[853] Pathology of the Urine, p. 550.
The elimination of lead by the kidneys is favoured by certain medicines, such, for example, as potassic iodide. Annuschat found in dogs poisoned by lead from 3·8 to 4·1 mgrms. in 100 c.c. of urine; but, after doses of potassic iodide, the content of lead rose to 6·9 and even to 14 mgrms. Lead appears to be eliminated by the skin, being taken up by the epithelial cells, and minute, insoluble particles coming away with these cells. If a person who has taken small doses of lead for a time be placed in a sulphur water-bath, or have his skin moistened with a 5 per cent. solution of sodium sulphide, the upper layer of the epidermis is coloured dark; but the perspiration excited by pilocarpin or other agency contains no lead.
§ 790. Fatal Dose—(a.) Sugar of Lead.—It may almost be said that it is impossible to destroy human life with any single dose likely to be taken or administered. In three cases an ounce (28·3 grms.) has been taken without fatal result. Although it must be allowed that repeated moderate doses, extending over some time, are more dangerous to health and life than a single large dose, yet there seems to be in some individuals a great tolerance of lead. Christison has given ·18 grm. in divided doses daily for a long time without any bad effect, save the production of a slight colic. Swieten has also given daily 3·9 grms. (60 grains) in ten days without observing toxic effects. That, in other cases, less than a grain per gallon of some lead compound dissolved in drinking-water, or in some way introduced into the economy, causes serious illness, is most inexplicable.
(b.) The Basic Acetate in solution is more poisonous apparently than the acetate—60 c.c. (11⁄2 drms.) have caused serious symptoms.
(c.) The Carbonate of Lead.—Doses of anything like 28 grms. (an ounce) would probably be very dangerous to an adult; the only case of death on record is that of a child who took some unknown quantity, probably, from the description of the size of the lump, about 10 grms. (21⁄2 drms.).
§ 791. Antidotes and Treatment.—Soluble sulphates (especially magnesic sulphate) have been given largely in both acute and chronic cases; in the acute, it stands to reason that it is well to ensure the presence of plenty of sulphates in the stomach and intestines, in order to form the sparingly soluble lead sulphate, should any residue remain; but to expect this double decomposition to go on in the blood and tissues is not based upon sound observation. The chronic lead-poisoning is best treated by removal from the source of mischief, the administration of large quantities of distilled water, and medicinal doses of potassic iodide.
§ 792. Localisation of Lead.—In a dog, which was killed by chronic lead-poisoning, Heubel found in the bones 0·18 to 0·27 per 1000 of lead; in the kidneys, 0·17 to 0·20; liver, 0·10 to 0·33; spinal cord, 0·06 to 0·11; brain, 0·04 to 0·05; muscles, 0·02 to 0·04; in the intestines traces, 0·01 to 0·02; in the spleen, the blood, and the bile, he also only found traces. Ellenberger and Hofmeister found in the kidneys of the sheep, 0·44 to 0·47; liver, 0·36 to 0·65; pancreas, 0·54; salivary glands, 0·42; bile, 0·11 to 0·40; bones, 0·32; fæces, 0·22; spleen, 0·14; central nervous system, 0·07 to 0·18; blood, 0·05 to 0·12; flesh, 0·05 to 0·08; urine, 0·06 to 0·08; and in the unstriped muscles and the lungs, 0·03 per 1000 of lead.
Without going so far as to say that lead is a natural constituent of the body, it is certain that it may be frequently met with in persons who have been apparently perfectly healthy, and quite free from all symptoms of lead-poisoning. Legrip found in the liver and spleen of a healthy person, 5·4 mgrms. of lead oxide in every kilogram; Oidtmann, in the liver of a man fifty-six years of age, 1 mgrm. of lead oxide per kilogram, and in the spleen 3 mgrms. per kilogram. Hence, the analyst, in searching for poison, must be very careful in his conclusions. Grave and serious errors may also arise from complications; suppose, e.g., that a deceased person previous to death had partaken of game, and inadvertently swallowed a shot—if the analyst had not carefully searched the contents of the stomach for solid bodies, but merely treated them at once with acid solvents, he would naturally get very decided lead reactions, and would possibly conclude, and give evidence to the effect, that a poisonous soluble salt of lead had been administered shortly before death.
