2. If the copper be extremely minute in quantity, sulphuretted hydrogen

will not act upon it in a fluid much charged with organic matter. To meet this possible case, which may occur when the subject of analysis is an organ of the human body into which the poison has been conveyed by absorption,—let the liquid be evaporated to dryness, and charred in the following manner. Heat in a porcelain basin a quantity of nitric acid equal in weight to the residuum, together with a fifteenth of chlorate of potash. Add the dry residuum in successive portions of such magnitude as not to occasion too great effervescence. When it has been all added, heat the product till it become dark-red and thick. It will then, or soon afterwards, begin suddenly to char, and at length a thick vapour will arise in dense clouds; upon which, the charring being complete, the heat must be withdrawn. Pulverise the carbonaceous mass; boil it with nitric acid diluted with its own volume of water; and evaporate the filtered fluid to dryness, so as to expel any excess of acid. Dissolve the saline residuum, and test the solution with the usual reagents. The first branch of this process is nearly the same with the one adopted in the last edition of the present work. The second is derived from a process lately proposed by Orfila.[1089] The principles on which it is founded are these. 1. Of the numerous organic compounds formed by vegetable and animal principles with the salts of copper, all either dissolve in very weak acetic acid, or part with their oxide of copper to it. This was pointed out by me in my last edition. 2, Weak acetic acid, as already mentioned (p. 356), has been shown by M. Devergie to be incapable of dissolving that copper which is contained naturally in the tissues, at least so as to render it discoverable by the subsequent steps of the process. 3, According to Orfila, copper naturally present in organic substances, is never indicated by the second branch of the process, provided the charred product of the action of nitric acid and chlorate of potash be not heated to incineration. It does not appear why the charring process, when so conducted, should separate adventitious copper, and not that which is present naturally. But the empirical fact may be accepted in the mean time, as it rests on apparently careful experiments. Orfila does not use acetic acid in the first branch of his process, but merely infuses the suspected matter in cold water, and if copper be not thus found, he has recourse to boiling water. But this method introduces needless complexity; and besides neither maceration, nor boiling with mere water, will dissolve out the whole oxide of copper. Acidulation with acetic acid dissolves it all; and Devergie has shown that this advantage is gained without any additional fallacy arising from the possible presence of copper as a natural ingredient of the substance under examination (p. 356). SECTION II.—_Of the Action of Copper, and the Symptoms it excites in Man._ The symptoms caused by copper have at least two varieties in their character. One class arises from its local action on the alimentary canal; the other from its operation on distant organs. This double influence is proved by the experiments of Drouard on animals, published in his inaugural dissertation at Paris in 1802; and by those of Orfila in his Toxicology. When Drouard gave twelve grains of verdigris to a strong dog fasting, he observed that it caused aversion to food, efforts to vomit, diarrhœa, listlessness, and death in twenty-two hours; and that the stomach was but little inflamed. When two grains dissolved in water were injected into the jugular vein of another dog, it caused vomiting and discharge of fæces in seven minutes, then rattling in the throat, and death in half an hour; and there was no particular morbid appearance in the body.—Half a grain killed another in four days; and in addition to the preceding symptoms, there was palsy of the hind legs for a day before death. Six grains of the sulphate introduced into the stomach killed a dog in half an hour, without producing any appearance of inflammation.[1090] These experiments prove that it is not by causing local irritation that this poison proves fatal. But its mode of action is more distinctly shown in the later and more accurate experiments of Orfila. He found that twelve or fifteen grains of the neutral acetate generally killed dogs within an hour; and that besides the usual symptoms of irritation in the stomach, they often had insensibility, almost always convulsions, and immediately before death rigidity, or even absolute tetanus. He likewise remarked violent convulsions and insensibility when a grain of this salt was injected into the veins; and death was then seldom delayed beyond ten minutes. In no case was there any particular morbid appearance, except loss of contractility in the voluntary muscles.[1091] More recently results nearly the same have been obtained by Mitscherlich; and when doses of two drachms of sulphate of copper were given, he observed after death pale blueness of the villous coat of the stomach, mingled with brownness,—the apparent effect of chemical action.