On the Presence of Arsenic in Mineral Waters, and in the Deposits Near Their Sources

Art. IX. On the Presence of Arsenic in Mineral Waters, and in the Deposits near their Sources. By MM. Chevallier, Gobley, Schauefele, and Filhol. (Annales d'Hygiene, T. xxxix., p. 172, ct xl., p. 224. 1848.) It is known that, notwithstanding the multiplied researches made on mineral waters, different principles capable of communicating active properties to these liquids have remained long un- known ; and that it is only in the nineteenth century, that the existence of bromine, iodine, and arsenic in these waters has been established. The discovery of arsenic in mineral waters, which was made in 1839, is due to M. Tripier, principal Pharmaceutist at Algiers, who found that the thermal waters of Haman Mescoutin, which supply the baths called Cursed Baths, Enchanted Baths, contain arsenic. The performance of M. Tripier gave rise to new researches and further discoveries. In 1846, M. Walchner, member of the directory of the mines in the Grand Dutchy of Baden, announced the presence of this metal, not only in the deposits left by old ferruginous springs, but in the ochrey sediments of mineral waters the most commended for their salutary effccts. According to M. Walchner, the waters or the ochrey mixtures which contain this metal proceed from the springs of Griesbach, of Rippoldsau, of Teissach, of Rothenfelds, of Cannstadt, of Wiesbaden, of Schwalbach, of Ems, of Pyrmont, of Lanischied, and of the Valley of Brohl, near Andernach. An account of the discovery of the presence of arsenic in the waters of Wiesbaden was published in this Journal, in April 1847, volume sixty-seventh, p. 575. In 1847, M Chatin was the first to make known the presence on the Presence of Arsenic in Mineral Waters. 125 of copper and arsenic in the waters of a chalybeate spring in the Park of Versailles; and thereby to give confirmation to the fact announced by M. Walchner. In the course of the same year, M. Lemonnier ascertained the presence of arsenic in the deposits of the ferruginous spring of Bagneres-de-Bigorre. M. Buchner announced the presence of this metal in the yellow-brownish deposits of the springs of Ragoczi, and of Pandour, at Kissingen. M. Caventou found the metal in a deposit collected near the ferruginous spring of Plombieres. M. Langlois, Pharmaceutist-in- chief to the Military Hospital at Metz, found arsenic in a ferruginous spring which issues near the village of Lorry. M. Bayard announced the presence of this metal in the waters of Pongues at Chateau-Gonthier. In. 1848, M. Henry announced the presence of arsenic in the waters of Cassuejouls; M. Meniere of Angers, in the waters and springs of L'Eperviere, department of Maine and Loire ; and M. Victor Audouard of Beziers, in the waters of Villecelle, near Lamalon, Herault. In the month of September 1847, M. Chevallier, who, with his son, and with M. Gobley, had undertaken a journey into Belgium and Prussia, caused to be collected the deposits formed at the different springs of Spa. They visited the beautiful springs of Chaudefontaine, between Spa and Liege, the deposits of which they have not hitherto been able to obtain. They planned a work which is partly completed. Shortly afterwards, M. Chevallier, in company with M. Schaue- fele, Pharmaceutist at Thann, in the Upper Rhine, visited Bus- sang. They collected deposited sediments, and took steps to obtain the products of the evaporation of the waters of the mineral springs of Alsace, and the sediments which are found near these sources, in order to inquire if these waters contained arsenical preparations. The labours undertaken by MM. Gobley, Schauefele, and Chevallier, are considerable. They make known the existence of arsenical preparations in a great number of springs which are situate in different departments of France. Here is given a short exposition of the researches of these Pharmaceutists.

Of the first memoir, which was presented to the Academy of Sciences by MM. Chevallier and Schauefele, the subject is the waters of Bussang. From the researches made on these waters, it follows:? 1. That the waters of Bussang contain an arsenical salt. 2. That this salt, though in solution in the water at the time at which is drawn, becomes in part insoluble at the end of a certain space of time. 126 MM. Chevallier, Gobley, Schauefele, and Filhol, 3. That the sediments taken at the springs of Bussang contain arsenic in a perceptible manner, and very minute quantities of copper. 4. That the most minute quantities of these principles, which we find in these waters, may be regarded as the partial cause of the salutary effects which are obtained from the use of these waters ; but that they cannot inspire the slightest subject of ap- prehension. 5. That it is, without doubt, to the presence of this active principle in these waters, that must be ascribed their efficacy in the removal of certain diseases.