§ 793. Detection and Estimation of Lead.—A great number of fluids (such as beer, wines, vinegar, water, &c.), if they contain anything like the amount of one-tenth of a milligramme in 100 c.c., will give a very marked dark colour with SH2. It is, however, usually safest in the first place to concentrate the liquid, to add an acid, and deposit the lead on platinum, in the way to be shortly described. Nearly all the lead from oils and fatty matter may be dissolved out by shaking up the fat with dilute nitric acid; if necessary, the fat should previously be melted.
If (in the usual course of routine research) a hydrochloric acid solution is obtained from the treatment or destruction of organic substances by that agent, and lead sulphide (mixed possibly with other sulphides) is filtered off, any arsenical sulphide may first be extracted from the filter by ammonia, and any antimonious sulphide by sodic sulphide; then the sulphide may be extracted by warm hydrochloric acid, which will leave undissolved such sulphides as those of copper and mercury. On diluting the liquid, and filtration at a boiling temperature, crystals of lead chloride will be deposited on cooling.
If, however, organic matters are specially searched for lead, hydrochloric acid is not the best solvent, but nitric should always be preferred; and, if there is reason to think that the lead exists in the form of sulphate, then the proper solvent is either the acetate or the tartrate of ammonia; but, in either case, the solution should contain an excess of ammonia. It must, however, be remembered that organic matters retain lead with great tenacity, and that in all cases where it can with any convenience be effected, the substances should be not only carbonised, but burnt to an ash; for Boucher has shown[854] that carbon retains lead, and that the lead in carbon resists to a considerable extent the action of solvents.
[854] Ann. d’Hygiène, t. xli.
In the case of sulphate of lead, which may be always produced in an ash from organic substances by previous treatment with sufficient sulphuric acid, a very excellent method of identification is to convert it into sugar of lead. To do this, it is merely necessary to boil it with carbonate of ammonia, which changes it into carbonate of lead; treatment with acetic acid will now give the acetate; the solution may (if the lead is in very small quantity) be concentrated in a watch-glass, a drop evaporated to dryness on a circle of thin microscopic glass, and the crystals examined by the microscope; the same film next exposed to the fumes of SH2, which will blacken it; and lastly, the solution (which should be sweet) tasted. A crystalline substance, possessing a sweet taste, and blackening when exposed to SH2, can, under the circumstances, be no other substance than acetate of lead.
If the analyst does not care for this method, there is room for choice. Lead in solution can be converted into sulphide; in this case it is, however, absolutely necessary that there should be no great excess of acid, since as little as 2·5 per cent. of free hydrochloric acid will prevent all the lead going down. On obtaining the sulphide, the latter, as already described, can be converted into chloride by hydrochloric acid, and the crystalline chloride is extremely characteristic.
From the solution of the chloride the metal may be obtained in a solid state by inserting a piece of zinc in the solution contained in a crucible; the lead will be deposited gradually, and can be then collected, washed, and finally fused into a little globule on charcoal. A lead bead flattens easily when hit with a hammer, and makes a mark on paper. Solutions of the chloride also give a heavy precipitate of lead sulphate, when treated with a solution of sodic sulphate.
When lead is in very minute quantity, an electrolytic method is generally preferable; the lead is precipitated on platinum by using exactly the same apparatus as in Bloxam’s test, described at p. 566; the liquid to be tested being placed in the inner cell, the lead film may now be identified, dissolved in nitric acid, and estimated by a colorimetric process. For the estimation of the minute fractions of a grain by a colour method, it is merely necessary to have a very dilute solution of acetate of lead, to add a known volume of SH2 water to the liquid to be tested in a Nessler cylinder, noting the colour, and add to another a known quantity of the standard lead solution and the same quantity of SH2 as was added to the first.
The process has an advantage which is great, viz., that it either detects copper, or proves its absence at the same time; and there are few cases in which the analyst does not look for copper as well as for lead. Lead, if in sufficient quantity, may be most conveniently estimated as oxide, sulphate, or chloride; the chief properties of these substances have been already described.