[1092] Allied to these results are those obtained by my late colleague, Dr. Duncan, and by Mitscherlich, when the sulphate was applied to a wound. Dr. Duncan observed that death took place in twenty-two hours, and the body was every where in a healthy state. Mitscherlich found that a drachm of either sulphate or acetate proved fatal in four hours, with symptoms of extreme prostration. The experiments of M. Smith, repeated by Orfila, are at variance with these; for one or two drachms of the acetate applied to a wound in the thigh of a dog caused only local inflammation, and no constitutional symptoms.[1093] It follows from the researches now detailed, that the salts of copper act in whatever way they are introduced into the system, and the more energetically, the more directly they enter the blood. The inquiries of Mr. Blake farther show, that when injected into the blood-vessels, they act with peculiar force in exhausting muscular irritability, and occasion death by paralysing the heart if they are injected into a vein. Six grains of the sulphate injected into the jugular vein of a dog reduced the force of the heart’s contractions, and fifteen grains arrested them in twelve seconds, leaving in the dead body distension of the heart, loss of contractility, and florid blood in the left cavities. Ten grains injected into the aorta through the axillary artery caused no sign of obstruction in the capillary system; and small doses of three or four grains occasioned vomiting, dyspnœa, and stiffness of the limbs; and immediately after death the muscles had lost their irritability.[1094] Copper has been sought for, with variable success, in the blood of animals poisoned with its salts. Drouard was unable to detect it in the blood. But this need not excite surprise, because the same physiologist could not detect it, even when he had injected it into a vein.—Lebküchner, who published a thesis at Tübingen in 1819, on the permeability of the living membranes, succeeded in discovering it. He introduced four grains of the ammoniacal sulphate into the bronchial tubes of a cat, and five minutes afterwards, when the animal was under the action of the poison, he drew some blood from the carotid artery and jugular vein; and he detected copper in the serum of the former, but not in the latter, by sulphuretted-hydrogen and hydrosulphate of ammonia.[1095]—Afterwards Dr. Wibmer of Munich also succeeded in discovering it. In a dog which had taken from four to twenty grains of the neutral acetate daily for several weeks, he found the metal in the substance of the liver, but not anywhere else. In the charcoally matter left by incinerating the liver, nitric acid formed a solution, which when neutralized gave the characteristic action of the salts of copper with sulphuretted-hydrogen, ferro-cyanate of potash, and ammonia.[1096] Fischer also found copper in the blood of a dog which in forty-three days had got gradually-increasing doses of acetate of copper, till at length twelve grains were taken daily.[1097] Orfila has recently often detected copper in the liver, spleen, heart, kidneys, and lungs of animals poisoned with its salts.[1098] These facts are not all invalidated by the late discovery of the presence of copper in the animal tissues of men and animals not poisoned with its preparations. For in the experiments of Wibmer and of Orfila the quantity found in cases of poisoning was much larger than in the ordinary state of things; and the poison was accumulated in particular organs, especially the liver. The absorption of copper may therefore be considered as fully substantiated; and it is equally important whether it be regarded as a physiological or medico-legal fact. Dr. Duncan’s experiment on its effect when applied to a wound shows that it may prove fatal when applied externally. Yet in small quantities, the sulphate is daily used with safety for dressing ulcers. As to the preparations of copper which are poisonous, it is pretty certain that, like all other metals, it is not deleterious unless oxidated, and that its soluble salts are by far the most energetic. Portal, indeed, has related the case of a woman who, while taking from a half a grain to four grains of copper filings daily, was seized with symptoms of poisoning.[1099] But it is probable the filings were oxidated; for Drouard gave an ounce to dogs without injuring them at all,[1100] and Lefortier more lately observed that two drachms had no effect.[1101] The same explanation must be given of the injury sustained by those artisans who prepare and use what is called “bronze dust” in printing and paper-staining. If the substance employed be nothing else than an alloy of copper and zinc, as is alleged, the injurious effects to be mentioned presently can only be explained on the supposition that the copper becomes oxidated either before or after coming in contact with the body. It deserves to be added, that many persons have swallowed copper coins and retained them for weeks without having any symptoms of poisoning. The sulphuret is equally innocuous with the metal if pure; but it appears probable that it becomes oxidated by long exposure to the air, and passes into the state of sulphate. Orfila found that an ounce of recently prepared sulphuret had no effect on a dog; but half an ounce of a parcel which had been long kept caused vomiting, and yielded a little sulphate to water.