Part 8

As the smoke of the fluid lava is perfectly neutral, that is, neither acid nor alkaline, so the fumaroles at the first period of their existence with sublimations of sea-salt, mixed frequently with oxide of copper either in black powder or in shining laminæ, ought also to be neutral. But if the fumarole continues active, hydrochloric acid issues with the smoke, and often some time after sulphuric acid. Then the sublimations turn first yellow, then green, and more rarely azure. The chemical reactions show that these sublimations are chlorides or sulpho-chlorides, and sometimes sulphides, and they afford reactions, indicative of soda, magnesia, copper, lead, and traces of other substances, not excluding ammonia, which I must speak of separately. This, I have observed, is the general law with the fumaroles of the tranquil lavas, which occur with long and moderate eruptions--for instance, the lavas of 1871, and even those of 1872, preceding the 26th April.

But in the great lavas of the great conflagrations of Vesuvius, chloride of iron more or less in combination with all the other substances above mentioned changes the appearance of the sublimations. The fumaroles in the lava of the 26th April frequently indicated chloride of iron. Sulphuretted hydrogen, by reaction of sulphurous acid, is decomposed, and sulphur sublimed, having a particular aspect, collects on the scoriæ. This is never found but in fumaroles of the smaller lavas; it was therefore absent in those of 1871, but frequently occurred in those of 1872.

Although the sublimations are generally mixtures, yet sometimes distinct and crystallized chemical or mineral species are found, such as sulphur, sal ammoniac, _tenorite_, _cotunuite_, etc. Micaceous peroxide of iron (feroligiste), so common near eruptive cones, is very scarce on lava; any found in it has been carried down from the craters, and proofs of this transport are very abundant and striking in the lavas of this last eruption. Even the iron found in the bombs is evidently transported; there is a fumarole on the ridge of the lava in the Fossa di Faraone which contains micaceous peroxide of iron, and this, at first sight, appears to oppose what I have affirmed; nevertheless, it gives additional force to my statement. This fumarole is only a bomb or rounded mass of enormous size, four or five metres in diameter. Smoke and hydrochloric acid issued from the aperture in its envelope, and being partly broken it was seen to contain lapilli and pieces of antecedent lava, covered with micaceous peroxide of iron. The internal temperature of this mass was very high; the hydrochloric acid which it discharged had, in some places, covered the micaceous iron with a yellow coating of chloride of iron. From small apertures, on the lower side of the mass, white and green stalactites of chloride of calcium were visible. In one spot only of lava I found a fumarole, with a small quantity of micaceous peroxide of iron, evidently in a state of formation; but this was the very spot where the lava became eruptive, and whence issued the column of smoke which was so well photographed--the place under the hill of Apicella. (See Plate 4a.)

I have enumerated the products which are constantly collected in fumaroles, although they are not all found at the same time or place, in order to show that the sublimations follow a certain law in their appearance. _Tenorite_, for instance, was formerly considered an accidental product of certain eruptions, and I have always found it; but if you visit the fumarole when the acids have had time to transform it, you will no longer see it. I found the crystallized chloride of lead, or "cotunuite," as it is called, for the first time in the lavas of 1855, and thought it a singular circumstance; but from that time I recognised it in all the lavas, though not always so beautiful and abundant; and even when not found as a distinct substance, I observed it in combination with chloride of copper. In the lavas of the 26th April _cotunuite_ and _tenorite_[E] were not very abundant, because the chloride of iron disturbed the greater number of the sublimations. I found sal ammoniac very abundantly on the fumaroles of the lavas that invaded the cultivated ground. Although chloride of ammonia, contrary to opinion, was not wanting in the sublimations of the fumaroles of the lavas deposited on other lavas, yet it was neither abundant nor crystallized, but combined in small quantities with other substances. It appeared in great abundance in all the fumaroles of lavas which covered cultivated or woody ground. At first it was scarce enough, and mixed with chloride of sodium; but when the rains came the sea-salt was washed away, and sal ammoniac formed beautiful crystals, nearly free from adventitious matters, as was the case with the fumaroles of the last lava. Afterwards, when chloride of iron was produced, ferro-chloride of ammonia was found. Crystals of sal ammoniac were sometimes found of a beautiful amber yellow. This colour was, in the opinion of my colleague, Professor Scacchi, produced by such small traces of chloride of iron that neither Professor Guiscardi nor I, nor indeed any other chemists to whom I submitted specimens for examination, could detect any. What I can affirm with certainty is, that these limpid crystals of a yellow colour were almost always attached to an amorphous substance, soluble in water, composed of various chlorides, in which iron was often detected.