§ 794. The Detection of Lead in Tartaric Acid, in Lemonade, and Aërated Waters.—To detect lead in tartaric acid a convenient method is to burn it to an ash, digest in a little strong sulphuric acid, and then add either sodic chloride or a drop of HCl; lead, if present, is precipitated as chloride, giving a pearly opalescence. Lemonades often contain minute quantities of iron and copper as well as lead. Neither copper nor iron are precipitated by ammonium sulphide in presence of potassic cyanide. On the other hand, the sulphide of lead is not soluble in the alkaline cyanides. Hence a liquid which, on the addition of potassium cyanide and then ammonium sulphide, becomes dark coloured, or from which a precipitate separates, contains lead.[855]
[855] F. L. Teed, Analyst, xvii. 142-143.
2. COPPER.
§ 795. Copper, Cu = 63·5; specific gravity, from 8·921 to 8·952; fusing-point, 1091° (1996° F.). Copper in analysis occurs either as a film or coating on such metals as platinum, iron, &c., or in a state of fine division; or, finally, as a bead. In thin films, copper has a yellowish or a yellowish-red colour; it dissolves readily in nitric, slowly in hydrochloric acid. If air be excluded, hydrochloric acid fails to dissolve copper, and the same remark applies to ammonia; but, if there be free access of air, ammonia also acts as a slow solvent. Metallic copper in a fine state of division can be fused at a white heat to a bright bluish-green globule, which, on cooling, is covered with black oxide.
§ 796. Cupric Oxide (CuO = 79·5; specific gravity, 6·5, composition in 100 parts, Cu 79·85, O 20·15) is a brownish-black powder, which remains in the absence of reducing gases unaltered at a red heat. It is nearly insoluble in water, but soluble in ClH, NO3H, &c.; it is hygroscopic, and, as every one who has made a combustion knows, is readily reduced by ignition with charcoal in the presence of reducing gases.
§ 797. Cupric Sulphide, CuS = 95·5, produced in the wet way, is a brownish powder so insoluble in water that, according to Fresenius, 950,000 parts of water are required to dissolve one part. It is not quite insoluble in ClH, and dissolves readily in nitric acid with separation of sulphur. By ignition in a stream of H it may be converted into the subsulphide of copper. It must always be washed by SH2 water.
§ 798. Solubility of Copper in Water and Various Fluids.—The solubility of copper in water and saline solutions has been very carefully studied by Carnelley.[856] Distilled water exerts some solvent action, the amount varying, as might be expected, according to the time of exposure, the amount of surface exposed, the quantity of water acting upon the copper, &c. It would appear that, under favourable circumstances, 100 c.c. of distilled water may dissolve ·3 mgrm. of copper (·2 grain per gallon).
[856] Journ. Chem. Soc., 1876, vol. ii. p. 4.
With regard to salts, those of ammonium exert a solvent action on copper more decided than that of any others known. With the others, however, the nature of the base exerts little influence, the action of the salt depending chiefly on the nature of its acid radical. Thus, beginning with the least effective, the following is the order of dissolving strength:—Nitrates, sulphates, carbonates, and chlorides. It will then at once be evident that a water, contaminated by sewage, and therefore containing plenty of ammonia and chlorides, might exert a very considerable solvent action on copper.
Almost all the oils and fats, as well as syrups, dissolve small quantities of copper; hence its frequent presence in articles of food cooked or prepared in copper vessels. In the very elaborate and careful experiments of Mr. W. Thompson,[857] the only oils which took up no copper, when digested on copper foil, were English neats’-foot oil, tallow oil, one sample of olive oil, palm-nut oil, common tallow oil, and white oil, which was protected from the air by a thick coating of oxidised oil on its surface.
[857] “Action of Fatty Oils on Metallic Copper,” Chem. News, vol. xxxiv. pp. 176, 200, 313.
The formation of copper compounds with the fatty acids takes place so readily that Jeannel[858] has proposed the green colouring of fats by copper as a test for the presence of copper; and Bottger[859] recommends a copper holding brandy to be shaken up with olive oil to free it from copper.