From the second memoir read to the National Academy of Medicine, in the name of MM. Chevallier and Gobley, the following results may be stated. The researches made with the purpose of continuing the inquiries undertaken by Tripier and Walchner, have given rise to the presentation of two memoirs, containing evidence of the following inferences:? 1. That arsenic exists in the cold, acidulous, ferruginous mineral waters of Royat, Hauterive, of Provins ; in the thermal waters of Vichy, of Saint Mart, of Plombieres, of Mont D^r, of Bour- bonne. 2. That arsenic exists in the sediments collected at the springs of Royat, of Provins, of Jaude, of Saint Mart, of Hermonville, of Martigne-Briant; in the clays and in the sediments collected upon the walls of the basin of the fountain of the Civil Baths of Bourbonne; in the sediment of the fountain of Fenu. 3. That arsenic exists in the sediments collected at the new springs which have come forth at Spa. 4. That arsenic does not exist in the waters of Passy and in their sediments, old and new springs; nor in the water of Forges, nor in its sediment; in the water of Saint Allyre, nor in its sediment; in the sediments of the waters of Chateau-Thierry, of Colommes, of Pargny, of Jouy, of Boursault, of Montigny, of Amiens, of Cande ; in the water and clays of St Amand. 5. That though these chemists have not obtained arsenical stains with the product of the evaporation of a litre of mineral water of Contrexeville, of Chateldon, of Pougues, of Marequerie, of Saint Remi-PHonore, of Enghien, of Saint Alban, of Balaruc, of Bonnes, ofCauterets, of Bareges, ofChalles, ofSeltz, of Horn- bourg, of Marienbad, of Fachingen, of Pullna,of Seidlitz, it ought not to be concluded that these waters do not contain arsenic. 6. That the law promulgated by Walchner cannot be regarded as well founded. In point of fact, according to different experi- ments, certain ochrey sediments are formed only by oxide of iron ; on the Presence of Arsenic in Mineral Waters. 127 besides traces oilier ochrey sediments contain, iron, of copper > and others, besides iron, contain copper and arsenic. 7. That arsenic is contained not only in ferruginous or chalybeate waters, but also in those which do not sensibly contain iron. 8. That the quantity of arsenic which is present in mineral waters exerts, undoubtedly, an action on the animal economy, but that, by reason of its very small amount, it can never give rise to bad accidents. When this memoir was read, some observations were made, tendino- to prove that the waters containing the arsenic are mine- ialized?by the carbonates, and not by the sulphates. In reply to these observations, a note from the authors was afterwards read, containing the following inferences: 1. Among the waters which have been hitherto ascertained to furnish arsenic, a sufficiently great number contain sulphates. Such, for instance, are the waters of Vichy, of Saint Mart, of Mont D'or, of Plombieres, of Bourbonne, of Spa, of Soultzbach, and some others. 2. The number of mineral waters in which the arsenic is mineralized by sulphate of iron, is very small. These are the waters of Passy, of Cransac, of Rennes, of Selles, of Bourges,* of Alle- vard, and of Aix. 3. The springs mineralized by crenated or carbonated iron, are, on the contrary, very numerous. They are, at the lowest present computation, in number sixty. 4. Among the carbonated or crenated waters, nevertheless, several do not contain arsenic. Such are those of Forges, of Chateau-Thierry, of Coulommes, of Pargny, of Montigny, of Boursault, of Amiens, and some others. 5. One fact recently ascertained comes farther to contradict the opinion expressed. This is the presence of arsenic in the sediments of the waters of Cransac, which contain sulphate of iron.

