METALLOID IRRITANTS

PHOSPHORUS

Poisoning by this substance is more common in France than in England. In England, the deaths due to this poison are more frequently the result of accident, from the incautious use of phosphorus paste for the destruction of vermin. These pastes generally contain from 3 to 4 per cent. of phosphorus. Children have also been poisoned by sucking the heads of lucifer matches. In one case, that of a child, death followed from sucking about forty matches. It has most frequently been employed as a means of suicide, but seldom for the purpose of homicide. One case, however, occurred at the Bodmin Assizes in 1857. Kopf relates a case of a young woman, aged twenty-four, who died on the fourth day after swallowing the heads of six packets of lucifers (Allg. Wien. Med. Ztg., No. 47, 1819; Schmidt, vol. cv. p. 296). The size of the packets is not stated. In this case the bowels were confined, and the post-mortem revealed only the redness of inflammation in the stomach and bowels. Death has followed inunction of phosphorus paste.

General Characters.—There are two kinds—ordinary waxy, crystalline phosphorus, and a peculiar form known as red allotropic or amorphous phosphorus, prepared by heating waxy phosphorus to a temperature of 240° C., in an atmosphere free from oxygen. The ordinary yellow phosphorus is poisonous, the red or amorphous non-poisonous. As found in the shops, phosphorus is preserved in water in the form of translucent white or slightly yellow-coloured cylinders. It is sparingly soluble in oil, alcohol, and other hydrocarbons, but greatly so in bisulphide of carbon. White vapours are given off when it is exposed to the air, these consisting of phosphorus and phosphoric acids.

Symptoms.—Phosphorus acts as an irritant poison, but some days may elapse after the poison is taken before the injurious effects become apparent. The symptoms occur in three stages.

First stage: The patient complains of a garlic-like taste in the mouth, peculiar to poisoning by this substance. This is followed by a burning sensation in the throat, accompanied with severe pain in the stomach, and intense thirst. The belly becomes swollen, and there is vomiting, in some cases, of blood from the stomach, which may continue till death. The vomited matters are of a dark green or black colour, with an odour of garlic, and sometimes appearing phosphorescent in the dark. This condition may also be observed in the motions passed. There is intense thirst. The pulse is feeble, the countenance anxious, and the surface of the body bathed in a cold sweat. In males, priapism is not infrequent. The nervous and muscular debility is intense, and the patient may die in a state of collapse or during a fit of convulsions.

Second stage: This is a stage of intermission of the symptoms which may last for three days or more, the patient seems as if going to recover, and only suffers from general malaise. A case is recorded where the intermission lasted nine weeks. In cases proceeding to a fatal termination the intermission is followed by the third stage.

Third stage: Jaundice is the most notable symptom and rapidly increases; the liver becomes much enlarged and the abdomen distended; epigastric pain is severe and there is vomiting of grumous black material consisting of altered blood; purging may be present and the motions contain blood. There is a marked tendency for hæmorrhages to occur from the mucous membranes and subcutaneously, producing purpuric spots. The urine is diminished, high coloured, contains bile pigments, albumen, blood, and casts. There are great prostration, a quick weak pulse, sleeplessness, coldness of the surface, gradually increasing weakness, apathy, convulsions, and coma, followed by death about the fifth or sixth day.

The liver may diminish in size before death. It is rare for recovery to take place after enlargement of the liver and jaundice have supervened. It is by no means always easy to diagnose acute yellow atrophy of the liver or malignant jaundice from phosphorus poisoning. In phosphorus poisoning, the early symptoms, those of acute gastritis, are more severe, are developed more rapidly, and run their course more quickly than in acute atrophy, and there is a marked interval between these and the appearance of the jaundice; in acute yellow atrophy this interval is wanting, and from the beginning, on the contrary, there are gradual malaise, slight gastric catarrh, and jaundice. The jaundice and suffering, together with the increased action of the heart in phosphorus poisoning, are wanting in malignant jaundice, but the cerebral symptoms are more marked in the latter than in the former. Acute yellow atrophy most frequently occurs in women, especially during pregnancy. In acute atrophy leucin and tyrosin are present in the urine; in phosphorus poisoning they may occur, but generally in the urine voided just before death.