Lehmann has made some useful researches on the amount of copper taken up by fats under different conditions. 100 c.c. of strongly rancid fat dissolved in fourteen days 8·7 mgrms. of copper; but when heated to 160° for one hour, and then allowed to stand, a similar amount was found. Some rancid butter was rubbed into a brass bowl of 90 c.c. capacity, and then allowed to stand for twenty-four hours; the butter became of a blue-green colour. Into this dish, thus partially attacked by fatty acids, 50 c.c. of rancid butter was poured in a melted condition, and allowed to stand for twenty-four hours. The amount taken up was found to be equal to 10 mgrms. of copper for every 100 c.c. of fluid butter.
Hilger found a fatty soup, which had stood twelve hours in a clean copper vessel, to contain 0·163 per cent. copper. According to Tschirch, the easiest fatty salt to form is the oleate, hydrated copper oxide dissolving in oleic acid with great ease, and even copper oxide dissolving to some extent; the palmitate and the stearate are not so readily produced; hence the amount of copper dissolved is greater in the case of olive oil and butter (both rich in oleic acids) than in the case of the firmer animal fats. Acid solutions, such as clarets, acetic acid, vinegars, and so forth, as might be expected, dissolve more or less copper. The amount likely to be dissolved in practice has been investigated by Lehmann. He steeped 600 square metres of copper sheeting or brass sheeting in vessels holding 2 litres of acid claret; the sheets were in some of the experiments wholly immersed, in others partly so. More copper was dissolved by the wine when the copper was partly immersed than when it was wholly immersed; and more copper was dissolved from brass sheeting than from pure copper sheeting. With a sheet of copper, partly immersed, claret may contain as much as 56 mgrms. per litre. Lehmann also investigated the amount of copper, as acetate, which could be dissolved in wine before the taste betrayed its presence: with 50 mgrms. per litre no copper taste; with 100 mgrms. there was a weak after taste; with 150 mgrms. it was scarcely drinkable, and there was a strong after taste; with 200 mgrms. per litre it was quite undrinkable, and the colour was changed to bluish-green. Vinegar, acting under the most favourable circumstances on sheet brass or copper, dissolved, in seven days, 195 mgrms. of copper per litre from the copper sheet, 195 from the brass sheet.
Lehmann discusses the amount of copper which may be taken at a meal under the circumstance that everything eaten or drank has been artificially coppered, but none “coppered” to the extent by which the presence of the metal could be betrayed by the taste; and the following is, he thinks, possible:—
| 300 c.c. of soup boiled in a copper vessel, | 20 | mgrms. Cu. |
| 1 litre of wine which has been standing in a copper vessel, | 50 | „ |
| 50 c.c. vinegar which has been kept in a copper vessel, | 10 | „ |
| 50 grms. of fat which has been used for frying in a copper vessel, | 5 | „ |
| 200 grms. of strongly coppered peas, | 50 | „ |
| 500 grms. of strongly coppered bread, | 60 | „ |
The total only amounts to 195 mgrms. of copper, which only slightly exceeds a high medicinal dose. The metal is tasted more easily in liquids, such as wine, than in bread; bread may be coppered so that at a meal a person might eat 200 mgrms. of a copper compound without tasting it.
It is pretty well accepted that cooking in clean bright copper vessels will not contaminate any ordinary food sufficiently to be injurious to health.
§ 799. Copper in the Vegetable and Animal Kingdom and in Foods.—Copper is widely distributed in the vegetable kingdom, and is a constant constituent of the chief foods we consume; the following quantities, for example, have been separated from the chief cereals:—
| Wheat, | 5 | ·2 | to 10·8 mgrms. | per kilo. | |
| Rye, | 5 | mgrms. | „ | ||
| Oats, | 8 | ·5 | mg„ | „ | |
| Barley, | 11 | ·8 | mg„ | „ | |
| Rice, | 1 | ·6 | mg„ | „ | |
| Bread, | 1 | ·5 | to 4·4 mgrms. | „ | |
It has also been found in vermicelli (2-10 mgrms. per kilo.), groats (1·6-3 mgrms. per kilo.), potatoes (1·8 mgrm. per kilo.), beans (2-11 mgrms. per kilo.). In similar small quantities it has also been found in carrots, chicory, spinach, hazel-nuts, blackberries, peaches, pears, figs, plums, tamarinds, black pepper, and many other fruits and spices. The most common food which has a high copper content is cocoa, which contains from 12 mgrms. to 29 mgrms. per kilo., the highest amount of copper being in the outer husk; copper has also been found in many supplies of drinking water, in aërated waters, in brandies, wines, and many drugs.
