Poisons, Their Effects and Detection / A Manual for the Use of Analytical Chemists and Experts

Diarrhœa does not seem, as a rule, to follow when the salt is administered by subcutaneous injection to animals; but Gmelin’s rabbits had considerable diarrhœa when 1·9 grm. was introduced into the stomach. The same quantity, injected beneath the skin of a dog, caused loss of appetite, and, after six days, there was a dry exanthem on the back, and the hair fell off in patches; there was, however, neither diarrhœa nor vomiting. Bichromate of potash causes (according to the researches of Pelikan)[962] symptoms similar to those produced by arsenic or corrosive sublimate; it acts as a powerful irritant of the stomach and intestinal canal, and may even cause inflammation; on its absorption a series of symptoms are produced, of which the most prominent are albuminuria, bloody urine, and emaciation. From ·06 to ·36 grm. (1-5¹⁄₂ grains) is fatal to rabbits and dogs.

§ 888. Effects of some of the Chromium Salts on Man—Bichromate Disease.—In manufacturing potassic bichromate, the workmen exposed to the dust have suffered from a very peculiar train of symptoms, known under the name of “bichromate disease.” It was first described in England by Sir B. W. Richardson.[963] It appears that if the workmen inspire the particles chiefly through the mouth, a bitter and disagreeable taste is experienced, with an increase of saliva. This increase of the buccal secretion gets rid of most of the poison, and in that case but little ill effect is experienced; but those who keep the mouth closed and inspire by the nose, suffer from an inflammation of the septum, which gradually gets thin, and ultimately ulcerated; finally the whole of the septum is in this way destroyed. It is stated that when a workman has lost his nasal septum, he no longer suffers from nasal irritation, and has a remarkable immunity from catarrh. The Chemical Works Committee of Inquiry report (1893) that the manufacture of bichromate of potash or soda is practically in the hands of three firms at Glasgow, Rutherglen, and Falkirk, and that they visited all of them, and found “that almost all the men working where dust was prevalent, more especially between the furnaces and the dissolving tanks, had either perforation of the septum of the nose, or had lost the septum altogether.” The bichromate also causes painful skin affections—eruptions akin to eczema or psoriasis; also very deep and intractable ulcerations. These the workers call “chrome holes.” These cutaneous maladies start from an excoriation; so long as the skin is not broken, there seems to be little local effect, if any. The effects of the bichromate are also seen in horses employed at the factories; the salt getting into a wound or crack in the leg, produces ulceration: horses may even lose their hoofs.

§ 889. Acute poisoning by the chromates is rare. In the ten years ending 1892, in England and Wales, 4 accidental deaths are ascribed to potassic bichromate and 1 to chromic acid. Falck has, however, been able to find in medical literature 17 cases, 6 of which were suicidal, 10 accidental, and in 1 the bichromate was used as an abortive. In a case of poisoning by the chromate of potash (related by Maschka),[964] in which a woman, aged 25, took for a suicidal purpose a piece of potassic chromate, which she described as the size of a hazel-nut (it would probably be at least 6 grms. in weight), the chief symptoms were vomiting, diarrhœa, pain in the stomach, and rapid collapse; death took place fourteen hours after swallowing the poison.

In poisoning by potassic bichromate, there may be much variety in the symptoms, the more usual being those common to all irritant poisons, i.e., vomiting, diarrhœa, and collapse, with cramps in the limbs and excessive thirst; and the rarer affecting more especially the nervous system, such as narcosis, paralysis of the lower limbs, and dilatation of the pupils; occasionally there is slight jaundice.

In a case recorded by Dr. Macniven,[965] a man took a lump of bichromate of potash, estimated to be over 2 drachms (7·7 grms.). The symptoms commenced in fifteen minutes, and consisted of lightness in the head, and a sensation of great heat in the body, which was followed by a cold sweat; in twenty minutes he vomited; he then suffered from great pain in the stomach, giddiness, specks before the eyes, a devouring thirst, and there was loss of power over the legs. These symptoms, again, were followed by severe rigors and great coldness of the extremities. On the patient’s admission to hospital, two hours after taking the poison, it was noted that the pupils were dilated, the face pale and cold, and the pulse feeble. He complained of intense epigastric pain, and a feeling of depression; there was some stupor; the stomach was emptied by emetics and by the stomach-pump, and the patient treated with tepid emollient drinks, whilst subcutaneous doses of sulphuric ether were administered. He made a good recovery.