From these remarks, it is evident that in the tranquil lavas the sublimations appear with a certain order of succession, and in the violent lavas, and those which flow most copiously, they are more complicated, and render both chemical analysis and spectroscopic researches more difficult. Notwithstanding, I observed traces of lithium and thallium, which I had previously perceived in some sublimations of 1871. I purpose submitting many sublimations which I have collected to more complete spectroscopic investigation, although I am persuaded that the discovery of traces of certain bodies in the sublimations or in the lavas is a matter of small importance to the science of volcanoes. I must say, however, that calcium was discovered on this occasion in great abundance, not only by the spectroscope, but also by chemical analysis. Sulphate of lime has often been found in larger or smaller proportions, but this was the first time I had observed chloride of calcium both close to the craters, and also in the sublimations of the fumaroles upon the lavas. The white stalactites which I collected beneath the great mass or bomb above described were almost exclusively composed of chloride of calcium, and only a few green drops manifested, with the usual re-agents, the presence of iron.

I did not fail to look often at the spectrum of the flowing lavas covered with the smoke which issued from them, but I always had a continuous spectrum. The spectroscope employed was Hoffmann's construction, with direct vision; but I think it would be better on other occasions to use a spectroscope combined with a telescope, like those used by astronomers.

But avoiding minute particulars of these sublimates, let us see what is the general direction and the order of their appearance. Sublimations are generally oxides, chlorides and sulphates, sometimes sulphides. Among the oxides, we must enumerate in the first place "tenorite" and _feroligiste_ or micaceous peroxide of iron. The first is almost always found at the commencement of activity in the fumaroles, simultaneously with the sublimation of chloride of sodium; the second--which is, perhaps, never wanting in eruptive cones that are often found lined with it inside--is seldom generated in the fumaroles of the lava, and therefore it is not easy to define the moment of its appearance. Sometimes one collects micaceous peroxide of iron on the lava, but it is often transported there from the mouths of eruption, as happened on this occasion.

Trustworthy writers are of opinion that all the oxides are derived from the decomposition of the chlorides, but I think I have clearly demonstrated that, with regard to copper and lead, the opposite statement may be affirmed; for the oxides are changed into chlorides, and hydrochloric acid liberated. Oxide of copper forms sublimates at the beginning, at the same time as the sea-salt; and if the fumarole be anhydrous or, as Deville would say, _dry_, this oxide does not change into either a chloride or a sulphate; but if the fumarole gives watery vapour, after a little hydrochloric acid is formed, which changes the oxide into a chloride, and if whilst this is going on oxide of lead be developed, it is changed into the chloride of lead, so frequently found in combination with chloride of copper. Then the sublimations change from white to red or yellow, and specimens when carried away gradually turn light blue, but when heated on platinum over a spirit lamp they resume their yellow tint. Sometimes the yellow colour remains longer, and in time changes to green; this also happens on the fumarole itself, the green commencing at the zones furthest removed from the centre, where the temperature is highest. When these sublimations are greenish, they become far less soluble than at first. The yellow, so common at a certain period on the fumaroles of the tranquil lavas, never attracted attention before I first examined it, doubtless, because it was considered chloride of iron, and yet in small eruptions this is only found close to the discharging mouths, and never in the sublimations of the fumaroles of the lava; but, on the other hand, it is the most copious and common product on the lavas of the great eruptions. This probably also accounts for the fact that lead, which is so obvious in the fumaroles of the lavas, had never previously been observed. In 1855, I noticed the crystallized chloride of lead in a fumarole in the Fossa della Vetrana, and this induced me always to look for it on the fumaroles of the later lavas; and I ascertained that, if it did not always appear as a distinct mineral, it was easily discovered in combination with other chlorides. The specimens which I have collected are not the most beautiful, but the presence of lead in the sublimations is not less common.