The third Memoir addressed to the Institute by MM. Cheval- lier and Schauefele forms a sort of conclusion to that which these authors addressed to the Academy of Sciences on the 29th November 1847. The results contained in it may be stated in the following manner:? 1. The waters of Chatenois contain traces of arsenic. 2. The waters of Soultzbach contain traces of arsenic. The sediment left by the waters of Soultzbach contain perceptible quantities of arsenic. 3. 4. The waters of Soultzmatt contain very minute traces of * water of The the spring of St. Firmin, designated as sulphated, has been examined since the time referred to, and it has been found to contain carbonate, and not sulphate, of iron. 128 MM. Chevallier, Gobley, Schauefele, and Filhol, arsenic. 5. The ochrey sediment formed by these waters contain1 very minute traces of arsenic. 6. The waters of Wattweiler contain traces of arsenic. 7. The sediment left by these waters contains very great quantities of arsenic. 8. The waters of Niederbronn contain only minute quantities of arsenic. 9. The deposit left by these waters contains perceptible quantities of arsenic. The publication of the researches of MM. Chevallier, Gobley, and Schauefele has given rise to a new observation. It has be- come a subject of inquiry to establish, that if they had not found arsenic in the clays of St Amand, undoubtedly arsenic exists in these clays in the state of sulphuret, and that its presence is not in this state capable of being demonstrated by the means adopted by experimentalists. To this observation the authors of the Memoir render the following answer. I. They indicate that they had, by the processes employed, extracted from the clays of Bourbonne-les-Bainsr and from the clays of Hermonville, Department of the Marne, arsenic which existed in these clays. 2. If the experimentalist takes very pure sulphuret of arsenic, obtained from the precipita- tion of arsenious acid by sulf-hydric acid, if it be mingled with an organic matter, and if it be treated with concentrated sulphuric acid, following the ordinary method, he obtains a charcoal^ which, when taken up by water with the aid of heat, furnishes a liquid, which, when introduced into the apparatus of Marsh, causes the formation of numerous arsenical stains and rings. The question, to know whether waters mineralized by the sulphate of iron contain arsenic, having been raised at the Aca- demy, has induced MM. Chevallier and Gobley to solicit physicians, pharmaceutists, and inspectors of mineral waters who are settled near sulphated ferruginous springs, and especially near the springs of Rennes, of Salles (Fontaine-Levy), of Bourges, of Allevard, and of Aix in Savoy, to make several trials with the intention of resolving the question. We mention here the method to be pursued in order to determine the point, and to ascertain whether the sediments left by the waters contain copper. Researches for Arsenic in the Waters.?The waters are evapo- rated to dryness; then the residue is treated by sulphuric acid, with the assistance of heat, in order to destroy all organic matters. The sulphuric product, treated by water, is introduced, after filtration, into a simple Marsh's apparatus, when it is desired only to collect stains or spots, and into a Marsh tube apparatus when it is desired to obtain an arsenical ring. Arsenic in Inquiry for the Sediments.?The process should be conducted in the same manner; only it is necessary to take care? 1st, to destroy, by means of sulphuric acid, all the organic matter, on the presence of Arsenic in Mineral Waters. 129 which is more abundant in the sediments, in order that the liquid, when it is introduced into the apparatus of Marsh, tnay not give rise to the formation of froth;?2d, to filter the water which has been used to treat the sulphuric residue only after complete cool- ing, in order to allow the deposition of the sulphate of lime, which is then separated, as the presence of this sulphate would constrain the experimenter when he is using the apparatus of Marsh. Examination for Copper in the Sediments.?After having employed different processes in order to search for the presence of copper in the sediments, MM. Chevallier, Gobley, and Schaue- fele have fixed on the following method as the most eligible. The sediment is treated with hydrochloric acid in excess; the hydrochloric liquor is filtrated; it is then subjected to a stream of chlorine gas, in order to peroxidate the iron. To the liquor is then added ammoniacal gas in excess, which causes the precipita- tion of the iron and the copper, in the state of oxyde. The excess of ammonia redissolves the copper, which remains in the liquor; the precipitate is then filtered and washed, and the opera- tor searches for the copper in the filtrated liquid.