In a case recorded by Mr. Wilson,[966] a man, aged 64, was found dead in his bed twelve hours after he had gone to rest. During the night he was heard to snore loudly; there were no signs of vomiting or purging, and bichromate of potash was found in the stomach.[967]

§ 890. Chromate of lead has also caused death. In one case[968] the breathing of chromate of lead dust seems to have been fatal; and there is also a double poisoning recorded by Dr. Linstow,[969] of two children, aged three and a half and one and three-quarter years respectively, who ate some yellow ornaments,[970] which were used to adorn a cake, and which contained chrome yellow (chromate of lead). The younger died in two and the elder in five days. The symptoms were redness of the face, dulness, and an inclination to sleep; neither complained of pain; the younger one had a little diarrhœa, but the elder neither sickness nor purging.

§ 891. Post-mortem Appearances.—We possess some very exact researches[971] upon the pathological changes induced by subcutaneous injections of solutions of potassic bichromate on animals, and especially on the changes which the kidneys undergo. If the animal is killed, or dies a few hours after the injection, there are apparently no striking appearances, but a closer microscopical examination shows considerable changes. The epithelium of the tubuli contorti exhibits a yellow cloudiness, and the outline of the cells is irregular and jagged. The glomeruli are moderately injected, and their capsules contain an albuminous exudation; the canaliculi are filled with round cells imbedded in a fluid which, on heating, coagulates, and is therefore albuminous or fibrinous; probably this is the first stage of the formation of fibrinous casts.

In the case quoted of the woman who poisoned herself with potassic chromate, very striking changes were found in the stomach and intestines. The stomach contained above a litre of dark chocolate fluid of alkaline reaction; the mucous membrane, in the neighbourhood of the cardiac and pyloric extremities, was swollen and red in sharply defined patches; portions of the epithelial layer were detached, the rest of the mucous membrane was of a yellow-brown colour, and the whole intestine, from the duodenum to the sigmoid flexure, was filled with a partly bloody, partly treacly-looking fluid; the mucous membrane, throughout its entire extent, was swollen, with numerous extravasations, and in places there were losses of substance. Similar appearances to these have been found in other instances; the anomalous case recorded by Mr. Wilson (ante) is an exception. In this instance a pint of inky, turbid liquid, which yielded to analysis potassic bichromate, was found in the stomach; but there were no marked changes anywhere, save a slight redness of the cardiac end of the gullet. In Linstow’s two cases of poisoning by lead chromate, there were found in both fatty degeneration of the liver cells, and red points or patches of redness in the stomach and intestines. In the elder boy the changes in the duodenum were very intense, the mucous membrane was swollen and easily detached, in the upper part strongly injected with blood; in one place there was a perforation, and in several places the membrane was extremely thin. In the younger boy the kidneys seem to have been normal, in the elder congested and containing pus. Although it was clear that the two children died from lead chromate, a chemical analysis gave no result.

§ 892. Detection of the Chromates and Separation of the Salts of Chromium from the Contents of the Stomach, &c.—If in the methodical examination of an acid liquid, which has been already filtered from any precipitate that may have been obtained by sulphuretted hydrogen, this liquid is made alkaline (the alkali only being added in slight excess), and hydrated chromic oxide is thrown down mixed, it may be with other metals of the second class, the precipitate may then be fused with nitre and potassic carbonate, and will yield potassic chromate, soluble in water, and recognised by the red precipitate which it gives with silver nitrate, the yellow with lead acetate, and the green colour produced by boiling with dilute sulphuric acid and a little alcohol or sugar. If by treating a complex liquid with ammonium hydrosulphide, sulphides of zinc, manganese, and iron are thrown down mixed with chromic oxide, the same principles apply. If a chromate is present in the contents of the stomach, and the organic fluid is treated with hydrochloric acid and potassic chlorate, chromic chloride is formed, and dissolving imparts a green colour to the liquid—this in itself will be strong evidence of the presence of a chromate, but it should be supplemented by throwing down the oxide, and transforming it in the way detailed into potassic chromate.

A general method of detecting and estimating both chromium and barium in organic matters has been worked out by L. de Koningh.[972] The substances are burnt to an ash in a platinum dish. The ash is weighed; to the ash is added four times its weight of potassium sodium carbonate and the same amount of potassium nitrate; and the whole is fused for fifteen minutes. The fused mass is boiled with water and filtered; if chromium is present, the filtrate is of a more or less pronounced yellow colour, but manganese may produce a green colour and mask the yellow; this colour is removed by boiling with a little alcohol. The liquid is concentrated down to 20 c.c., filtered into a test-tube, and a colorimetric estimation made of the chromium present by imitating the colour by a solution of potassium chromate of known strength. To prove that the colour is really due to chromium, acetic acid and lead acetate are added, when the yellow chromate of lead is at once thrown down. (If lead was in the ash, a yellow precipitate may appear on the addition of acetic acid.) To the portion of ash insoluble in water strong hydrochloric acid is added, and to the acid solution a large excess of calcium sulphate is added; this precipitates barium as sulphate free from lead sulphate, for, if the latter should be present, it does not, under the circumstances, come down, being soluble in strong hydrochloric acid.