[1102] The power of the oxides has not been ascertained. They are certainly poisonous; and Lefortier found that both the red dioxide and black protoxide undergo solution in no long time in the stomachs of dogs.[1103] The hydrated protoxide is probably more active. From some experiments made at the hospital of St. Louis in Paris, it appears that twelve grains will cause nausea, pain in the stomach and bowels, vomiting and diarrhœa.[1104] There is no doubt that the carbonate or natural verdigris, the phosphate, and even the subphosphate, though quite insoluble in water, are capable of acting as poisons, because Lefortier found that they are soon dissolved in the stomachs of dogs, and in small doses cause severe vomiting in the course of fifteen minutes.[1105] But it is chiefly in the soluble salts that we are to look for the full development of the action of this poison. A very small quantity of the sulphate will prove fatal; for, as already noticed, Drouard found that six grains killed a dog in half an hour. The symptoms caused by the soluble salts of copper in man are, in a general point of view, the same with those caused by arsenic and corrosive sublimate. But there are likewise some peculiarities. According to the cases related by Orfila in his Toxicology, the first symptom is violent headache, then vomiting and cutting pains in the bowels, and afterwards cramps in the legs and pains in the thighs. Sometimes throughout the whole course of the symptoms there is a peculiar coppery taste in the mouth, and a singular aversion to the smell of copper. Drouard notices this in his thesis; and says, that, having himself been once poisoned with verdigris, the smell of copper used to excite nausea for a long time after.[1106] Another symptom, which occasionally occurs in this kind of poisoning, and never, so far as I know, in poisoning with arsenic or corrosive sublimate, is jaundice. It likewise appears that, when the case ends fatally, convulsions and insensibility generally precede death. A set of cases illustrating the slighter forms of poisoning with copper has been published by M. Bonjean of Chambéry. The cause was the preparation of an acid confection in a copper vessel. Two women suffered from severe headache, constriction of the throat, nausea, colic, and extreme weakness. Two young men, who had eaten the confection more freely, had for some hours excruciating colic, severe pain in the mouth and throat, impeded breathing, and hurried irregular pulse; and for twenty-four hours they suffered severely from headache and prostration of strength.[1107] The following case communicated to Professor Orfila by one of his friends will convey a good idea of the symptoms in severe cases, which do not prove fatal. A jeweller’s workman swallowed intentionally half an ounce of verdigris, suspended in water. In fifteen minutes he was attacked with colic pains and profuse vomiting and purging. When seen by the physician eight hours afterwards there was not much vomiting, but frequent eructation of a matter containing verdigris, some salivation, a small pulse, and blueness about the eyes. In sixteen hours jaundice began to appear. In the course of the night he was a good deal relieved from the colic pains by three alvine discharges; and next morning he had ceased to vomit, and the pain had disappeared. But he complained of a taste of copper in his mouth, and the jaundice had increased. From this time he recovered rapidly, and on the fourth day convalescence was confirmed.[1108] When the poisoning ends fatally, convulsions, palsy, and insensibility, the signs in short of some injury done to the brain, are very generally present. This is illustrated by a good example in Pyl’s Essays and Observations. It was the case of a confectioner’s daughter, who took two ounces of verdigris, and died on the third day under incessant vomiting and diarrhœa, attended towards the close with convulsions, and then with palsy of the limbs. This case, however, is chiefly valuable for the dissection, which will be noticed presently.[1109] But two cases of the same description are related in greater detail by Wildberg in his Practical Manual, which clearly show the action of this poison on the brain. They are the cases formerly alluded to of a lady and her daughter who were poisoned by sour-krout kept in a copper pan. Soon after dinner they were attacked first with pain in the stomach, then with nausea and anxiety, and next with eructation and vomiting of a green, bitter, sour, astringent matter. The pain afterwards shot downwards throughout the belly, and was then followed by diarrhœa; afterwards by convulsions, at first transient, then continued; and finally by insensibility. The daughter died in twelve hours, the mother an hour later.[1110] In these three cases, although there was not any jaundice noticed during life, the skin was very yellow after death.