Chronic poisoning, accompanied with all the symptoms just mentioned, may result from the action of the vapour on those engaged in the manufacture of phosphorus or of lucifer matches. In persons thus employed, necrosis of the jaws and caries of the teeth are not of infrequent occurrence. The lower jaw is more commonly affected. Mr. Lyons states that this form of necrosis cannot attack persons who have perfectly sound teeth, but only those whose teeth are carious (St. Bartholomew‘s Hospital Report, vol. xii.).

Post-mortem Appearances.—Those of acute irritant poisoning, including extensive destruction of the coats of the stomach, by softening, ulceration, and perforation, terminating in gangrene. The stomach may contain a quantity of white vapour, having a strong smell of garlic. This white vapour has been noticed to pass from the vagina and anus of those poisoned by phosphorus. The blood appears to be thoroughly disorganised; the blood-cells are colourless and transparent, their colouring matter being dissolved in the uncoagulated liquor sanguinis; hæmorrhages may be present beneath the serous membranes and in the pleural and pericardial cavities, and thromboses are frequently present, due to a tendency for the blood-cells to agglutinate. In a case recorded in the British Medical Journal, 1873, fatty degeneration of the liver and kidneys was found a week after the poison was taken. In phosphorus poisoning, the liver is enlarged, of a dull appearance, doughy, uniformly yellow, with the acini well marked; in acute atrophy, the liver is diminished in size, greasy on the surface, leathery, of a dirty yellow colour, with traces only of the obliterated acini. In the former, also, the hepatic cells are either filled with oil globules or entirely replaced by them; in the latter, the cells are filled with a fine granular detritus, and their structure replaced by newly-formed connective tissue. Putrefaction rapidly supervenes on death. Hæmorrhages may be found on the surface of the brain and spinal cord, and the grey matter of the cortex and basal ganglia rose-pink in colour. Fatty changes have been found in the walls of the capillaries and the large cortical cells.

Chemical Analysis.—The smell of phosphorus is characteristic, as is also its luminosity when exposed in the dark. The following process, suggested by Mitscherlich, may be adopted for its detection:

To render the suspected matter quite fluid water is added, previously acidulated with sulphuric acid, in order to neutralise any ammonia present. The liquid is then transferred to a glass retort, fitted with a long condensing tube passing into a receiver containing solution of nitrate of silver. Distillation is conducted in the dark, when the minutest trace of phosphorus may be detected by the luminous appearance of the vapour during condensation. Other modifications of this process have been suggested, in order to increase the space occupied by the phosphorescence.

By the above process, one part of phosphorus may be detected in 100,000 parts of substance. Another method for the detection of this poison in very minute quantities is that proposed by Dussart (Compt. Rend., xliii. 1126), and modified by Blondlot (Compt. Rend., lii. 1197). The test is based on the fact that when phosphorus is exposed to the action of nascent hydrogen in a Marsh‘s apparatus, it burns with an emerald-green flame. In order to avoid the yellow colouring of the flame produced by the sodium in glass, Blondlot recommends the use of a platinum jet. As the green colour is more or less interfered with by the presence of organic matters, he passes the gas through a solution of nitrate of silver; the resulting precipitate is then placed in another hydrogen apparatus, as just mentioned, and the colour of the flame of the issuing gas noted. Phosphorus may become decomposed in the body; and as phosphoric acid is taken in most articles of food, the only satisfactory evidence of phosphorus having been taken is to produce it in its free state, or at least to exhibit its luminosity. The detection of the colouring matter of lucifer matches in the stomach or vomited matters will point to the probable nature of the poison, and whence it was derived.

