intended as a reliable work of reference in connection with the chief mineral waters, and also to give the character and locality of such other waters as are in use.

In many of the books published upon the subject the analyses given do not represent the present composition of the waters. They have been copied from work to work for years. Not only has every error been transmitted with the most religious fidelity, but,

IV PREFACE.

in some cases, they are merely copies of interested puffs, carrying with them little or no weight.

We have endeavoured to avoid these rocks a-head. In all the chief waters we have either re-examined the hottled waters ourselves, or have made use of recent analyses performed by analysts whose names were a guarantee.

The new analyses are nearly one hundred in number, and represent work which has extended over a period of about three years.

We frequently meet with a class of books dealing with the individual experience of an author applied to a certain district. They are generally readable, and often contain valuable information, but they can hardly be looked upon as works of reference; the restricted area of their explorations, in nine cases out of ten, is a cause of weakness. Excellent as guide-books to the district, they in no way fulfil the objects the writers of the present work contemplate in bringing it out.

The Therapeutic Chapters, by Dr. Trosser James, have been penned after a practical knowledge obtained at the source of many of the most important waters. The analyses are from the waters supplied by export ; and a chapter has been added upon Artificial Mineral Waters, as being a subject intimately connected with the Natural Springs.

The writer of this Preface must acknowledge his indebtedness to the following works : — Watt's " Dictionary of Chemistry,'' Dr. Candelle's " Manuel Pratique de Medecine Thermale," Dr. Madden's " Spas and their Uses," Dr. Oliver's " Mineral Waters of Harrogate,'' and numerous pamphlets.

C. E. C. T.

Dublin, May, 1883.

My contribution to this little volume consists of the Chapters on the Therapeutical action and uses of the several Mineral Waters. These are Chapters 2, 4, 6, 8, 10, 12, 14, and 1G.

In writing them I have supplemented information acquired at the Spas by my experience of the use of the imported waters in London practice. In discussing the properties of the waters I have had before me Professor Tichborne's new analyses.

P. J.

Works by Dr. Frosser James.

SORE THROAT, its nature, varieties, treatment, and Connection with other Diseases. Fourth Edition, illustrated with Hand-coloured Plates, 6s. 6d.

LARYNGOSCOPY and RHINOSCOPY; including the Diagnosis and Treatment of Diseases ok the Throat and Nose. Third Edition, illustrated with Hand-coloured Plates, 5s. 6d.

A VISIT to VICHY; with a Sketch of its Mineral Springs and Thermal Establishment. Fourth Edition.

THE CLIMATE of SAN REMO and OTHER WINTER STATIONS ok the MEDITERRANEAN, including Nice, Mentone, Cannes, and Hyeres. Is. 6d.

THE PROGRESS of MEDICINE: being the Introductory Lecture delivered at the Opening of the 89th Session (1873-74) of the London Hospital Medical College. Is.

Contents

Introductory. — Commercial Importance of Mineral Waters ; Changes observed in Mineral Waters ; Application of the Spectroscope to Water Analysis ; Indications of Decaying Organic Matter observed in some Waters ; Theoretical Arrangement of the Elements in Analyses ; Therapeutics of Mineral Waters ... ... ... ... 9

Chapter I. — Chemical Classification of Mineral Waters ; Different Modes in Use ; Salines, or Aperient ; Alkaline, or Antacid ; Ferruginous ; Sulphurous ; Potable, and Indifferent ; Wanklyn's Ammonia Process ; Home Waters ; Mineral Constituents of the Blood ... ... ... ... 12

Chapter II. — Therapeutics of the Classes of Mineral Waters mentioned in the last Chapter ; Action of Pure Water ; Temperature at which Water should be Drunk ; Mineral Water Drinking ; Salines ; Alkaline Waters ; Chalybeate Waters ; Sulphurated Waters ; Table Waters ... ... 23

Chapter I. Chemical Characters Op The Mineral Waters, In Classes

The classification of mineral waters is a subject that presents great difficulty, and has been treated in different ways. The alphabetical arrangement would perhaps get over all difficulties, but would hardly facilitate the inquiries of the medical man. Mineral waters often differ in their temperature when examined at their source. Thus we have all degrees, from the Malvern waters below the atmospheric temperature, to the boiling springs of Iceland — from the almost ice-cold waters of Silesia, to the hot Sprudel of Bohemia : attempts have been made to classify them from these degrees of temperature. Such a classification might amuse the crotchets of our ancestors ; whilst of little use even to those who use the waters locally, it is utterly worthless for the purposes of these articles.