In consequence of the discovery by M. Walchner of small portions of copper and arsenic in the ferruginous deposits of various mineral waters, and the confirmation of this fact by the researches of MM. Figuier, Chatin, Henri, and others, M. Filhol, Professor of Chemistry and Pharmacy at the preparatory Medical School of Toulouse, proposed to himself to inquire, whether the oxyde of iron which is deposited as a sediment by several springs in the Pyrenees and the Infra-Pyrenean basin, do not also contain traces of copper and of arsenic. He was desirous further to know, whether the proportion of those two metals in ferruginous mineral waters was in such considerable proportion, that physicians could reasonably ascribe to them part of the efficacy of these waters in the removal of diseases. His attention was first directed to the ferruginous springs which flow in that part of the Pyrenean Mountains included in the De- partment of Ariege, where are found rich and abundant mines of iron, which are worked on the Catalan method. As previous trials had taught him that specimens proceeding from the mines of this country contain arsenic, he was naturally led to believe that the ferruginous springs in these parts would themselves be arsenical. M. Filhol analyzed first the sediments of a spring which rises at a short distance from Foix, and which is known in the neighbourhood by the name of the spring of M. Ruffie. This sediment formed a paste, which was dried to 100 degrees. The VOL. LXXIV. NO. 184. I 130 MM. Chevallier, Gobley, Schauefele, and Filhol, dry residue weighed 800 grammes. A minute analysis showed- that 100 parts contained the following substances:? Anhydrous oxyde of iron . Water * Organic matter Carbonate of lime of ,, magnesia Gelatinous silica, soluble in dilute acids Manganese .... Copper .... Arsenic .... Insoluble residue (sand)

100- The organic matter consisted of a small quantity of the acids known under the names of crenic and apocrenic acid; but almost the whole amount of this matter differed from these two acids, and could in no manner be confounded with them. M. Filhol states that it is impossible for him to explain himself on the nature of this substance, as, in order to know it properly, it would have required a careful examination, which he was then unable to undertake. The presence of a considerable proportion of gelatinised silica, which is easily dissolved in dilute mineral acids, the author re- gards as a fact which ought, according to his researches, to be very often reproduced, at least as to those sediments which are left by the ferruginous mineral springs of the Pyrenean chain and the infra-Pyrenean basin, for he has found it in all the water examined. M. Filhol next examined the hydrate of iron, which is deposited from the spring of St Quitterie of Tarascon, department of Ariege. He found, without difficulty, the existence of arsenic and copper; but he was able to estimate the proportion of neither metal, in consequence of the small quantity of the sediment on which he operated. M. Filhol also discovered traces of copper and of arsenic in the saline and ferruginous waters of Aulus, department of Ariege. In this instance, also, however, from the same cause, he was able to determine neither the proportion of copper nor that of arsenic. M. Filhol further analysed the sediments of two ferruginous springs, situated in the environs of Toulouse. The first of these is known under the name of Sainte Madeleine de FJourens. The sediment left by this spring, dried to 100?, furnished, in 100 parts, the following constituents :? on the Presence of Arsenic in Mineral Waters. 131 Oxyde of iron, Water, Carbonate of lime, ? magnesia, Organic matter, Gelatinous silica, Arsenic, Alumina, Insoluble residue,

100- In this instance, it may be observed, the arsenic is not accompanied with copper. The second spring issues at a short distance from Toulouse, at the foot of the hills which bound the right bank of the Garonne. The analysis of the precipitate, dried to 100?, gave the following results :? Oxyde of iron, . ? 53*100 Water, . . . 19*508 Carbonate of lime, . ? 4*503 . 0*675 ? magnesia, Gelatinous silica, . . 4*200 Organic matter, . ? 12*327 Alumina, . . . 2*910 Arsenic, . ? 0*052 Insoluble residue, . , 2*719