Micaceous peroxide of iron, when found on the lava, has been mostly conveyed from the eruptive mouths, as I have already stated, and perhaps never so abundantly and evidently as on this occasion. The lava of the 26th of April carried along a large quantity of round masses or bombs, varying in size, among which were found antecedent lava more or less covered with micaceous iron, either collected in the cavities of the lava, or incorporated with its mass. Sometimes the micaceous iron appears like little veins in the paste of new lava enveloping the exterior of these rounded masses, an exterior compact and lithoidal, and not resembling scoriæ. Among these spherical masses I found one of enormous size, four to five metres in diameter, which, having broken up where the exterior envelope was thinnest, I found filled with a great mass of lapilli and fragments of other lavas covered with micaceous iron. This bomb still preserves (June 5th) an elevated temperature within, and emits smoke and hydrochloric acid, which, meeting the micaceous iron discovered by breaking the envelope with blows of a hammer, transforms it superficially into chloride of iron, showing most clearly how, on some occasions at least, chloride of iron is formed from the oxide which precedes it. That those lapilli and the pieces of lava were solid when enveloped in the paste of the new lava, we infer from seeing the impressions on the inside of the said envelope. The chloride of calcium, which I found in this spherical mass almost pure, caused me to suspect that the sulphate of lime which is so often found on Vesuvius is a transformation of the chloride produced by the contact of sulphurous acid, which easily becomes transformed into sulphuric acid. The hydrochloric acid which escapes from a fumarole coming into contact with the scoriæ near its mouth, produces chloride of iron, which is, therefore, not always obtained by sublimation, although, when the temperature is very high, chloride of iron is conveyed from the interior of the lava, and sublimes on the exterior and colder parts; for instance, the chloride of iron which issues from the eruptive cones is sometimes found sublimed on the rocks of Monte di Somma. When chloride of iron has been produced by sublimation, we may collect it inside a glass bell placed over the fumarole, or upon a piece of brick; but when it is produced by the action of hydrochloric acid on the scoriæ, it will only be found on the scoriæ themselves.

If, therefore, the origin of micaceous peroxide of iron were due to the decomposition of the sesqui-chloride of iron requiring a more elevated temperature for its decomposition, it would follow that its genesis would be easier near the discharging mouths, and more difficult on the lavas, but there the fact was verified: for example, in the great bomb on the fumarole, where we observed micaceous iron transformed into chloride of iron. We may therefore consider it _proved_ that some chlorides--for instance, chloride of sodium--issue from the lava itself, either being there pre-existent, or being formed there; and that others are derived from the oxides which precede them, as undoubtedly is the case with chloride of copper; hence, the theory that derives the oxides always from the chlorides cannot be considered true. Granting that this theory might be applicable to the origin of micaceous iron, we should still want to know how it is found with the paste of the new lava itself, which forms the exterior coating of the bombs above described.

Many of these rounded masses, which have been rolled along by the lava, contain scoriæ partly decomposed by the long action of the acids found on the fumaroles of the craters. They disintegrate easily, and have a more or less yellowish tint. In the greater number of cases the interior of these masses is formed of leucitic lava, with cavities lined with micaceous iron. In short, their contents appeared to me quite similar to the material of the cone of 1871 and 1872, which in all probability was engulfed in the large crevasse or fissure that opened below it; and the fragments having thus fallen down into the lava, were enveloped by it and carried out by it after having been more or less rounded. The external envelope of these spheres is not at all scoriaceous, but compact and lithoidal, and sometimes composed of concentric folds or plaits.