3. THALLIUM.

4. ALUMINIUM.

§ 896. Aluminium and its Salts.—A strong solution of acetate of alumina has irritant properties, and has given rise to accidents. The term alum, in a chemical sense, is given to a class of bodies of the type of AlKSO₄. Common alum is at the present time ammonia alum, NH₄Al(SO₄)₂ + 12H₂O; when made anhydrous by heat it is known by the name of burnt alum, and possesses caustic properties.

§ 897. Action of Alum Salts.—Death or illness has hitherto only taken place from the ingestion of large doses of alum or the acetate, and the symptoms in these cases have been those of an irritant poison; we are, however, indebted to Paul Siem[975] for a research on the absorbed substance, in which the local effects as far as possible have been reduced.

Siem’s research was made on frogs, cats, and dogs. For frogs he employed a double salt, consisting of sodic and aluminic lactate, to which he ascribed the formula Al₂(C₃H₅O₃)₃(C₃H₄NaO₃)₃, equal to 15·2 per cent. of Al₂O₃. Twenty to thirty mgrms., administered by subcutaneous injection to frogs, caused death in from ten to twenty-four hours. After the injection there was restlessness, and, ultimately, general paralysis of the central nervous system. The circulation was not affected; the heart was the last to die.

For warm-blooded animals he used the double tartrate of sodium and aluminium. Beginning with a small dose subcutaneously administered, he gradually increased it, and found, under these circumstances, that the lethal dose for rabbits was 0·3 grm. per kilo. of body weight; for dogs 0·25 grm., and for cats 0·25 to 0·28 grm.; if, however, a single dose was administered, then cats could be killed by 0·15 grm. per kilo. The symptoms commenced ten to twelve hours after the injection of a large dose, but with a medium dose the symptoms might be delayed for from three to four days, then there was loss of appetite, constipation, emaciation, languor, and a disinclination to move. Vomiting and loss of sensation to pain followed, the power of swallowing even saliva was lost, and a condition supervened similar to bulbar paralysis. However true this picture may be when large doses are given subcutaneously, it does not follow that hydrate of alumina in small doses, given by the mouth, mixed with food, produces any symptoms whatever.

Alum baking-powders, containing from 30 to 40 per cent. of alum mixed with carbonate of soda, are in commerce, and have been for a long time, many tons being sold yearly. When water is added to such powders decomposition takes place, the result being sodic sulphate and aluminic hydrate, carbonic acid being given off. Were the hydrate, in small doses, capable of producing indigestion or disease of the central nervous system, it seems astonishing that, considering the enormous number of persons who use alum baking-powders, there should not be some definite evidence of its effect. The author and his family for months together have used alum baking-powders without any apparent injury, and there is little doubt that alumina hydrate passes out of the system mainly by the bowel, without being absorbed to any great extent. In a trial with regard to an alum baking-powder at Pontypridd (1893), the prosecution advanced the theory, and supported it by eminent scientific opinion, that aluminium hydrate was dissolved by the hydrochloric acid of the gastric juice, forming chloride of aluminium, some of which might be absorbed and enter the circulation; that which was not absorbed in the stomach passed on, and, meeting the alkaline fluids of the intestines, was again separated as aluminium hydrate, and as such absorbed.

If this does occur, still there is no direct evidence of its toxic influence in the small quantities used in baking-powder. It may be pointed out, also, that with regard to the possible lethal effect of a non-corrosive salt of alum, presuming that the lethal dose for man is the same as that for a cat, the amount of alumina to kill a 68-kilogramme man would have to be equal to 17 grms., or about 3 ozs. of ammonia alum. This important question can only be settled by careful feeding of animals carried on for a long period of time.

§ 898. Post-mortem Appearances.—In the few cases in which persons have been killed by large doses of alum or its salts there have been found corrosion of the mouth, throat, and stomach, and hyperæmia of the kidneys and intestine. In the animals experimented upon by Paul Siem, hyperæmia of the intestine, fatty degeneration of the liver and hyaline degeneration of the kidneys were the chief changes noted.

