COPPER-BLUE VITRIOL. SYMPTOMS. POST-MORTEM APPEARANCES-TREATMENT. POISONING BY VERDIGRIS-SUBCHLORIDE OF COPPER-CARBONATE-SCHEELE'S GREEN. CHEMICAL ANALYSIS-TESTS-SPECIAL CHARACTERS OF THE SALTS. COPPER IN ORGANIC LIQUIDS -IN ARTICLES OF FOOD.

ALL the salts of copper are poisonous. The two most commonly known are the SULPHATE or BLUE VITRIOL, and the SUBACETATE or VERDIGRIS. These substances have been frequently taken and administered in large doses for the purposes of suicide and in attempts at murder. In the latter case the attempt has been immediately discovered, owing to the very strong metallic taste possessed by the salt. This would in general render it impossible that the poison should be taken unknowingly. With the exception of these salts, poisoning by copper is usually the accidental result of the common employment of this metal for culinary purposes.

SULPHATE OF COPPER.

Symptoms.-Sulphate of copper has been frequently given for the purpose of procuring abortion. In doses of half an ounce and upwards, it acts as a powerful irritant on adults, and a much smaller quantity would suffice to destroy infants or children. The salt speedily induces vomiting of the most violent kind: this sometimes expels the poison from the stomach, and the person recovers. The vomited matters are remarkable for being generally of a blue or green colour; and broken crystals of blue vitriol have been discovered in them, when the poison was taken in a loosely pulverulent state. If the green colour of the vomited liquids be owing to altered bile, it will not acquire a blue tint on adding to a portion of the liquid a strong solution of ammonia; but if it be caused by a salt of copper, this change of colour will serve to indicate the fact. There is headache, pain in the abdomen, with diarrhoea; the pain is of a colicky character; and in aggravated cases there are spasms of the extremities, and convulsions. Dr. Percival met with a case where the most violent convulsions were produced in a young female by two drachms of the sulphate of copper. Paralysis, insensibility, and even tetanus, have preceded death, when the poison was administered to animals. Among the symptoms casually met with in the human subject, may be mentioned jaundice. This has been observed to attend poisoning by the sulphate, as well as by Scheele's green. The medicinal dose of sulphate of copper as an emetic, is from five to fifteen grains, and as a tonic from one to three or four grains.

There are but few instances in which this poison has proved fatal in the human subject. In 1836, a girl, sixteen months old, put some pieces of Blue stone (sulphate of copper) which were given her to play with, into her mouth. In a quarter of an hour, the child vomited a bluish-green coloured matter, with pieces of sulphate of copper in it; the skin was alternately cold and hot, but there was neither diarrhoea nor convulsions. The child died in four hours, and was insensible before death. (Med. Gaz. xviii. p. 742.) The coroner and jury did not consider it necessary that an inspection should be made; and yet in the event of murder being committed by the administration of this substance, it would be somewhat unreasonably expected that medical witnesses should be fully acquainted with the post-mortem appearances produced by it!

Post-mortem appearances.-In poisoning by the salts of copper, the mucous membrane of the stomach and intestines has been found more or less thickened and inflamed in the few fatal cases which have been hitherto examined: the mem

VERDIGRIS.

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brane has been also found eroded and softened in poisoning by verdigris. The œsophagus has presented an inflammatory appearance. In a case of poisoning by Verdigris, quoted by Orfila, the stomach was inflamed and thickened, especially towards the pylorus, the orifice of which, from the general thickening, was almost obliterated. The small intestines were throughout inflamed, and perforation had taken place, so that part of the green liquid was effused into the abdomen. The large intestines were distended in some parts and contracted in others, and the rectum was ulcerated on its inner surface. (Toxicologie, i. 623.) The lining membrane of the alimentary canal is often throughout of a deep green colour, owing to the small particles of verdigris adhering to it. It has been said that this is an uncertain character of poisoning by copper; since a morbid state of the bile often gives a similar colour to the mucous membrane of the stomach and duodenum. This objection cannot apply, when the green colour is found in the oesophagus, and throughout the intestines; and, under any circumstances, the evidence, from the presence of a green colour would amount to nothing, in the judgment of a prudent witness, unless copper were freely detected in the parts so coloured. It is well to remember, that the green stain, if due to copper, would be turned blue by ammonia. In death from arsenite of copper, the inflammatory appearances would probably be more strongly marked.