As to the gaseous emanations of fumaroles, watery vapour with few exceptions comes first; this conveys the material which first appears in the sublimations, viz., sea-salt, and for the most part oxide of copper. If the fumarole continue active, it passes from the neutral period to the acid period, and first hydrochloric acid is produced, which, in small lava streams, never conveys chloride of iron, and rarely attacks the scoriæ to form that salt, but expends its force in changing the sublimations already there. For this reason chloride of iron, though completely absent in the lavas of 1871, was abundantly found in those of the 26th April, 1872. Sulphurous acid follows hydrochloric at a later period, and sulphuretted hydrogen occasionally succeeds.

Having examined the gases of fumaroles by means of a graduated tube, and the pyrogallate of potash, I always found that it contained less oxygen than the surrounding atmosphere.

For several years I wished to see whether the fumaroles of the lavas had a period of evolution of carbonic acid, as sometimes happens with fumaroles near the craters, but I have always obtained negative results. I often found that the atmosphere on the lavas contained an excess of carbonic acid, but as these lavas had burnt many trees, and it was probable that carbonic acid springs had formed under the lava, I never considered it safe to form any conclusion on the subject.

IV.

BOMBS, LAPILLI AND ASHES.

The bombs ejected from the craters are like those carried down by the lavas, but of smaller size, and they seldomer contain a nucleus similar to those found in the latter. With the bombs properly so called, many pieces of incandescent lava were thrown up, and in their fall went beyond the base of the cone. A quantity of small scoriæ varying in size accompanied these projectiles, and those fragments, which we call _lapilli_, fell at a greater distance. With the lapilli, and sometimes without them, the smoke carried a very minute dust or sand, which is generally called ashes. These ashes, when washed with water, lose soluble constituents which they have collected in the smoke--such as chloride of sodium and other chlorides and often free acids. The insoluble part originates in the detritus of lava, and with the microscope we can detect abundant fragments of those crystals which most frequently occur in the lava of the same eruption.

The lavas of 1871, which were eminently leucitic, and almost entirely deprived of pyroxene, resembled the ashes, which appeared to be fragments of crystals of leucite, more or less enveloped in the paste of the lava, so that having triturated the scoriæ of the lava, and looked at the powder through the microscope, it was apparently quite the same as the ashes.

But at the beginning of the eruption of the 26th April, a white sand fell in the Atria del Cavallo, close to the Crocella[5], which on the dark scoriæ of 1871 looked like snow. Its fall had a limit so well defined that one passed without any gradation from white to black. Having collected some of this sand that very morning, I put it up in white paper, for at that moment it was impossible for me to examine it. Taking it out some days after, I found it had become reddish, and having put it under the microscope, I observed that it was exclusively formed of little pebbles more or less round, of a transparent vitreous matter, partly covered with a red substance. Fragments of green crystals occurred in this sand, upon which no red was perceptible. I consulted our eminent crystallographer, Arcangelo Scacchi, whether these little pebbles were leucite, as I suspected, and whether the green particles were pyroxene: he confirmed my suspicion, and remarked that the red colour was superficial only. We then washed a little of the sand in hot water, and saw the pebbles become whitish; but having heated some on platinum, we observed that they first turned black and then became perfectly white, proving that the red was a deposit of organic matter. To see these leucites, rounded like small pebbles transported by a torrent, deprived of the soluble chlorides which generally accompany Vesuvian ashes, is a matter worthy of attention. Whilst heating this sand upon platinum, decrepitation was audible, which indicated the cracking of some of the little pebbles. It is evident, therefore, that crystals of leucite raised to a certain temperature may break, and thus we can understand how almost all Vesuvian ashes contain fragments of the said crystals enveloped in the paste of the lava. It is evident that the soluble part of the ashes is obtained from the smoke through which it passes. On this occasion the smoke from the craters did not apparently contain much acids, for no bad smell was perceptible, and the water in which I washed the ashes scarcely reddened litmus paper. Even chloride of iron, which was so abundant in the lavas, was scarcely perceptible in the smoke, which almost exclusively deposited sea-salt on the surrounding rocks; I say sea-salt advisedly, and not chloride of sodium, to show that I include all that sea-salt contains. The slight disturbance it manifested with chloride of barium, and the small precipitate with oxalate of ammonia, reveal sulphate of lime, without excluding the possibility of the chloride.