§ 899. Detection of Alumina.—In all operations for the detection of alumina, glass and porcelain vessels are to be avoided. The substances should be burned to an ash in a platinum dish, the ash treated with hydrochloric acid, the acid driven off by heat, and a few drops of nitric acid added, and dissolved in hydrochloric acid, and the solution boiled and filtered. If organs of the body are operated upon, iron and phosphoric acid will be present in the ash; this will, indeed, be the case with most organic substances. The filtered solution is boiled, and, while boiling, poured into a strong solution of sodic hydrate contained in a silver or platinum dish; the iron will now separate as oxide, and can be filtered off. To the filtrate is added a little sodic phosphate; it is then feebly acidified with hydrochloric acid, and ammonia added just sufficient to render it alkaline; a light whitish cloud of alumina phosphate, should alumina be present, is thrown down, and can be collected, thoroughly washed, dried, ignited, and weighed as alumina phosphate.[976] The alumina phosphate is then fused with sodic sulphate in a platinum dish or crucible, and the fused mass treated with hot water; the sodic phosphate dissolves, and the alumina oxide may be filtered off and dissolved in a little hydrochloric acid or sulphuric acid.

A solution thus prepared has the following properties:—

Ammonium sulphide; white precipitate of hydroxide.

Potash or soda; white precipitate, soluble in excess.

Ammonia; white precipitate, only slightly soluble in excess.

There is also a blowpipe-test: if a little of the hydroxide be collected, moistened with cobalt nitrate, and heated on charcoal by the oxidising flame, alumina, under these circumstances, becomes of a blue colour.

5. URANIUM.

§ 902. The soluble salts of barium are undoubtedly poisonous, and are of frequent occurrence in the arts. The chloride of barium is used in the staining of wool, the nitrate and the chlorate in the green fires of the pyrotechnist, the oxide and the carbonate in the manufacture of glass. The chromate is used by artists under the name of “yellow ultramarine,” while the sulphate, technically known as “permanent white,” is, on account of its weight and cheapness, occasionally used as an adulterant of white powders and other substances. Barium sulphide, under various names, such as Bottcher’s depilatory, Thompson’s hair destroyer, Poudre épilatoire, and other names, is in commerce, and has caused poisonous symptoms.[978]

§ 903. Chloride of Barium, BaCl₂2H₂O 208 + 36; anhydrous, Ba, 65·86 per cent., Cl, 34·14; specific gravity, 3·75, is in commerce in the form of white, four-sided, tabular crystals; water dissolves about half its weight at ordinary temperatures, three-fourths at 100°. Its solution gives a white precipitate with sulphuric acid, quite insoluble in water and nitric acid.

§ 904. Baric Carbonate, BaCO₃ = 197; specific gravity, 4·3; BaO, 77·69 per cent., CO₂, 22·31, in its native form termed Witherite, is a dense, heavy powder, insoluble in pure water, but dissolving in acetic, nitric, and hydrochloric acids, the solution giving the reactions of barium.

§ 905. Sulphate of Barium, BaSO₄; specific gravity, 4·59; BaO, 65·66 per cent., SO₃, 34·34 per cent., is a pure white powder when recently precipitated, absolutely insoluble in water, and practically insoluble in cold dilute acids. It is quite unalterable in the air at a red heat; on ignition with charcoal, it may be converted almost entirely into sulphide of barium; and by ignition with CaCl₂ into chloride.

§ 906. Effects of the Soluble Salts of Barium on Animals.—One of the early notices of the poisonous characters of barium compounds was by James Watt,[979] who found that witherite, given to dogs, produced vomiting, diarrhœa, and death in a few hours. Sir Benj. Brodie[980] administered barium chloride, and noticed its paralysing effect on the heart. Orfila[981] made several experiments, and observed that 4 grms. of the carbonate produced death in dogs in periods varying from one to five hours; but in these experiments the gullet was tied. The later investigators have been Gmelin, Onsum, Cyon, and Böhm.[982] Gmelin found barium carbonate and barium chloride act in a very similar manner; and, indeed, it is improbable that barium carbonate, as carbonate, has any action, but, when swallowed, the hydrochloric and other acids of the stomach form with it soluble compounds. J. Onsum made eight experiments with both barium carbonate and chloride on animals. The respiration was quickened and, at the same time, made weak and shallow; the heart’s action was accelerated; the animals became restless: and there was great muscular prostration, with paralytic symptoms; convulsions did not occur in any one of the eight animals. He found, on post-mortem examination, the right side of the heart full of blood from backward engorgement; he describes a plugging of the small arteries with little fibrinous coagula, having an inorganic nucleus, with constant hæmorrhagic extravasations. Onsum seems to have held the theory that the baryta salts circulated in the blood, and then formed insoluble compounds, which were arrested in the lungs, causing minute emboli, just in the same way as if a finely-divided solid were introduced directly into the circulation by the jugular vein.