It has been calculated that the ordinary daily food of an average man contains the following:—
| Copper. | ||
|---|---|---|
| 900 grms. bread, | 0·45 | mgrm. |
| 260 grms. meat, | 0·25 | „ |
| 200 grms. fruit and vegetables, | 0·25 | „ |
| 0·95 | mgrm. | |
That is to say, that, neglecting altogether foods artificially contaminated with copper, each of us eats daily about 1 mgrm. of copper (0·015 grain).
In the animal kingdom it is a constant and natural constituent of the blood of the cephalopods, crustacea, and gasteropods, and is nearly always present in the liver and kidneys of domestic animals, as well as in men. Dr. Dupré[860] found ·035 to ·029 grain (1·8 to 2 mgrms.) in human livers, or about 1 part in 500,000. Bergeron and L. L’Hôte’s researches on fourteen bodies, specially examined for copper, fully substantiate those of Dr. Dupré; in twelve the copper was found in quantities of from ·7 to 1·5 mgrm.; in the remaining two the amount of copper was very minute, and was not estimated.[861] Copper is also found normally in the kidneys, and Dupré [862] detected in human kidneys about 1 in 100,000 parts; it is also found in the bile, and in minute traces in the blood.[863]
[860] Analyst, No. 13, 1877.
[861] Compt. Rendus, vol. lxxx. p. 268.
[862] Op. cit.
[863] Hoppe-Seyler, Handbuch der physiologisch. Analyse, p. 415.
In the kidneys and livers of the ruminants copper may always be found, a sheep’s liver containing about 1 part in 20,000.[864] Church found copper in the feathers of the wings of the turaco; melopsitt in the feathers of a parroquet (Melopsittacus undulatus).[865] In these cases the copper enters into the composition of the colouring matter to which the name of “turacin” has been given. Turacin contains 7 per cent. of copper, and gives to analysis numbers which agree with the formula of C82H81Cu2N9O32.
Copper has been discovered in aërated waters, its presence being due to the use of copper cylinders, the tin lining of which had been rendered defective by corrosion.[866]
[866] “On the Presence of Lead and Copper in Aërated Waters,” by Dr. James Milne, Chem. News, xxxi. p. 77.
Accidents may also occur from the use of copper boilers. Mr. W. Thompson found in one case[867] no less than 3·575 grains in a gallon (51 mgrms. per litre) in water drawn from a kitchen boiler.
[867] Chem. News, xxxi. No. 801.
At Roubaix, in France, sulphide of copper had been deposited on the roof, as a consequence of the use of copper flues; the sulphide was changed into sulphate by the action of the air, and washed by the rain into the water-tank.[868]
[868] Author’s Dictionary of Hygiène, p. 167.
That preserved vegetables are made of a bright and attractive green colour by impregnation with copper, from the deliberate use of copper vessels for this purpose, is a fact long known. Green peas especially have been coloured in this way, and a number of convictions for this offence have taken place in England.
§ 800. The “Coppering” of Vegetables.—The fact that green vegetables, such as peas, beans, cucumbers, and so forth, preserve their green colour, if boiled in copper vessels, has long been known. In this “coppering” the French have been more active than the English traders; the French operate in two different ways. One method is, to dip from 60 to 70 litres of the green vegetables in 100 litres of 0·3 to 0·7 per cent. of copper sulphate, to leave them there for from five to fifteen minutes, then to remove them, wash and sterilise in an autoclave. A second method is to put the vegetables into a copper vessel, the wall of which is connected with the negative pole of an electric current, the positive pole dips in a solution of salt in the same vessel, the current is allowed to pass for three minutes, and the vegetables are afterwards sterilised. Fruits are simply allowed to stand with water in copper vessels, the natural acidity of the juice dissolving sufficient copper.
