Part 46
Mr Blyth says: "It is found that the post-mortem change into orpiment is never quite complete, so that for the detection of arsenic in solid organic substances, such as the tissues of the body, the best general method is most decidedly to convert the arsenic, if present, into the volatile chloride; and according to Dr Taylor, there is always sufficient arsenic (if present at all) unchanged into sulphide to ensure success. The only necessary caution is that the substance be thoroughly dried, and that the reagents be pure. After drying it is placed in a retort with fuming hydrochloric acid, and slowly distilled by the heat of a sand-bath. The distillate contains chloride of arsenic (if arsenic was present), and may be submitted to further tests."
_Estim._ This may be effected in various ways:--
1. GRAVIMETRICALLY:--Arsenic is usually WEIGHED under the form of arsenate of lead, arsenate of sesquioxide of iron, tersulphide of arsenic, (metallic) arsenic, or (directly) as arsenious anhydride. The last three only, as the more simple and convenient, will be noticed here:--
As trisulphide:--The whole of the arsenic being precipitated by a stream of sulphuretted hydrogen, with the necessary precautions, in the manner already noticed, the precipitate, after being carefully collected, washed, and dried, is purified by redissolving it in pure ammonia water, and evaporating the resulting solution in a weighed watch glass or capsule by the heat of a water-bath. It is then dried at a temperature not above 212° Fahr., and finally weighed. Each grain of the tersulphide so found corresponds to ·80487 gr. of arsenious acid, or ·61 gr. of metallic arsenic.
As (metallic) Arsenic:--Obtained by one of the processes already given. Each gr. represents 1·32 gr. arsenious acid.
As Arsenious anhydride:--Obtained in a weighed capsule or tube, either by the crystallisation or sublimation test. The weight is the answer sought for arsenious anhydride. Each gr. of this is equiv. to ·75758 gr. of metallic arsenic.
VOLUMETRICALLY. (Method of F. Mohr.) This depends on the fact that an aqueous solution of arsenious acid, or of an alkaline arsenite, when mixed with an excess of saturated solution of pure bicarbonate of soda and a little starch-paste, has its arsenious acid converted into arsenic acid by a solution of iodine. A standard solution of iodine is, therefore, an appropriate arsenim'eter for the above mixture. The solution of iodine is added until the blue starch-reaction just begins to appear, the arsenious solution having been previously exactly neutralised with pure carbonate of soda if acid, or with pure hydrochloric acid if alkaline. The results are accurate when no substance capable of oxidising or decomposing iodine is present in the liquid tested.
_Phys. eff., &c._ Arsenious anhydride or white arsenic is alike destructive to vegetable and animal life. Seeds soaked in any but a very weak solution of it lose their power of germination, and buds plunged in it become incapable of expanding into flowers. When applied to the leaves, roots, or stems, absorption takes place, and the plant soon perishes. On combustion it evolves the characteristic garlic-like odour of arsenic, and arsenic may be discovered in its substance by chemical tests. According to Jäger, Gilgenkrantz, and Pereira, a few of the lower order of the algæ are occasionally developed in solutions of arsenious acid. To all animals, from the infusoria up to man, arsenic proves deleterious, although in different degrees, the highest susceptibility of its effects existing in man on account of the superiority of his development. In all of them death is preceded by inordinate actions and increased evacuations, especially from the mucous surfaces. Difficult respiration, thirst, vomiting, and convulsions are the leading symptoms which gradually develope themselves as we approach the higher grades of the system. (Jäger.) In very small or therapeutical doses, properly administered, it is a valuable medicine, and acts as a tonic, alterative, and antispasmodic attenuant, and externally as an escharotic. In slightly increased medicinal doses, or long-continued small doses, nausea, vomiting, purging, griping, debility, emaciation, and all the effects of slow-poisoning, occur in succession--a gradual sinking of the powers of life, without any violent symptom; a nameless feeling of illness, failure of the strength, an aversion to food and drink, and to all the enjoyments of life. Redness of the conjunctiva and eyelids, headache and giddiness, spasms, eczematous eruptions, numbness and paralysis of the limbs, and ptyalism, are also frequent and well-marked symptoms of slow poisoning by arsenic. In an excessive or poisonous dose the symptoms are rapid and violent, usually indicating extreme gastro-intestinal inflammation and disorder of the cerebro-spinal system, and often occasioning death in from one to three days. The smallest fatal dose found recorded by Christison is 4-1/2 gr., taken in solution. The subject was a child 4 years old, and death occurred in six hours. 2-1/2 gr. destroyed a robust girl in 36 hours. (Letheby.) 2 gr., in solution, are suspected to have caused the death of a full-grown woman. 2 or 3 gr. may be a fatal dose. (Dr A. Taylor.) Notwithstanding these facts much larger quantities have been taken, under peculiar circumstances, with comparative impunity; and cases are not wanting in which even enormous quantities have produced very trifling effects.