Their general, or most marked chemical character appears to us to present the most feasible method of classifying mineral waters. One well known work proposes to classify them on this principle : but suggests the rather crude division of sulphurous, chalybeate, and taline. We propose as the main or primary classes five, namely : 1, saline or aperient ; 2, alkaline or antacid ; 3, ferruginous or chalybeate ; 4, sulphurous ; 5, potable or in different.

CHEMISTRY OF MINERAL WATERS. 13

1. The saline or purgative waters mainly owe their medicinal virtues to the large quantities of magnesium, or sodium sulphate, as in the Hunyadi Janos, where these two salts occur in nearly equal proportions and in large quantities. When the magnesian sulphate and chloride occur in large proportions the waters generally are known on the Continent as bitter waters, as they owe their bitterness to the above-named salts.

In the Kreuznach water of Prussia we have a saline water of another class in which, according to the published analysis, we have about 900 grains of salines to the gallon, and which is absolutely free from the presence of alkaline or magnesian sulphates. We are not justified in dividing such waters from the other saline waters, because if we exclude any special action of the other ingredients they still remain purgative waters, and very frequently are generally associated chlorides and sulphates ; perhaps we might further classify the saline water as "haloid saline/' sulphuric saline, or, when combined, as " sulphuric-haloid saline."

2. The alkaline waters generally owe their alkalinity to the carbonates or bi- carbonates of the alkaline earths conjointly with the potassic or sodic carbonates. The antacid properties are, of course, more marked with those waters which contain a sensible quantity of the alkaline carbonates, chiefly sodic and potassic bicarbonates ; whilst the lithium, and other alkaline earths, are specially indicated in urinary diseases.

The term " alkaline acidulated springs " is sometimes used in connection with these waters'. We confess we hardly understand the term or the sense in which it is used, because, in many lists, it seems to be applied indefinitely, and just according to the caprice of the writer.

14 CHEMICAL CHARACTERS

We find in waters similarly constructed, some are so named, whilst others are not. Almost all these waters, from a geological necessity, must contain free carbonic acid gas, and, in a sense, are acidulated ; but the loss of the excess of that gas must result, probably, in au alkaline condition, but certainly in a neutral liquid.

3. Ferruginous or chalybeate waters contain the iron, in three conditions, either as a ferrous or protocarbonate of iron, or as a basic or neutral sulphate. It is generally present in either of the two first conditions, and although the protocarbonate is considered the most useful and valuable form, (it is certainly the one most pleasant to take), it is not so permanent a water for bottling.

4. Sulphurated. — The iron in chalybeate or ferruginous waters is frequently the result, or at least is associated with the decomposition of organic matter ; and this remark also applies to the next class, which are called sulphurous waters (belter sulphurated waters). It has been the custom in days gone by (the dark days of science) to value a water which smells like rotten eggs according to the vileness of that smell. Now, it is self-evident that although its odour may in a degree be a measure of the quantity or presence of sulphur, if that sulphur is produced from the reduction of mineralised sulphates by the decomposition of organic bodies, we must also take it as evidence of a very large proportion of matter in a most objectionable form. Sewage often smells strongly of sulphurated hydrogen, and we are bound to say, that unfortunately many of the so-called sulphur springs owe their sulphuretted hydrogen and alkaline sulphides to precisely the same cause. Such a water is simply poisonous, and the prolonged use of it must end in lamentable results. Fortunately Wanklyn'3 albuminoid

OF MINERAL WATERS. 15

ammonia process presents an easy and certain mode of determining this point. But the process when applied to sulphuretted waters requires a little modification. In an ordinary water it is usual to distil off the free ammonia from a given quantity of water, and to estimate this free ammonia by Nessler's test ; the residual water is then distilled with an alkaline solution of permanganate of potassium which has previously been purified from ammonia. Any ammonia now found in this second distillate must proceed from the oxidisation of nitrogenous organic matter, the nitrogen in such a case coming off in the form of ammonia. But as the sulphuretted hydrogen would and does interfere with the reaction of the Nessler, we distil off in a flask the free ammonia, adding after the process has continued a short time, a few drops of a pure solution of peroxide of hydrogen. The free ammonia is thus lost, but is of no consequence to our experiment. In such waters free ammonia in reasonable quantities may be neglected.