The amount of copper taken up in this way is appreciable, but yet not so much as might be expected; the prosecutions for selling “coppered” peas in England have been based upon quantities varying from 1 to 3 grains per lb.; the highest published amount of copper found in peas artificially coloured is 0·27 per kilo., or 18·9 grains per lb.
The reason why vegetables preserve their green colour longer when treated with a copper salt has been proved by Tschirch[869] to be owing to the formation of a phyllocyanate of copper.
[869] Das Kupfer, Stuttgart, 1893.
Phyllocyanic acid is a derivative of chlorophyll, and allied to it in composition; the formula of C24H28N2O4 has been ascribed to it. Under the action of acids generally, mineral or organic, chlorophyll splits up into this acid and other compounds. Copper phyllocyanate, (C24H27N2O4)2Cu, contains 8·55 per cent. of copper; it forms black lamellæ, dissolving easily in strong alcohol and chloroform, but insoluble in water; it is a little soluble in ether, insoluble in petroleum ether, and dissolved neither by dilute acetic acid, nor by dilute nor concentrated hydrochloric acid. The compound dissolves in caustic alkali on warming. In alcohol it forms a beautiful non-fluorescent solution. A solution of 1 : 100,000 is still coloured strongly green.
This solution, in a stratum of 25 mm. thick, gives four absorption bands when submitted to spectroscopic observation, and Tschirch has worked out a process of estimation of the amount of copper phyllocyanate based upon the disappearance of these bands on dilution.
Green substances, so carefully treated that they only contain phyllocyanate of copper, would yield but small quantities of copper, and probably they would not be injurious to health; but the coppering is usually more extensive, and copper leguminate and other compounds are formed; for the vegetables, when exhausted by alcohol, give a residue which, successively exhausted by water, by soda-lye, and lastly by hydrochloric acid, parts with copper into the three solvents mentioned.
It might be argued that, from the insoluble character of the phyllocyanate of copper, and especially seeing that it does not dissolve in strong hydrochloric acid, that it would be perfectly innocuous; but Tschirch has proved that, whether the tartrate of copper (dissolving easily in water), or copper oxide (not dissolving at all in water, but soluble in hydrochloric acid), or phyllocyanate of copper (insoluble both in water and in hydrochloric acid) be used, the physiological effect is the same.
Copper may be found in spirits, owing to the use of copper condensers, a remark which applies also to the essential oils, such as oleum cajepute, menthæ, &c.[870] In France, it has been added fraudulently to absinthe, to improve its colour.[871] Green sweetmeats, green toys, green papers, have all been found to contain definite compounds of copper to a dangerous extent.
[870] According to Eulenberg (Gewerbe Hygiene, p. 716), Oleum cajepute, Menth. pip., Melissæ, Tanaceti, &c., are almost always contaminated with copper.
[871] Tardieu, Étude Méd. Lég. sur l’Empoisonnement.
§ 801. Preparations of Copper used in Medicine and the Arts.
(1) Medicinal Preparations:—
Sulphate of Copper, Cupri Sulphas, CuSO45H2O.—This well-known salt is soluble in water at ordinary temperature, 3 parts of water dissolving 1 of the sulphate; but boiling water dissolves double its weight; 1 part of copper sulphate dissolves in 21⁄2 of glycerin; it reddens litmus, and is slightly efflorescent; its solution responds to all the usual tests for copper and sulphuric acid. A watery solution of the salt to which twice its volume of a solution of chlorine has been added, gives, when treated with ammonia in excess, a clear sapphire-blue solution, leaving nothing undissolved, and thus showing the absence of iron. Besides iron, sulphate of copper has been found to contain zincic sulphate.
Nitrate of Copper, Cu(NO3)23H2O, is officinal; it is very soluble.
Cuprum Aluminatum.—A preparation, called cuprum aluminatum (Pierre divine), is in use in France and Germany, chiefly as an external wash. It is composed of 16 parts cupric sulphate, 16 potassic nitrate, 16 alum, fused in a crucible, a little camphor being afterwards added.