_The dose for animals is_--CATTLE, 5 to 10 grains. HORSE, 5 to 10 grains. SHEEP, 1 to 2 grains. PIG, 1/2 to 2 grains. DOG, 1/15th to 1/10th of a grain.
Under all circumstances arsenious anhydride is, undoubtedly, one of the most powerful of the mineral poisons; and in whatever form or way it is introduced into the system it exerts the same deleterious influence. In all cases, in sufficient doses, its action is to increase the secretions, diminish the contractility of the voluntary muscles, and to produce convulsions, prostration and death.
Arsenic is a non-accumulative, irritant poison, and exerts no decided chemical or corrosive action on the tissues. (Taylor.)
_Pois., &c.--Symp._ These sometimes begin to appear within half an hour after the poison has been taken, or even sooner; but much more generally, not until after the lapse of some hours. They usually commence with nausea and distress at the stomach, followed by thirst, often intense, and a sense of burning heat in the bowels; then come on constriction of the [oe]sophagus, violent vomiting, severe colic pains, tenesmus, and excessive and painful purging, the stools being occasionally bloody; but pain, vomiting, &c., do not invariably occur. The pulse is generally quick, small, feeble, and irregular--sometimes scarcely perceptible, and the heart's action is irregular and tumultuous. The tongue is dry and furred; the respiration difficult and panting; the urino-genital apparatus is often affected; there is pain and difficult micturition, and sometimes entire suppression of urine; faintings, coldness of the limbs, and cold sweats, with other signs of debility, intervene. Itching, and eczematous eruptions of the skin, trembling, painful cramps, and contractions of the extremities, and violent convulsions often follow; and after these, a greater or less prostration of strength, which induces a deceitful calm. At length the heart's action abates, the skin becomes suffused with a cold clammy sweat, and the sufferer dies from exhaustion. The progress, succession, and precise character of the symptoms are modified by the idiosyncrasy of the individual, the quantity of the poison, and the manner in which it has been taken; and are seldom all present in the same person.
_Treatm._ If vomiting has commenced it should be promoted by tickling the throat, and administering a large quantity of gelatinous hydrated peroxide of iron, or other appropriate antidote, in divided doses, mixed with a large quantity of warm or tepid water, strongly sweetened with sugar. If vomiting has not commenced, which is rare, it must be excited by administering 15 to 20 gr. of sulphate of zinc, or ipecacuanha (or in the absence of these, a teaspoonful of flour of mustard) in a tumbler of tepid water, and tickling the throat as before. If these means fail in rapidly inducing copious vomiting, the dose must be repeated, or the stomach-pump had recourse to. Altogether as much as 16 to 18 _oz._ of the hydrated peroxide of iron may be administered. If the poison has been swallowed several hours previously, and hence may have passed the pylorus, a strong dose of castor oil or a purgative clyster may be administered, and, after its action, another clyster containing the antidote. As soon as the stomach and bowels are cleared, diuretics and sudorifics should be given in abundance. Lastly, any remaining irritation must be relieved by demulcent and soothing remedies; or if urgent, by slight general or local bleeding, which cannot be earlier practised without danger; and opium, camphor, and ether, followed by tonics, may be had recourse to, to recruit the system.
_Lesions._ Redness and inflammation of the whole primæ viæ; and sometimes of the mouth, fauces, and [oe]sophagus, but more usually the contrary. Sometimes also, though seldom, there is no marked appearance of inflammation in the stomach and intestines. The stomach is usually highly injected, and frequently marked with extravasations; lungs gorged with blood; mucous lining of trachea reddened; heart generally flabby, and exhibiting deep red or blackish stains, and the right cavities more or less loaded with blood; the conjunctiva is sometimes very vascular; and redness, extravasation of blood, and effusion of serum is occasionally seen in the brain. The blood is frequently, though not invariably, fluid after death, and dark coloured. Under certain circumstances, the mucous membrane of the stomach and intestines is lined with a multitude of brilliant points or grains, which have been mistaken for arsenious anhydride; but which, according to Orfila, are composed of fat and albumen. Placed on burning coals, they decrepitate on drying, and produce a species of explosion or detonation. These grains are also met with in the stomach of persons who have not been poisoned. Digested in water, the liquid obtained from them does _not_ show the presence of arsenic when submitted to reagents.