—In some instances it would appear that narcotic symptoms form the commencement and irritant symptoms the termination of the poisoning. This unusual relation occurs in a case of recovery related by M. Julia-Fontenelle, and also, though less remarkably, in a fatal case mentioned by Wibmer. The subject of the former was a man who intentionally took a solution of copper in vinegar, prepared by keeping several sous-pieces seven days in that fluid. In three hours he was found in a state of insensibility, with the jaws locked, the muscles rigid and frequently convulsed, the breathing interrupted, and the pulse small and slow. In half an hour he was so far roused that he could tell what he had done; and soon after taking white of eggs the convulsions ceased: but next day the belly was hard and tender, and the repeated application of leeches was required to subdue the abdominal irritation that ensued.[1111] In the fatal case by Wibmer, that of a girl of 18, who was poisoned by a dish of beans having been cooked in a copper vessel, sickness, pain of the belly and vomiting speedily arose, but were soon followed by convulsions and loss of consciousness. Next day there was little pain, but extraordinary paralytic weakness of the arms and legs: the abdomen afterwards became distended and painful; and death took place in seventy-eight hours.[1112]—A case where convulsions were produced by two drachms of blue vitriol is mentioned by Dr. Percival.[1113]—In other instances it would appear that no nervous affection occurs at all, as in the case of a young lady related by Percival, who, when poisoned with pickled samphire containing copper, suffered chiefly from pains in the stomach, an eruption over the breast, general shooting pains, thirst, a frequent small pulse, vomiting, hiccup, and purging. Death occurred on the ninth day, without stupor or convulsions.[1114] Besides these effects when introduced in considerable doses and in the form of soluble salts, copper is said to produce other disorders when applied to the body for a long time in minute quantities and in its metallic or oxidized state. Among those artisans who work much with copper various affections are thought to be gradually engendered by merely handling the metal. Patissier in his treatise on the diseases of artisans says, that copper-workers have a peculiar appearance which distinguishes them from other tradesmen,—that they have a greenish complexion,—that the same colour tinges their eyes, tongue, and hair, their excretions, and even their clothes through the medium of the perspiration,—that they are spare, short in stature, bent, their offspring ricketty, and they themselves old and even decrepit at their fortieth or fiftieth year.[1115] Mérat also asserts that they are liable to the painters’ colic, that peculiar disease soon to be noticed as a common effect of the long-continued application of lead.[1116] But these notions must be received with some limitation. At least the alleged effects on copper-workers are by no means invariable. For copper-workers now-a days in this country and elsewhere are by no means the unhealthy persons Patissier represents them to be. As to colica pictonum, it is very rare among them; and possibly the cases noticed by Mérat might have been produced by the secret introduction of lead into the body, if indeed they were not cases of common colic. A very singular set of cases was lately brought under notice by Mr. Gurney Turner, where poisoning seemed to have been occasioned by the external application or inhalation of the fine dust used for imitating gilding by painters, paper-stainers, and porcelain-painters, and which is said to be essentially brass in a state of fine division. The workmen who use it, are very apt to be attacked with irritation about the private parts, and a vesicular eruption about the hairs on the pubes,—with loss of appetite, tendency to vomiting, and other symptoms of irritation in the stomach,—with obstinate constipation,—with soreness and dryness of the throat and irritation in the nose,—and with want of sleep, and a remarkable greenness of the hair over the whole body.[1117] SECTION III.—_Of the Morbid Appearances caused by Copper._ The appearances found in the body after death by poisoning with copper are chiefly the signs of inflammation. Where death takes place very rapidly, however, it is probable, that no diseased appearance whatever will be perceptible. At least this was the case in the animals experimented on by Drouard and Orfila; and little doubt can therefore be entertained that the result would be the same with man also in similar circumstances. When death ensues more slowly, as in the only fatal cases yet on record of its action on man, the marks of inflammation coincide with the signs of irritation during life. The best account I have seen of the morbid appearances under such circumstances is in the cases related by Pyl, by Wildberg, by Wibmer, and by Dégrange. In Pyl’s case the whole skin was yellow. The intestines, particularly the lesser intestines, were of an unusual green colour, inflamed, and here and there gangrenous. The stomach was also green; its inner coat was excessively inflamed; and near the pylorus there was a spot as big as a crown, where the villous coat was thick, hard, and covered with firmly adhering verdigris. The lungs are likewise said to have been inflamed. The blood was firmly coagulated. In the cases related by Wildberg, which are very like each other, the skin on various parts, and particularly on the face, was yellow, but on the depending parts livid. The outer coat of the stomach and intestines