Scherer‘s Test is based on the reducing action of phosphorus on nitrate of silver, which it blackens. The suspected material should be placed in a flask or in a Dowzard‘s apparatus for Gutzeit‘s test for arsenic, lead acetate is added to the material to fix the H₂S, and some lead acetate solution placed in each cell. A little ether is added to the mixture, and the flask or top of the apparatus capped with paper moistened with nitrate of silver, and set aside for some hours in a dark place. If phosphorus be present the paper will be blackened from deposition of metallic silver.

Fatal Period.—From half an hour to twenty days or more.

Fatal Dose.—One grain and a half. The smallest fatal dose recorded for an adult is one-eighth of a grain. An infant five weeks old died from sucking a single match head, which probably contained one-fiftieth of a grain of phosphorus. Recovery has taken place after four and six grains have been taken.

Treatment.—The stomach pump or syphon tube should be used as soon as possible, and the stomach well washed out with warm water containing a drachm of old oil of turpentine to the pint. If the turpentine be not readily obtained, “sanitas” should be used with the water, or a 1 per cent. solution of permanganate of potash. After washing the stomach, the old oil of turpentine, or the French oil of turpentine, or “sanitas” may be administered in half to one drachm doses in mucilage and water every fifteen minutes for several doses, and afterwards three or four times daily. The 1 per cent. solution of potassium permanganate may be administered in copious drinks.

According to some observers, turpentine is said to be of no value; but this failure in the use of turpentine has been shown to be due to the employment of different varieties of oil. The crude acid French oil, of the three kinds met with in commerce, appears to be the only one that acts as described below. With turpentine, phosphorus forms a spermaceti-like mass consisting of turpentine phosphorus acid. It has an acid reaction, and is converted, on exposure to the air, into a resinous substance smelling like pine-resin. With earths and metallic oxides it forms insoluble salts. The acid is not poisonous; doses of 0.03 to 0.3 gram may be given to dogs and rabbits without any other effect than that of lowering of the body temperature. To the formation of this compound, the antidotal properties of turpentine in phosphorus poisoning are attributed (Kohler a. Schempf Dingl., pol. Jcxcix.). Turpentine is said by some to be valueless if not given within twelve hours. Emetics of sulphate of copper may be administered, but the salt is liable to cause severe gastro-enteritis. Further treatment may consist of mucilaginous drinks containing magnesia and opium to relieve pain. Oils or fats should not be given because of their solvent action upon phosphorus.

Synopsis of the Effects due to
Poisoning by Phosphorus

1. Which variety of phosphorus is poisonous?—The ordinary yellow phosphorus usually kept in water. The allotropic form is inert.

2. What quantity is sufficient to kill an adult?—One grain and a half.

3. Symptoms as regards—

(1) Alimentary Canal.—Pain in the stomach and belly, eructation of gas smelling like garlic, vomiting, and sometimes purging, with other signs of irritation.

(2) Circulatory System.—Tendency to hæmorrhage from the mouth, stomach, lungs, bladder, &c. Petechiæ and ecchymoses may occur on all parts of the body. If the case be prolonged, anæmia may be present. Pulse small, weak, and scarcely perceptible.

(3) Nervous System.—Cramps, creeping sensations in the limbs, delirium, convulsions, paralysis, and extreme nervous prostration.

(4) Period of Invasion of the Symptoms.—Obscure and insidious; some hours or even days may elapse before the appearance of the symptoms.

(5) Period of Fatal Termination.—In some cases as short as four hours.

4. Post-mortem Appearances—

(1) Alimentary Canal.—Signs of irritation and inflammation in the stomach and intestines. Gangrene and perforation have been noticed. Strong smell of garlic when the abdomen is laid open. Appearances not unlike scurvy may be found.

(2) Cellular Tissue.—Ecchymoses may be present in the cellular tissue of the abdomen, chest, and other parts of the body.

(3) Muscular Tissue.—Fatty degeneration in the heart and other organs of the body has been noticed in several cases.

(4) Liver.—Fatty degeneration of the gland.