Any remaining products of sulphur are oxidised by the second part of the process into the perfectly stable sulphuric acid which no longer interferes with the reaction of Nessler's reagent. We generally add a given quantity of the water under examination when deprived of its free ammonia, and sulphuretted hydrogen to the action of a considerable excess of caustic soda (from sodium) and permanganate of potassium for some time in the cold ; and then distil and tritrate in the usual manner. Any ammonia now found in the distillate must proceed from nitrogenous organic matter present in the water, providing the chemicals employed are absolutely pure.

The term usually applied to these waters is sulphurous. Now although used in medical and other works, and by the profession generally, it is evidently a term so mis-

16 CHEMISTRY OF CLASSES

applied that we shall confine ourselves in future to the term sulphurated. " Sulphurous " from every chemical analogy would convey the idea that the sulphur in these waters was present as sulphurous acid, or as the class of salts known as sulphites (M'' SO )— whilst it really exists as sulphides (M S). These sulphides in the presence of water, or in their hydrated state give rise to the fcetid odour which is their chief characteristic. There are many modes in which we may suppose that these sulphides are produced geologically, for instance, the direct combination by igneous action of calcium rocks with sulphur, or sulphides, and the subsequent decomposition of the calcium sulphide by carbonate of sodium. Such a decomposition would be effected in the moist way if under pressure. The sulphur when in the assimilable form exists as sulphydrates of the alkalies and alkaline earths, which are easily decomposed, and give rise in such water to a fairly permanent smell of sulphuretted hydrogen—

2NaHS = Na 2 S + H 2 S

Sulphydrate Sulphide Sulphydric

of sodium. of sodium. acid.

On boiling such a solution this decomposition is much more marked, and we ultimately get a perfect decomposition, so —

= 2NaHO

+ H2S

Sulphide Water.

Hydrate

Sulphuretted of sodium.

of soda.

hydrogen.

The writer has in his previous researches proved that all salts in the mere act of solution are to a certain extent dissociated, and this fact is the cause of all soluble sulphides when in solution giving off sulphuretted hydro-

OF MINERAL WATERS. 17

gen, or their acidulous radical. As this becomes oxidised into the higher or prolythionic acid — combines it with the base and fresh proportions of sulphuretted hydrogen are set free as long as any sulphides are present. It is generally stated that when the sulphydric acid is chiefly combined with calcium it gives a more permanent sulphuretted water, then when present as a sulphide of sodium ; ceteris paribus, we doubt if this is strictly correct. The sulphydrate of calcium will give a more strongly smelling water by virtue of its more ready decomposibility.

We frequently find that sulphuretted waters of a true mineral origin have associated with their bases barium and calcium. This is the case in the Harrogate sulphuretted waters — one of the best waters of its class.

In fact it has been too much the fashion to run down the Home waters, and the Continental medical men are only too glad to make little of that which the professional men of this country seem to depreciate. This undesirable state of things has been induced, no doubt, by the very proper value which the medical man attaches to climatic influences and change of scene — items which should not, for a moment, be considered unimportant — but now that the bottling of mineral waters has become such a special trade, we see no just cause why English waters should not compete in this direction. The names of many foreign, but inferior waters, are well known in this country, and largely run after.

Candell^, in his useful Manuel Pratique de Medecine Thermale, 1879, disposes of the English waters in about six lines. He says, L'Anghterre est un des pays les plus ■pauvres en sources mddicinales. It will be part of our programme to dispell this illusion. His book is instructive as showing that even in the present day faith forms a.

18 CHEMISTRY OF CLASSES

very important factor in Mcdecine Thermale, as practised on the Continent.