Onsum stands alone in this view. Cyon found no emboli in the lungs, and refers the toxic effect to a paralysing influence on the heart and voluntary muscles, and also on the spinal cord. Cyon, to settle the embolic theory, injected into the one jugular vein of a rabbit barium chloride, and into the other sodic sulphate, but the small arteries and capillaries of the lungs remained clear. Böhm, operating on frogs, found a great similarity between the action of small doses of barium salts and that of certain organic poisons; as, for example, cicutoxin, ·012 to ·02 grm. subcutaneously injected into frogs, acted as a heart-poison. So also Blake[983] found the heart slowed, and concluded that barium chloride had a direct action on the cardiac muscle, and also a toxic influence on the nervous system. F. A. Falck, in experiments on rabbits, found a great reduction of temperature after poisoning with barium chloride (3° to 12·6°).

§ 907. Effects of the Salts of Barium on Man.—There were about fifteen cases of poisoning by barium salts on record by the end of 1883—three of which were suicidal, but most of them were due to accident or mistake. In three cases, barium chloride was taken instead of Glauber’s salts; in one, instead of Carlsbad salts; in another, a mixture of barium nitrate and sulphur, instead of pure sulphur; in a sixth case, a mixture of barium acetate and raspberry syrup, instead of sodic ethylsulphate; in a seventh, a chemist put a larger dose than was ordered by the prescription; and in four cases barium carbonate had been mixed with flour, and this flour used in the making of pastry. Of the fifteen cases, nine, or 60 per cent., proved fatal; the fifteen cases have now (1894) been increased to twenty-six.

Fatal Dose.—The recorded cases of poisoning have not satisfactorily settled the question as to the least fatal dose of the barium salts. 6·5 grms. (about 100 grains) of the chloride have destroyed the life of an adult woman in fifteen hours; 14 grms. (¹⁄₂ oz.) of the nitrate of baryta have killed a man in six and a half hours; and the carbonate of baryta has destroyed a person in the relatively small dose of 3·8 grms. (60 grains). On the other hand, certain Continental physicians have prescribed barium chloride in large medicinal doses; for example, Pirondi[984] and Lisfranc[985] have gradually raised the dose of barium chloride from 4 decigrams up to 3 grms. (48 grains) daily, given, of course, in divided doses. Pirondi himself took in a day 7·7 grms. (119 grains) without bad effect.

§ 908. Symptoms.—The local action of barium salts must be sharply distinguished from the action of the absorbed salts. Kobert divides the symptoms into seven groups:—

(5) Digitalin-like influence on the heart and blood-vessels, showing itself in great slowing of the pulse, præcordial anxiety, and strong beating of the heart (not only sensible to the patient, but which can be heard and felt by the bystanders). The arteries are incompressible and rigid, the blood-pressure strikingly raised. The blood-vessels of old people do not stand the pressure, hence hæmorrhages in the lungs, stomach, and other organs. Frogs die with the heart in systole.

(6) Catarrhal affection of the conjunctiva, the mucous membrane of the respiratory tract, and the nose.

(7) Formation of insoluble baryta salts in the blood-vessels, according to Onsum. This has not been observed in man, and the fact is disputed (see ante).

In Dr. Tidy’s case,[986] in which a man, suffering from rheumatism, but otherwise healthy, took a mixture of barium nitrate, flowers of sulphur, and potassic chlorate, instead of sulphur, the symptoms were blisters on the tongue, a burning pain in the gullet and stomach, with vomiting, diarrhœa, convulsions, aphonia, and coldness of the extremities. A case, copiously detailed by Seidel,[987] in which a pregnant woman, twenty-eight years old, took carbonate of baryta for the purpose of self-destruction, is interesting. She probably took the poison some little time before six in the evening; she vomited and had great pain in the stomach, but slept during the night without further sickness. The next morning, after drinking some coffee, the sickness was renewed; nevertheless, at 7 A.M., she repaired to her employment, which was distant an hour’s walk; she probably suffered much on the way, for she did not arrive until 9 A.M. The vomiting, accompanied by diarrhœa, continuing, she was sent to bed at 2 P.M. She was very cold, and complained of great weakness; the vomiting now ceased. At 8 P.M. she shivered violently, could scarcely swallow, and the respiration was oppressed. At 11 she seemed a little improved; but at 3 A.M. she was found much worse, breathing rapidly, but fully conscious; at 4 A.M. she was again seen, but found dead; she thus lived about thirty-four hours after taking the fatal dose.