(5) Blood entirely disorganised, the cells transparent, and their contents dissolved in the uncoagulated liquor sanguinis. The colour, cherry-red.

5. Name special affection produced by phosphorus in lucifer match makers—Necrosis of the jaws, usually of the lower jaw. The disease begins in a decayed tooth.

6. Name a natural disease which phosphorous poisoning has been supposed to resemble—Acute yellow atrophy of the liver.

IODINE

Iodine is seldom used as a poison, owing to the difficulty experienced in disguising its colour. In the form of a strong solution it has been, however, employed for throwing on the person with intent to cause grievous bodily harm, as in this form it is corrosive, and destroys the part which it touches.

General Characters.—Iodine is a dark grey solid, with a bright metallic lustre. It melts at 107° F., boils at 175° F., and gives off at the ordinary temperature a faint odour not unlike chlorine. But slightly soluble in pure water, it is, however, readily dissolved when a soluble iodide is added to the water.

Symptoms.—Those produced by irritant poisons generally; the severity of the symptoms being increased by the strength of the solution, iodine possessing corrosive as well as irritant properties. The vomited matter will be stained with the iodine, and starchy material turned blue or black.

Post-mortem Appearances.—Those the result of acute irritant poisoning.

Fatal Period.—Two days.

Fatal Dose.—One fluid drachm of the tincture has proved fatal; recovery has taken place after taking one fluid ounce of the tincture.

Treatment.—The stomach should be emptied by the aid of the stomach pump, and then diluent drinks—arrowroot and barley water—may be given.

Chemical Analysis.—Add bisulphide of carbon to the suspected mixture, and shake them together. The sulphide will dissolve out the iodine, which may be obtained on evaporation and sublimed. The characteristic reaction of iodine, the development of a blue colour on the addition of a small quantity of starch, will be conclusive evidence of its presence. If chloroform be added to iodine in aqueous solution and shaken up, the chloroform is coloured crimson by the iodine, and falls to the bottom as the mixture is allowed to settle.

IODIDE OF POTASSIUM

This salt is largely used in medicine; and though poisonous effects may be produced, due probably to some constitutional idiosyncrasy, it has seldom been used as a poison. It must, however, be placed among noxious irritant substances.

General Characters.—Iodide of potassium—hydriodate of potash—occurs in cubical crystals of a white or faint yellow colour, very slightly deliquescent when pure, and with a feeble odour of iodine.

Symptoms.—Iodide of potassium acts as an irritant in large doses, producing also many of the symptoms which attend a violent catarrh, with profuse discharge from the nose, lachrymation, and swelling of the eyelids, also pustular eruptions like acne on the face and body generally. Small doses—three to five grains—have produced in some persons most unpleasant and even alarming symptoms. In chronic poisoning, certain glands, the mammary and testicles, are said to waste away. Salivation is not infrequently present. I have seen the administration of the salt produce a severe bullous and hæmorrhagic eruption, simulating hæmorrhagic smallpox, with sloughing. (See also the account in British Medical Journal, 1878, of a case of purpura in a child five months old, after a dose of two and a half grains of the salt.)

Treatment.—The use of emetics and the stomach pump, starch, &c.

Chemical Analysis.—In solution, iodide of potash gives the following characteristic reactions:

1. With a salt of lead	Bright yellow precipitate.
2. With corrosive sublimate	Bright scarlet precipitate.
3. With strong nitric acid and starch	A blue colour.

In organic mixtures the mode of detecting it is more complicated.

Sulphuretted hydrogen should be first passed through the mixture in order to convert any free iodine into hydriodic acid. The excess of the gas is then driven off by the application of heat, and potash added, the resulting liquor filtered, and the filtrate evaporated to dryness. To get rid of any organic matter, the residue left after evaporation is charred at a low red heat, reduced to powder, and dissolved in water. This solution is then concentrated, and strong nitric acid and solution of starch added, when, if iodine be present, the blue colour will be developed.