5. Potable Waters. — We have now to notice waters which are often spoken of in medical works as unimportant, that is, of indifferent waters, or waters in which the therapeutic action is not sufficiently pronounced to be used in the direct treatment of disease. Some of these waters may contain infinitesimal quantities of ingredients, which by their constant use might produce remedial effects ; but it is their use as potable waters, or for table drinking, that from our view renders this section of mineral waters most important. The great increase in the use of mineral waters in everyday life is desirable, providing we can insure that the water is perfectly free from organic impurities, and providing that the mineral matters are sufficiently definite in character.

The miueral salts in a table water should not, as a rule, much exceed 1,000 grains per gallon. When it exceeds this quantity it should not be indulged in too freely. All waters should be used judiciously, according to the idiosyncracy of the consumer, and the peculiarities of the water. The medical man is the proper person to determine this point : another of the many reasons that the mineral water question should be put definitely before the profession. .

The remarks made in connection with the presence of nitrogenous organic matter in sulphurated waters and chalybeate waters, apply with double force in the case ot these potable waters — waters which are drunk freely and constantly— and it is absolutely necessary that a water which becomes an inmate of our house should be like Ciesar/s wife, beyond suspicion. In the days of Liebi" and even in the early analyses of Fresenius, these points

OF MINERAL WATERS 19

were not sufficiently investigated, and it is our intention to re-investigate analyses of that period. In some waters we find that very full and careful analyses have lately been done by men of acknowledged celebrity. la such cases we will give the most recent and careful analyses, stating at the same time our authority.

Directly we accept the desirability of using a mineral water in its potable sense, we must at once consider it simply as a food product, and, therefore, the nearer it resembles the mineral constitutents of the blood the more generally it may be relied upon.

In a previous paragraph we cursorily referred to the composition of the blood by stating that if mineral waters were used constantly at the table their constituents should bear a certain relation to the ash of the blood. This fact has been made use of on more than one occasion amongst the numerous puffs and advertisements put forward by the proprietors of mineral waters, and although like every other theory or proposition of this kind, it is frequently carried to an absurd extent, an abnormal amount, or any abnormal ingredient would be no recommendation to the extensive use of a water for table purposes. Owing to the laws of exosmosis and endosmosis the salts in the blood never undergo any more than a very temporary change in mineral composition, but we can readily perceive that where a copious and constant inroad of fluids highly charged with easily diffusible salts takes place into the stomach — from physical laws alone a certain and unnecessary strain is put upon the animal economy, which must be objectionable. Chloride of sodium and the alkaline chlorides are the most diffusible of all salts, and therefore, from this reason may be considered in reasonable quantities not to be injurious. The alkaline

20 CHEMISTRY OF CLASSES

sulphates are not so diffusible, and this probably will account for their more energetic purgative properties.

In the writers' opinion the chlorides of the alkaline earths should never amount to anything very considerable. In excessive quantities some writers on therapeutics are of opinion that these salts interfere with the digestive functions, but on chemical grounds alone we are dealing with bases which, presented in their more soluble condition, have a tendency to form more insoluble compounds, which may give rise to difficulties in the emunctory organs if used in a superabundant quantity over that necessary for bone deposition. The physicians may, however, see cases where such a condition might be desirable. In reference to the analogy desirable between waters for drinking purposes, and blood, we will briefly detail the composition of the fluid. According to Schmidt, 1,000 parts of man's blood contains 513 parts of moist corpuscle?, and 486-98 of serum, both rich in salts. The mineral matter of the corpuscles amounts to 81 - 2 per cent., whilst that of the serum is 85'5 per cent. The potassium salts seem to accumulate in the first, whilst in the serum the potassium and sodium salts seem about equally divided. According to the latest researches of A. Jarisch, 1877, the following are the normal mineral constituents of blood. The acidulous radicals are as follows : —

Phosphoric (Pj O5 )

. 861

Sulphuric (SO3 ) .

. 11-44

Chlorine (CI.)

. 28-63

The writer will add to this list fluorine, which he believes is always present, and must be considered a

OP MINERAL WATERS. 21

normal constituent, just as it is of bone. The bases are : —

Sodium (Na 2 0)

. 26-06

Potash (K 2 0) .