VERDIGRIS. SUBACETATE OF COPPER.

This salt produces symptoms somewhat similar to those caused by the sulphate. There is a strong styptic metallic taste, with a sense of constriction in the throat, followed by severe colicky pains,-vomiting of a green-coloured liquid, diarrhoea, and tenesmus. In a case reported by Phyl, a woman who took two ounces of verdigris died in three days: in addition to the symptoms above described, there were convulsions and paralysis before death. Niemann relates that a female, aged twenty-four, swallowed half an ounce of verdigris, and died under symptoms of violent gastric irritation in sixty hours. (Taschenbuch, 458.) In consequence of the great uncertainty of its operation, subacetate of copper is not employed internally.

SUBCHLORIDE OF COPPER.

This is a rich green compound known as Oxychloride or BRUNSWICK GREEN. It is formed when common salt has been used in a copper vessel, and has thus given rise to accidental poisoning. It is also used as a pigment.

CARBONATE OF COPPER.

A case of poisoning by this substance has been reported by M. Desgrange, of Bordeaux. A man died in about six hours, as it was supposed, from the effects of an unknown quantity of this poison which he had taken. When first seen he was comatose; he had sustained some violence from a fall, and there was great coldness of the extremities. There was neither vomiting, purging, nor pain in the abdomen on pressure. On inspection, the oesophagus and stomach were covered with a green-coloured substance. The larger extremity of the stomach was vascular, and the mucous membrane of the intestine, as well as the liquid contained in them, was green. Carbonate of copper was found in the stomach, and traces of the metal existed in the urine-none was found in the blood. (Med. Gaz. xxxi. 495.) It is remarkable that in this case there should have been neither vomiting nor diarrhoea. The poison seems to have acted more like a narcotic than an irritant.

ARSENITE OF COPPER.

This compound, which is known under the name of SCHEELE'S,-EMERALD or MINERAL GREEN, contains about half its weight of arsenic. It is extensively used as a pigment in the arts; it is also improperly employed to give a green colour to wafers and articles of confectionary.

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TESTS FOR SOLUTIONS OF COPPER.

Symptoms and Effects.-A child, aged three years, swallowed a small capsule of Scheele's green, used by his father as a pigment. In half an hour he complained of violent colic: there was frequent vomiting, with diarrhoea, cold sweats, intense thirst, and retraction of the parietes of the abdomen. The mouth and fauces were stained of a deep green colour. Hydrated sesquioxide of iron was given: in about an hour the vomiting and diarrhoea ceased, and soon afterwards the thirst and pain in the abdomen abated. The next morning the child was well. In another case, a child, a year old, ate several pieces of a cake of arsenite of copper, used for colours. There was immediate vomiting, the liquid containing green-coloured particles of the arsenite, but there were no other urgent symptoms. White of egg with sugared water was given to it. After a short time the child became pale, and complained of pain in the abdomen; the pulse was frequent, the skin cold, and there was great depression. Copious diarrhoea followed, soon after which the child recovered. (Galtier, i. 636.)

In the cases of two children poisoned by confectionary coloured with this substance, the chief symptom was incessant vomiting of a light green-coloured liquid, resembling bile diluted with water. Mr. Bulley, of Reading, who reports these cases (Medical Times, April 28, 1849, page 507,) describes the symptoms as very severe, although the quantity of poison swallowed was small. Under the use of an emetic of ipecacuanha the children recovered. A case was communicated to me in July 1849, by Mr. J. B. Hicks, in which a child, aged seven years, ate a slice of cake with part of a green ornament on it. There was severe pain with thirst, burning sensation in the throat, with constant vomiting, but no purging. The child recovered in three days. The green pigment was found to be pure arsenite of copper mixed with sugar. (Guy's Hosp. Reports, Oct. 1850, p. 218. See also Med. Gaz. vol. xliii. p. 304.) In a case which was the subject of a criminal trial, this deadly compound was proved to have caused the death of a gentleman by reason of its having been employed to give a rich green colour to some confectionary served at a public dinner. It was ignorantly used to give a colour to some blanc-mange :-the party who employed it considering that emerald or mineral green was nothing more than an extract of spinach! It led to death under the usual symptoms, and the parties were convicted of manslaughter and sentenced to imprisonment. (Reg. v. Franklin and Randall, Northampton Summer Assizes, 1848.) Most of the colours used for confectionary are of a poisonous nature: the pink colour given by cochineal or madder is the only one which can be regarded as innocent. [A case occurred under our observation some years ago. in which a boy five years old died, with all the symptoms of poisoning by copper, just two years after having swallowed a brass button: see Beck ii. 609, 610, for other like cases.--H.]