_Ant._ In the order of their assumed efficiency:--MOIST PEROXIDE OF IRON.--See under the preparations of IRON (Arsenici Antidotum, G.). Hydrated or gelatinous sesquioxide or peroxide of iron (for an adult--a tablespoonful, in water, every 8 or 10 minutes until 12 or 16 oz., or more, have been taken). Hydrated sulphide of iron (as the last). Gelatinous hydrate of magnesia (as the last). Calcined magnesia (taken as the first). Salad or olive oil, or almond oil, and oil or fats generally (ad libitum), are all highly effective in lessening, if not destroying the action of arsenious anhydride.[81] Albumen (white of egg), or liquids containing it (in cold water, ad libitum). Milk, wheat-flour, oatmeal gruel (with water, ad libitum). Lime water, with milk (as the last). Chalk, with milk and water (as the last). Infusion or decoction of bark, or better, of nut-galls (as the last). Sugar or syrup (ad libitum). See _Treatm._ (above); also the above substances under their respective heads.
[Footnote 81: Dr Blondlot, in a paper communicated to the Paris Academy of Sciences, has come to the conclusion that the slightest quantity of greasy matter in contact with arsenious anhydride reduces its solubility to about 1-20th of what it was before. This explains at once why, in certain judicial investigations, arsenic has been sought for in vain in the liquid contents of the stomach, when the food consisted partly of fatty substances, such as broth, milk, &c. It likewise explains how arsenious anhydride, taken in powder, may sometimes remain a long time in the stomach before it produces any deleterious effect; since, in such cases, its action is hindered by the presence of fatty matter. Jugglers often swallow arsenic with impunity, because, according to Dr Blondlot, they previously take the precaution to drink milk and eat fat bacon. Hence, in cases of poisoning by arsenic, oils and fatty substances may be administered as real antidotes, capable of suspending the action of the poison for a considerable time, until more radical means of effecting a cure can be applied. The people engaged in some of the arsenic-works regard salad oil as almost a certain antidote to this poison.]
_Uses, &c._ Arsenious anhydride and its compounds are extensively employed in the arts and medicine. It is used by the dyer, it furnishes the artist with several of his most beautiful pigments, and the glass-maker and enameller with a flux or material to whiten and decolour their wares. In _agriculture_, it is used (in solution) as an anti-smut for seed-wheat; and as an anti-vermin lotion or dipping for sheep and cattle. In small (therapeutical) doses it is a valuable remedy in intermittent fevers, chronic skin diseases (especially lepra and psoriasis), and in several nervous affections (as neuralgia, epilepsy, chorea, tetanus, &c.). It is the active ingredient of the tasteless ague-drop; of Fowler's and Pearson's solutions; and in the Tanjore pills, long celebrated in India for the cure of the bite of the cobra di capello and other venomous serpents, as well as of hydrophobia. It has been given in syphilis, chronic rheumatism, typhus, and several other diseases, with more or less advantage. Cautiously administered in phthisis, it frequently restores the appetite and strength and greatly retards, and in some cases arrests, the progress of the disease. It has been recently used to relieve toothache arising from caries. Externally, it is employed in the form of powder, lotion, and ointment, for the cure of cancer. Plunkett's ointment, Pâte arsénicale, Davidson's Remedy for Cancer, and several other like preparations, owe their activity to arsenious anhydride. Water in which white arsenic has been steeped has become a favorite cosmetic wash with many ladies, since its assumed property of softening the skin was announced in a certain popular periodical. It is also the prime ingredient in the papier moure, a popular fly paper. Its use, whether internal or external, is, however, attended with considerable danger in unskilful hands, and should, therefore, never be adopted but under proper advice.--_Dose_, 1/20 to 1/8 gr., made into pills with crum of bread and lump sugar; or in solution, 3 to 5 or 6 drops, twice or thrice daily, gradually and cautiously increased to 12, or even 15 drops. As a rule, arsenical preparations should be taken soon after a meal, and by no means on an empty stomach. (Dr A. T. Thomson.) The dose should be suspended, or greatly reduced, as soon as the conjunctiva is affected (Hunt); or if dryness of the mouth or throat, or irritation of the stomach or bowels, ensues. Mr Maculloch found the pills more efficacious than the solution; they act differently, and cannot be substituted for one another.
Arsenic is a favorite tonic and alterative with farriers, who often administer it very carelessly to horses, to the serious injury of these animals. It is also a favorite with grooms, who have imbibed the notion that small doses of it contribute to improve the condition of the skin. The best-informed veterinarians, however, either wholly avoid it, or use it with very great caution.[82]--_Dose_ (for a HORSE), 2 to 5 or 6 gr., twice or thrice daily; in farcy or glanders, 10 to 12 gr. In solution it is often employed as a wash or dipping to destroy vermin in cattle and sheep; but its use is not free from danger, particularly to the shepherds or dippers.