. 22-92

Lime(CaO) .

. 1-24

Magnesia (Mg 0)

. 0-52

Ferric Oxide (Fe2 O3 ) .

. 7-03

Lead and copper have been stated as being present in the blood, but they are simply accidental ingredients just as lithium which appears in the blood after a course of lithia water.

"We now come to waters, which are special in their action from containing special ingredients in sufficient quantities to produce marked reactions.

Arsenious acid is one of the ingredients which gives any special therapeutic qualities to mineral waters, more particularly as the dose is small. The mineral waters containing arsenic are, as a rule, even more energetic than a granular dose of arsenious acid per se would be. Some of these arsenical waters are said to contain 28 mm. per litre. Lithium has been found in an immense number of the alkaline;.waters, which previous to the introduction of the spectroscope had not been found to give any reactions indicating the presence of that metal. We do not, however, mean by lithia waters such waters as these. Some of the lithia waters contain six to eight grains per pint, and exert very marked chemical reaction. Bromine and sodium are frequently found in mineral waters in considerable quantity.

Chapter II

THERArECTICS OF THE CLASSES OF MINERAL WATERS MENTIONED IN THE LAST CHAPTER.

It is considered desirable to append a few remarks on the remedial uses of mineral waters in classes before proceeding to treat of individual springs. In so doing we shall follow the order adopted in the chemical division of this work. Inasmuch, however, as the imbibition of more or less liquid exercises no slight influence on the body, we are met by the preliminary consideration of the internal use of pure water. An adult will in health take an average quantity of nearly four pints of fluid a day ; some thirsty souls take much more and some do with less. A few make simple water their chief fluid ; others consume much milk ; a larger number take a considerable proportion of tea, coffee, cocoa, or other simple beverage ; too many almost exclude the simpler fluids by the amount of alcoholic liquors in which they indulge. In this last case, of course, the effect of the alcohol masks that of the fluid, but we must not forget that the amount of liquid drunk and the time at which it is taken exercise some influence. Of course, the amount of liquid received has to be counter-balanced by that removed, so that the skin, lungs, and kidneys are called upon to get rid of the average four or five pounds of water a day, and of any excess that may be injested. As the water is taken into the system and is the vehicle for the removal of waste it may be regarded as in

THERAPEUTICS OF WATER. 23

some sense washing the tissues. It is commonly said that very little water passes directly through the pylorus into the intestines, but Kiiss is of a different opinion, and the writer of this chapter endorses his view — more especially when large quantities are taken.

But the water thus required to maintain the balance of the system is only a small part of that which is always at work in the economy. The quantity daily poured with the secretions into the alimentary canal, and again re-absorbed by the lymphatics and termini of the vena porta?, is variously estimated at 12 to 24 pounds. This water is the purveyor of various solids which are precipitated and left behind, and the solutions in question must contribute their share to the manufacture of the chyle. Water freely passes from the stomach into the vena porta? ; thence it goes through the liver, where it becomes charged with the products of that organ, and brings them again into the intestines where they are precipitated. Hence we may understand the repute of free water-drinking as a cholagogue, and as powerfully assisting the abdominal circulation. Apart then from its mechanical effect in the prim* viae, which varies with the quantity imbibed at a time, water may be regarded as the great diluent, solvent, and eliminant. It dilutes the contents of the stomach and intestines, and thus acts as an aperient. It also dilutes the whole mass of the circulating fluids ; but probably the blood is only influenced thus for a brief period, its specific gravity being maintained with tolerable uniformity. We have seen how it dilutes the bile and thus acts as a cholagogue. In the same way it is a diuretic and diaphoretic by dilution of the excretions of the kidney and skin, and the same may be said of its effect on all secretions. Add to its diluent its solvent powers, and we see why it is the

24 THERAPEUTICS OF WATER.

most valuable eliminant : dissolving various substances and increasing all the secretions by which they are removed it increases tissue changes, and thus loss of body-weight would ensue unless counteracted by the fresh arrival of aliment. It may thus increase appetite, and prove the best tonic ; but if appetite fail, or food cannot be obtained, it would hasten wasting. By removing waste tissues it is believed that it may thus affect morbid deposits, though this power is more frequently attributed to medicinal waters.