100* In this sediment, as in the preceding one, no copper was found. The organic matter, which accompanies the oxyde of iron in these two last springs, contains only traces of crenic acid ; and the water contains so little free carbonic acid, that the solubility of the iron can be explained only by the existence of this organic matter. M. Filhol ascertained the absence of arsenic and of copper in the ferruginous clays of one of the springs of Alet, department of Aude. This spring is known in the country under the name of Red Water. It is situate about two leagues from the baths of Rennes. He was unable to obtain sediments from the baths of Rennes. M. Filhol ascertained, in like manner, the absence both of copper and arsenic, in the sediment of a ferruginous spring which rises at a short distance from Montauban, and bears no particular name. From these analytical inquiries, M. Filhol thinks it may be concluded that the proportion of arsenic contained in the ferru- 132 MM. Chevallier, Gobley, Schauefele, and Filhol, ginous springs which he has examined, is too small to be capable of communicating to them great activity. The arsenic scarcely amounts to the twentieth part of one milligramme in the instance in which he determined the proportion with precision. M. Filhol is of opinion, that, if researches of the nature of those now mentioned, informed us subsequently, that the dose of arsenic in the greatest part of ferruginous mineral waters is about as small as that the analysis of which has now been given, it is evident that the experts ought not to be concerned regarding the use which may have been made of these waters by any individual who has died, after presenting symptoms of poisoning, and in whose dead body an inconsiderable quantity of arsenic may have been found. The examination of the ground which is traversed by the ferruginous springs, in the environs of Toulouse, leads M. Filhol further to think that, conformably to the opinion expressed by M. Chatin, the iron is carried away from the soil by the organic matters proceeding from the decomposition of the vegetables de- caying at its surface. The soil which surrounds these springs is indeed covered for a considerable extent with the debris of vegetables, which may furnish organic matters; it is further rich in oxyde of iron, and M. Filhol has satisfied himself that this oxyde is arsenical. The almost constant presence of arsenic in oxydes of native iron has led M. Filhol to think, that the question to ascertain, whether, certain grounds,?for instance, those of cemeteries,?contain arsenic, might be almost determined beforehand by simple in- spection of the ground. This is indeed the case in several instances. It has nevertheless happened to him to find arsenic in grounds which contained only very little iron, while he has found no arsenic in very ferruginous grounds. Analysis then becomes in all cases indispensable, if we wish to obtain perfect certainty on this question. Another reflection relative to the condition of arsenic in arsenical grounds which he subjoins is the following. "cIt is long since M. Ortila has demonstrated in the most decided manner, that arsenic contained in the earth of cemeteries is always found in them in the insoluble state, and cannot be conveyed either by the water of rains, or in any other mode, into the organs of the dead bodies there interred. Trials of the same kind, which I have made upon arsenical ferruginous earths, have led me to results perfectly agreeable to those of M. Orfila, and have satisfied me that in this, as in all other cases, the arsenic is completely insoluble, and cannot be conveyed into the dead bodies." 1 he following general inferences are stated. on the Presence of Arsenic in Mineral Waters. 133 1. Arsenic is present in a great number of springs both in the Pyrenean chain, and in the sub-Pyrenean basin. 2. Arsenic is not in all instances accompanied with copper. 3. The organic matter, the presence of which is proved by analysis, in the sediments of these springs, is not crenic acid. 4. Ferruginous grounds are not in all instances arsenical. 5. The arsenic which is found in the grounds of certain cemeteries, is always found in them in the insoluble state, and cannot, in any manner, be conveyed into the dead bodies interred in these grounds.

We subjoin, first, a table of the French Mineral Waters which contain arsenic; secondly, a list of the French Mineral Waters which are void of this mineral; and, thirdly, of the Belgian, Rhen- ish, and German Mineral Waters, which contain Arsenic.

French Arsenical Mineral Waters :?

Names of Springs. Authorities. Ferruginous Water of Bagneres de Bigorre, Lemonnier. Water of Cassuejouls, (Aveyron) O. Henri. Cay la, ibid. id. Villecelle, (Herault) V. Audouard. Source-Ruffie, (Ariege) Filhol. Sainte-Quitteric-de-Tarascon, (ibid.) id Aulus, ibid. id. Sain te-Mag(lelaine-de-F lourens. (Haut-Garonne), id Doulans (Creuse), O. Legrip. Pougues-de Chateau-Gouthier. (Mayenne), H. Bayard. Bussang, (Vosges), Chevailier, Schauefele, Gobley. Cransac, Blondeau, Chevailier, Gobley. l'Eperviere, (Maine-et-Loire) Meniere. Lorry, (Moselle), Langlois. Martigne-Briand, (Moselle), Chevailier,Gobley, Meniere. La Fontaine de Fenu, Bayard, Chevailier, Gobley. Royat, (Puy-de-Dome), Chevailier, Gobley. Saint-Mart, (Puy-de-Dome), id. Jaude, (Puy-de-Dome), id. Hermonville, (Marne), Chevailier, Gobley. Vichy, Spring of the Hospital, id. Spring of the Grand Grille, id. Celestins, id. Celestins Lardy, id. Spring of the Acacias, id. Spring of Puits-Carre, id. Water of Haute-Rive, id. Water of Cusset, Spring of the Hospital, id. Spring of the Abattoir, id. Spring of the Rotunda, id. Spring of Dames Pajot, id. 134 MM. Chevallier, &c. on Arsenic in Mineral Waters.