Chemical analysis of the Salts of Copper.-The salts of copper are generally known by their colour: whether in the solid state or in solution, they are either blue or green. The salts of one other metal are also of a green colour, namely nickel; but there are striking chemical differences between the salts of this metal and those of copper. There are three very soluble salts of copper; two of these are blue, the sulphate and nitrate,—and one green, the chloride. The solutions of the cupreous salts have generally an acid reaction. The salt should be dissolved in water, diluted, and the following tests may then be applied.

Tests.-1. Solution of ammonia: this gives, in a solution of copper, a bluishwhite precipitate, which is soluble in an excess of the test, forming a deep violetblue solution. 2. Ferrocyanide of potassium, a rich claret-red precipitate:-if the quantity of copper be small, the liquid acquires merely a light-red colour; if large the precipitate is of a red-brown colour, and of a gelatinous consistency. The ferrocyanide of potassium will act on the violet-blue solution produced by ammonia, provided it be much diluted, or an acid added (sulphuric) to neutralize the ammonia. One portion of liquid may thus be tried by the two tests. 3. Sulphuretted hydrogen gas, or hydro-sulphuret of ammonia, gives a deep

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chocolate-brown precipitate, even in an acid solution; or if the copper be in small proportion, merely a light-brown colour. 4. A slip of Polished Iron (a common needle) suspended by a thread in the liquid, is speedily coated with a layer of copper, even when the salt is in very small proportion. When much diluted, a drop of diluted sulphuric acid may be added. If the needle be left for some days in the liquid, the iron will be slowly removed, and a hollow cylinder of metallic copper will remain. This may be dissolved in diluted nitric acid, and tested with the foregoing tests; or the needle coated with copper, may be immersed in ammonia and exposed to air. The liquid then becomes slowly blue. Half a grain of sulphate of copper dissolved in sixteen ounces of water, may be thus easily detected. It was long since proposed by Orfila to substitute Phosphorus for polished iron. This substance most effectually separates metallic copper from its salts, even when they are dissolved in organic liquids. 5. The Galvanic test. If a few drops of the copper solution be placed on platina-foil, slightly acidulated with a diluted acid, and the platina be then touched through the solution with a thin slip of zinc, metallic copper, of its well known red colour, is immediately deposited on the platina. When the quantity of copper is small there is merely a brown stain; but a blue liquid is formed by pouring on it ammonia, and exposing it to air.

Copper in organic liquids.-The oxide of copper is liable to be precipitated by certain organic principles, as albumen, fibrin and mucous membrane: but some of these organic compounds are easily dissolved by acids or even by an excess of the solution of cupreous salt. A portion at least of the salt of copper is, therefore, commonly held dissolved. In such cases, there is one peculiar character possessed by these liquids, i. e. they have a decidedly green colour even when the copper-salt is in a far less than poisonous proportion.

Separation by iron.-We first filter the liquid, and save the insoluble portions for a separate operation. We may use as a trial-test either a needle, zinc with platina, or add to a portion, oxalic acid: the last gives a bluish-white precipitate only when the copper is in a moderately large quantity, and the liquid is not very acid. If the needle be not coated with copper in the course of a few hours, it is certain that there is no detectable quantity of the poison present in the liquid.

Separation as a sulphuret.-If the copper salt be present in large quantity, any of the trial-tests will indicate it immediately. We now destroy the viscidity of the liquid by diluting it if necessary, and pass into it a current of sulphuretted hydrogen gas in order to precipitate all the copper in the state of sulphuret. The black sulphuret may be collected, washed, dried, and then boiled in equal parts of nitric acid and water for a quarter of an hour. Nitrate and sulphate of copper are produced and dissolved, a fact indicated by the liquid acquiring a rich blue colour; and some sulphur is at the same time separated. This liquid, when filtered, will give the usual reactions with the tests for copper.