The temperature at which water is drunk has a great influence. Absorption appears to take place at about the temperature of the blood, and to secure rapid removal from the stomach by absorption it should be taken at about that point, and in small quantities at a time. Cold water in small quantities stimulates the stomach and assists digestion. A full draught is apt to impede that function— in weakly people " lies heavy " for a long time, and the danger of drinking very large quantities when the body is hot and exhausted, is well known. A glass of cold water early in the morning is an excellent aperient, stimulating the peristaltic action by its temperature, and promoting the secretions in the way already described ; a draught rich in carbonic acid is still more effectual. Cold water may be given even when the temperature is high, and it does not give rise to discomfort. On the other hand warm water is more grateful in many painful affections of the abdominal organs ; it is better to increase the action of the skin, to promote other secretions, and possibly to stimulate the absorption of morbid deposits ; as a cholagogue it is often efficient if taken regularly at bed time, or night and morning. In laryngitis and bronchitis the use of hot drinks is well known as a popular remedy. Warm beverages are also popularly regarded as more refreshing than cold. Excess in drinking liquids either warm or cold gives rise to certain complaints well-known to medical men, but as this work is intended to be restricted to the bottled waters, it seems unnecessary to describe the evils that are sometimes produced at certain springs.

We have next to consider the action of mineral waters. The effect of a glass of water containing a fixed amount of solid or gaseous substances might be supposed to be the same as a similar dose of the active ingredients. Usually more fluid is taken than in pharmaceutical preparations ; hence we have to do with the effect of the water as well as the medicine ; and with the variation induced in the latter by dilution. The former we have seen depends on the quantity drunk, the time at which it is taken, and its temperature. With regard to the latter, the effect of solids s perhaps better understood than that of gases. Some mineral waters are charged with large quantities of solids, for example, some of the stronger, bitter, saline, purging waters ; others contain an almost inappreciable quantity of mineral ingredients. These solids are absorbed with the water, and produce their usual medicinal effects, but it is to be remembered that dilution tends, as a rule, to increase that action. Thus a small dose of sulphate of magnesia or soda in a large quantity of water will prove as active a purgative as a large dose less diluted. Then, again, the frequency of repetition in many cases is an important question, for on this depends whether the ingredient be circulating in the system almost constantly, or only for a brief period. This depends in its turn on the rate of elimination and the frequency of the dose, a point which, in reference to mineral waters, has not been sufficiently attended to. The effect of the gases is less understood. Carbonic acid is an agreeable stimulant to the stomach,

c from which, however, most of it is speedily eructated, but some of it passes into the intestines and stimulates peristalsis. So marked is this effect that carbonated waters are advantageously substituted for salines in many cases in which the latter are still frequently prescribed. Constipation from torpor of the bowels is not amenable to the more irritating laxatives of saline waters, but may often be overcome by more simple remedies, such as the popular glass of cold water, fasting ; or the still more appropriate use of a highly carbonated, but not purgative, mineral water. Further, the carbonic acid gas has the power of holding other ingredients in solution, and making the dose more palatable. Of the effects of nitrogen, sometimes vaunted as an ingredient, nothing positive is known. Minute quantities of sulphuretted hydrogen are supposed to have a value as pronounced as the flavour of the water which contains this gas. Of other gases nothing need be said here.

Coming, then, to the effects of the individual classes, we may briefly sum up their commonly reputed remedial value prior to a fresh investigation of their merits.

1. Salines. — The so-called bitter or purging waters owe their aperient qualities to sulphate of magnesia and soda, the effects of which as medicines need not be described. In small repeated doses they can be made to induce an artificial diarrhcea ; in large ones they are more or les3 cathartic. The more freely diluted the more active they usually are, and in this class of waters, therefore, we have highly diluted saline laxatives, modified in their action by She other ingredients and the temperature at which they are taken. These waters are highly prized as occasional or habitual aperients, and are regarded as specially useful in congestion of the portal system, and in the condition