Names of Springs. Authorities. Water of Chateldon, Spring of Puits-Rond, Chevallier, Gobley. Spring of Puits-Carre, id. Water of Plombieres, Vosges, id. Bourbonne-les-Bains, (Haute-Marne), id. Chatenois, . . Chevallier, Scbauefele. Soultzbacb, . id. Soultzmatt, . . .id. Wattweiller, . . .id. Niederbronn, . . id.

Mineral Waters in France, void of Arsenic. Water of Passy (Seine), new and old Springs. Flandin, Chatin, Chevallier, Gobley. Forges, (Lower Seine), Chevallier, Gobley. Coulommes, (Marne), . id. Pargny, (Marne), . id. Jouy, (Marne), . id. Boursault, (Marne), . id. Montigny, (Marne), . id. Marequerie, (Lower Seine), id. Chateau-Thierry, (Aisne), id, Amiens, (Somme), id. Cande, (Vienne), . id. SainteRemy l'Honore, (Seine et Oise), id. Saint-Amaud, (Nord), . id. Cloys of Saint-Amand, (Nord), . id. Water of Allet, (Aude), . Filhol. Saint Allyre, (Puy-deDome), Chevallier, Gobley.

Arsenical Mineral Waters not in France. Names of Springs. Authorities- Water of Griesbach, Walchner. Rippoldsau, id. Rothen fields, id. Cannstadt id. Wiesbaden, Walchner, Mialhe, Figuier. Schwalbach, Walchner. Ems, id. Pyrmont, id. JLamscbied, id. Brobl, id. Ragoczy, Buchner, Younger. Pandour, id. Bruekenau, id. Water of Spa, Spring of Poulion, Chevallier and Gobley Spring of Groesbeeck, id. Spring of Sauviniere, id. Spring of Geronstere, id. Spring of New Tonnelet, id. Spring of Little Tonnelet, id. Spring of Old Tonnelet, id Spring of Barissart, id. Spring of Hotel de France, id.

It may be proper to observe before concluding this subject, that though M. Filhol expresses the opinion that in the waters of Dr C. Bell's Cases in Midwifery. 135 the springs of the Pyrenees, and the sub-Pyrenean chain, the arsenical impregnation is too small to produce any effect on the persons of those who drink these waters, such is not the opinion of other physicians and chemists, at least with regard to the Ger- man arsenical springs. M. Figuier is decidedly of opinion, that even in the very diluted dose in which the arsenic is found in these waters, it is capable of exerting effects both physiological and therapeutic. Then it ought to be borne in mind .that as these waters are drank for a considerable time, and the sys- tem becomes as it were charged with them, it is quite possible, nay, most likely, that they produce very decided effects upon and within the economy. This, however, we attempted to show on a former occasion. It ought also not to escape observation, that feeble as is the dosing of arsenic in mineral waters, its combination with iron is calculated to counteract any hurtful effects. It is indeed a fact, highly deserving attention, that while modern experience has shown that the most effectual antidote,?if such a term can be used, to the poisonous effects of arsenic, is the hydrate of iron; in mineral waters, the use of which experience has shown to be often beneficial in the treatment of disease, arsenic is combined, at least temporarily, with the same metal. It may not be perfectly safe to assert, that Nature appears to adopt this mode of administering a metal of extremely active properties, in order to render that metal therapeutic. But the fact is so significant as to the pro- bable explanation of the efficacy of certain mineral waters, that it assuredly deserves the attention of practical physicians.