was here and there inflamed; and the inner coat of the former was very much inflamed, and even gangrenous[1118] near the pylorus and cardia. The duodenum and jejunum, and likewise the gullet, were in a similar state. The blood in the heart and great vessels was black and fluid. In the case of the girl referred to by Wibmer, the skin was ochre-yellow, the stomach green, much inflamed, especially near the pylorus, the gullet and intestines also inflamed, the diaphragm red, the brain healthy, the lungs and heart “gorged with thick blood.” In the case of poisoning with carbonate of copper described by Dégrange [p. 348], in which, however, it is probable that death was accelerated by a fall, there was found congestion of the surface of the brain, arborescent redness of the gullet and a green sand over its surface, general greenness of the villous coat of the stomach, with vascularity of the fundus and points of superficial ulceration, greenness of the whole intestines, with black vascular ecchymosed spots and softening, except in the ileum, and redness of the inner surface of the heart. Copper was detected in the contents of the stomach and intestines. The intestines have been found perforated by ulceration, and their contents thrown out into the sac of the peritonæum. Portal has related one case where the small intestines were perforated, and several where the perforation was in the rectum, which portion of the intestines, as well as the duodenum, jejunum, and ileum, was also extensively ulcerated.[1119] The existence of verdigris in the form of powder lining the inside of the stomach after incessant vomiting for three days, is of course an important circumstance in the inspection of the body. But too much reliance ought not to be placed on mere bluish or greenish colouring of the membranes. For Orfila[1120] and Guersent[1121] have both observed, that the inside of the stomach as well as its contents may acquire these tints in a remarkable degree in consequence of natural disease. SECTION IV.—_Of the Treatment of Poisoning with Copper._ The treatment of poisoning with the salts of copper has been examined in relation to the antidotes by M. Drouard, M. Marcelin-Duval, Professor Orfila, and M. Postel. The alkaline sulphurets were at one time thought to be antidotes for the poisons of copper, but without any reason. Drouard found that fifteen grains of verdigris killed a dog in thirty hours, notwithstanding the free use of the liver of sulphur.[1122] Afterwards M. Marcelin-Duval was led from his experiments to infer that sugar was an antidote,[1123] and in the first editions of his Toxicology Professor Orfila agreed with him, and related some experiments of his own, which, along with those of Duval, seemed to place the fact beyond all doubt. Later and more careful experiments, however, satisfied Orfila, that it only acts as an emollient after the poison has been removed from the stomach, and that it has no effect at all if the poison is retained by a ligature in the gullet.[1124] Sugar being thus rejected as well as the sulphurets, he was led to try the effects of albumen; and his experiments induced him to recommend that substance as an antidote in preference to every thing else. He found that the white of six eggs completely neutralized the activity of between 25 and 36 grains of verdigris; so that even when the mixture was retained in the stomach by a ligature on the gullet no effect ensued which could be ascribed to the poison. He infers that white of egg is the best antidote for poisoning with copper.[1125] He likewise found the ferro-cyanate of potass not inferior.[1126] Since the publication of these inquires the subject has been again examined by M. Postel, who reverts to the original proposition of Duval, that sugar is really a good antidote; and he rests this conclusion partly on direct comparative experiments, showing that it is at least equally effective with white of egg, and partly on the singular fact ascertained by him, that sugar, which was believed to decompose the salts of copper only at the temperature of 212°, does actually accomplish this decomposition at the temperature of the human body, and throws down the copper in the form of oxide.[1127] According to the experiments of MM. Milne-Edwards and Dumas, metallic iron is likewise a good antidote: they found that when fifteen, twenty, and even fifty grains of sulphate of copper, acetate of copper, or verdigris, were given to animals, and an ounce of iron filings administered either immediately before, or immediately afterwards,—the gullet being tied to prevent the discharge of the poison,—death did not ensue for five, six, or even eight days, and consequently proceeded from the operation on the gullet; and that in one experiment, on the ligature being removed from the gullet, the opening healed up, and complete recovery took place.[1128] Before quitting the subject of the treatment, it is necessary to caution the practitioner particularly against the employment of vinegar,—a substance often ignorantly used for this, in common with many other, species of poisoning. On account of its solvent power over the insoluble compounds formed by the salts of copper with animal and vegetable matters, it must be injurious rather than useful.