But how can these ashes do so much injury to the vegetation of the ground they cover, especially at the first fall of rain? I think that the damage is due partly to the sea-salt, and partly to the acids contained either in the ashes or in the rain-water itself. Upon watering the tender tops of some plants with a saturated solution of the salt from Vesuvius itself, I noticed that they withered away after a few hours. But very often the rain alone which traverses the smoke of Vesuvius, or is produced by condensation from it, gives manifest acid reactions, and destroys the grass and the tops of the trees. The peasants believe that the rain is warm or of boiling water, from observing that the tender parts of the plants are, by its deposit, all burnt up. Vegetation is now recovering, but without flowers, and consequently without fruit.

V.

THE CRATERS AND THEIR FUMAROLES.

The greater part of the lava issued from the base of the great fissure in the cone which I have described; and although two other lava streams descended from the top of the mountain, neither proceeded from the crater, but from apertures near it. The great crater, divided in two as already described, opened wide on the morning of the 26th April, destroying the brim of the antecedent crater, and remaking it in another shape with ejected matter, except on the south-west side, where the brim was split. (See Plate 5.)

From this double crater, copious smoke, bombs and incandescent scoriæ, with ashes and lapilli, issued with violence, and from the depths below came dreadful detonations and bellowings, producing great terror. And yet the lava poured out into the Atria del Cavallo without any noise, and not even a column of smoke marked its origin of issue--namely, from the fissure.

When the eruption was over, the sight of the vertical walls of these deep craters, of almost horizontal strata of scoriæ and lithoidal masses, with a fracture fresh, and as if they had never undergone the action of fire or of acid vapours, without recent scoriæ and without fumaroles, was to me a marvellous spectacle. The fumaroles were almost all on the brims of the craters, with emanations of hydrochloric and sulphurous acid. In a few that were more removed from the brim, sulphuretted hydrogen was perceptible. In the sublimations, chloride of iron was most abundant, in combination with other chlorides, for example, of sodium, magnesium and calcium. This last chloride was frequent even among the sublimations of the fumaroles of the lavas, and it was the first time it was ever remarked, but I do not think it was the first time that it was ever produced: being in combination with chloride of iron, and very deliquescent, it did not attract attention from anyone. In a hollow fragment of scoriæ I observed a yellowish substance, which looked like sulphur in a viscid state, and which boiled at a temperature of 120°, and evolved hydrochloric acid. Having collected this substance and poured it into a glass phial, it quickly coagulated into an amorphous mass of the same colour; but before I reached the Observatory, I found that it had become liquid by deliquescence. It consisted of a mixture of the aforesaid chlorides, according to an analysis made by Professor Silvestro Zinno and myself. In some fumaroles, where I perceived the smell of sulphuretted hydrogen, I found sublimed sulphur under the scoriæ.

At the source of the lava stream that flowed towards the Camaldoli, on the seaward flank of Vesuvius, I observed large fumaroles of steam only, pure aqueous vapour.

There was no trace of carbonic acid in these fumaroles, but that fact does not imply that there was none at a later period, for, since the first investigations of Deville, it is known that carbonic acid is found under certain conditions on the very summit of Vesuvius.

VI.

THE ELECTRICITY OF THE SMOKE AND ASHES.