Separation by platina.-I have also found the following a very expeditious and simple method of obtaining copper from organic liquids. Having filtered the liquid, let a portion of it be placed in a clean platina capsule or crucible. A few drops of diluted sulphuric acid may be added, and a slip of zinc foil introduced. Wherever the platina is touched by the zinc, metallic copper is deposited; and after having in this way coated the platina capsule, the surplus liquid may be poured off and the capsule well washed out. The copper is then dissolved in diluted nitric acid, and the tests may be applied after the excess of acid has been driven off by heat. This is, perhaps, the most expeditious and certain method of detecting a salt of copper in an organic liquid. It is, however, less delicate

than the Iron-test.

Copper in articles of food.-The Medico-legal history of poisoning by copper would be incomplete without some remarks on the action of certain articles of food on this metal when used for culinary purposes. This is a not unfrequent form of accidental poisoning. The symptoms rarely appear until after the lapse

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of three or four hours. There is commonly nausea, with colicky pains and cramps in the limbs. It results from the experiments of Falconer and others, that metallic copper undergoes no change by contact with water, unless air be present, when a hydrated carbonate will be formed mixed with peroxide. If the water contain any acid, such as vinegar, or common salt, or if there be oily or fatty matter in contact with the metal, then the copper is more rapidly oxidized, and the liquid or fat acquires a green colour. If the copper vessel be kept perfectly clean, and the food prepared in it be allowed to cool in other vessels, there is not much risk of its acquiring a poisonous impregnation: nevertheless, no acid, saline, fatty, or oily liquid should be prepared as an article of food in a copper vessel. (See Ann. D'Hyg. 1832, i. 102.) Under the influence of heat and air, a portion of copper becomes dissolved, and the oily or other liquid acquires a green colour. The preparation of fruits, such as preserves, in copper vessels, is necessarily attended with some risk; for on cooling, a green crust is apt to form on the copper, just above the surface where the air and acid liquid meet. Some liquids while boiling appear to be but little liable to this impregnation:-thus, coffee, beer, milk, or tea, has been boiled for two hours together, in a clean copper vessel, without any portion of the metal being taken up by either of the liquids. (See Falconer, on the Poison of Copper, 65. London, 1774; also Orfila, i. 611.) Accidents of this kind are usually prevented by lining the copper vessel with tin; but in very large boilers this plan is not always adopted cleanliness alone is trusted to, and this is a sufficient preventive when properly observed.

It has been stated that an impure alloy used by some of the lower grade of dentists has been so largely composed of copper, as to affect the health of those who have used the plates for the support of artificial teeth. The acid and salts in the saliva would facilitate the production of a poisonous salt of copper.

In the making of preserved fruits and vegetable pickles, the salts of copper (blue vitriol) are sometimes used for the purpose of giving a rich green colour. Many of the green pickles sold in shops are thus impregnated with the vegetable salts of this metal, to which they owe their bright grass-green colour. If the fruit or pickle be placed in a solution of ammonia, and copper be present, the substance is speedily turned blue. The iron test is, however, more delicate. A bright needle immersed in the pickle, or plunged into the solid, will be speedily coated with copper. The quantity of copper contained in such articles may not be sufficient to cause fatal effects, but serious symptoms of gastric irritation are sometimes produced, and in very young subjects these may assume an alarming character. (See Falconer, 87.)

CHAPTER XIII.

TARTARIZED ANTIMONY-SYMPTOMS-RECOVERY FROM LARGE DOSES-POST-MORTEM APPEARANCES TREATMENT-CHEMICAL ANALYSIS-TESTS. ANTIMONY IN ORGANIC LIQUIDS. CHLORIDE OF ANTIMONY-ANALYSIS. POISONING BY SULPHATE AND CHLORIDE OF ZINC→→→→ CARBONATE OF ZINC. PREPARATIONS OF TIN-SILVER-GOLD-IRON-BISMUTH AND CHROME-BICHROMATE OF POTASH.

TARTARIZED ANTIMONY. TARTAR EMETIC. STIBIATED TARTAR. Symptoms and effects.-This substance, which is seen in the form of a white powder, or in crystals, is by no means so poisonous as it is often described to be. Forty grains have been given to an adult in twenty-four hours without causing serious mischief. When taken in a poisonous dose, a strong metallic