[Footnote 82: "As a therapeutic agent for horses, arsenious acid can be well dispensed with. It is, however, employed by some as a tonic, in doses of from 10 to 20 gr. daily; and by others as a vermifuge. When injudiciously administered death has been the result. By those of the old school it is extolled as a caustic, and a very powerful one doubtlessly it is; but there is this disadvantage attending its use--we cannot control its action, and, oftentimes, a most extensive and painful wound is caused by it. Occasionally it is resorted to for the eradication of warts; although a better plan is to extirpate them at once with the knife. When, however, this is inadmissible, 1 part of arsenious acid, in very fine powder, may be mixed with 4 parts of lard, and a (small) portion of the compound applied, with friction, over and around the excrescence every other day, for three or four times. This will excite such a powerful sloughing action, that in about 10 days the warts will be thrown off." (Prof. Morton.)]
_Gen. commentary._ The necessary length of the preceding article, owing to the great importance of the subject in its relations to toxicology and medical jurisprudence, has left us little space for further remark here. In addition to what has been said on arsenical testing, it may be useful to caution the reader of the absolute necessity of only employing tests and reagents which are themselves absolutely pure; and in which the operator has, by personal examination, failed to detect the slightest trace of arsenic. Commercial sulphuric, nitric, and hydrochloric acids, potash, soda, nitre, iron, and zinc, frequently contain arsenic; from which, however, they may be freed by chemical processes; or they may be purchased in the pure state from respectable dealers in chemicals. But no assurance of the vender should be regarded as a proof of their purity. In all judicial investigations the absence of arsenic in the several tests and reagents, and the apparatus employed, must be demonstrated and sworn to. We may further add, that the results afforded by no single test can be depended on. In matters of such vast importance, the most ample confirmatory evidence must be sought.
Marsh's, Reinsch's, Lassaigne's, the sulphur, and the Reduction Tests, and their modifications, are those now generally preferred by toxicological chemists; each of which, with its confirmatory tests, are amply sufficient for the indisputable identification of arsenic.
Modern toxicologists have abandoned most of the old processes for the detection of arsenic, and have adopted one of two, which have been found more expeditious as well as more certain. These are the tests of Marsh and Reinsch, preferably the latter.
HERAPATH'S METHOD is to obtain deposits by Reinsch's Test on 4 or 5 pieces of No. 13 copper wire; each piece being about 2-1/2 inches long, and previously flattened and planished with a polished hammer for about one half its length. The deposit, with some of the adhering copper, scraped from one of these coated pieces, is sealed up hermetically in a tube for future production. The scrapings from three pieces of wire are separately submitted to the sublimation test in tubes bent in the form of an obtuse V capillary at one end, and about 3/10ths of an inch in diameter at the other; the capillary leg being about three times as long as the larger one. The scrapings are placed in the bent part of the tube; and the flame of a small spirit lamp is so applied as to slowly drive the sublimate into the narrower portion of the tube, which is held rather higher than the other. If the deposit so obtained be mercury, it condenses in white shining globules;--if lead or bismuth, it does not rise but melts into a yellowish glass, which adheres to the copper; if tellurium, it falls as a white amorphous powder; if antimony, it does not rise at that low temperature; but if it be arsenic, it sublimes as arsenious anhydride, which condenses as minute octahedral crystals, looking, with the microscope, like very transparent grains of sand. One of these tubes containing the sublimed arsenious anhydride is then sealed up, like the first one, for future production. The capillary part of another tube containing the sublimate is then cut off, and carefully boiled in a few drops (10 to 15) of distilled water; and, when cold, 3 or 4 drops of the resulting solution is poured on a plate of white porcelain, and to this, by means of a glass rod, one drop of solution of ammoniacal sulphate of copper is added. The mixture is then carefully conducted on to a piece of white filtering-paper set on the surface of a smooth, clean, and dry chalk-stone, by which the moisture is absorbed, and the smallest portion of Scheele's green produced by the test rendered more conspicuous. The ammonio-nitrate of silver test is then applied, in a similar manner, to 3 or 4 drops of the remaining solution; after which the pieces of paper with the spots are dried, and sealed up in separate tubes, as before, observing to exclude the light from that containing the yellow precipitate of arsenite of silver. A stream of sulphuretted hydrogen is then passed through the remaining tube containing the arsenical sublimate, by which the latter is converted into the yellow tersulphide--this too is sealed up. Here are now five tests--the metal, the acid, arsenite of copper, arsenite of silver, and yellow tersulphide of arsenic.
It is now well known that certain soils contain arsenic, either as arsenite of lime or sulphide of arsenic; and which, under favorable circumstances, may permeate or be absorbed by a body, after interment. In judicial investigations following disinterment it is, therefore, necessary to examine portions of the cemetery-earth taken from the grave, as well as from parts more or less distant from it. For this purpose the earth should be thoroughly dried in a water-bath, drenched with pure and concentrated hydrochloric acid, and allowed to stand for twenty-four hours. The mixture is then distilled, and the distillate tested for arsenic by Reinsch's or Marsh's test. Should the product of one distillation yield no evidence of arsenic, it should be returned to the retort, if necessary, a second or even a third time, and the distillation repeated.