Regular and irregular medical practitioners, veterinary surgeons, farriers, and grooms, all use sulphate of copper (bluestone) as an application to wounds. Copper as an internal remedy is not in favour either with quacks or vendors of patent medicines. The writer has not yet found any patent pill or liquid containing it.
(2) Copper in the Arts.—Copper is used very extensively in the arts; it enters into the composition of a number of alloys, is one of the chief constituents of the common bronzing powders, is contained in many of the lilac and purple fires of the pyrotechnist, and in a great variety of pigments. The last-mentioned, being of special importance, will be briefly described:—
Pigments:—
Schweinfurt and Scheele’s Green[872] are respectively the aceto-arsenite and the arsenite of copper (see article “Arsenic”).
[872] The synonyms for Schweinfurt green are extremely numerous:—Mitic green, Viennic green, imperial green, emerald green, are the principal terms in actual use.
Brighton Green is a mixture of impure acetate of copper and chalk.
Brunswick Green, originally a crude chloride of copper, is now generally a mixture of carbonate of copper and chalk or alumina.
Mountain Green, or Mineral Green, is the native green carbonate of copper, either with or without a little orpiment.
Neuwieder Green is either the same as mountain green, or Schweinfurt green mixed with gypsum or sulphate of baryta.
Green Verditer is a mixture of oxide and carbonate of copper with chalk.
Verdigris is an acetate of copper, or a mixture of acetates. Its formula is usually represented as (C2H3O2)CuO. It is much used in the arts, and to some extent as an external application in medicine. Its most frequent impurities or adulterations are chalk and sulphate of copper.
§ 802. Dose—Medicinal Dose of Copper.—Since sulphate of copper is practically the only salt administered internally, the dose is generally expressed as so many grains of sulphate. This salt is given in quantities of from ·016 to ·129 grm. (1⁄4 to 2 grains) as an astringent or tonic; as an emetic, from ·324 to ·648 grm. (5 to 10 grains).
The sulphate of copper is given to horses and cattle in such large doses as from 30 up to 120 grains (1·9 to 7·7 grms.); to sheep, from 1·3 to 2·6 grms. (20 to 40 grains); rabbits, ·0648 to ·1296 grm. (1 to 2 grains).
§ 803. Effects of Soluble Copper Salts on Animals.—Harnack has made some experiments on animals with an alkaline tartrate of copper, which has no local action, nor does it precipitate albumin. 1⁄2 to 3⁄4 mgrm. of copper oxide in this form, administered subcutaneously, was fatal to frogs, ·05 grm. to rabbits, ·4 grm. to dogs. The direct excitability of the voluntary muscles was gradually extinguished, and death took place from heart paralysis. Vomiting was only noticed when the poison was administered by the stomach.[873] The temperature of animals poisoned by copper, sinks, according to the researches of F. A. Falck, many degrees. These observations are in agreement with the effects of copper salts on man, and with the experiments of Orfila, Blake, C. Ph. Falck, and others.
[873] On the other hand, Brunton and West have observed vomiting produced in animals after injection of copper peptone into the jugular vein.—Barth. Hosp. Rep., 1877, xii.
Roger[874] experimented on the effect of copper leguminate which was administered subcutaneously; he found gradual increasing paralysis of the motor spinal tracts, which finally destroyed life by paralysis of the breathing centre. The heart beat after the breathing had stopped. The irritability and contractility of the muscles of frogs were lost, while sensibility remained. He also found that, if the copper was injected into the intestinal vessels, the dose had to be doubled in order to destroy life; this is, doubtless, because the liver, as it were, strained the copper off and excreted it through the bile. Roger was unable to destroy life by large doses of copper given by the mouth, for then vomiting supervened and the poison in great part was removed.
[874] Revue de Médecine, 1877, xii.
Bernatzic[875] considers that the poisonous properties of copper are similar to those of zinc and silver. He says: “Silver, copper, and zinc are, in their medicinal application, so much allied that, with regard to their action, they graduate one into the other and show only minor differences; copper, which is a little the more poisonous of the three so far as its remote action is concerned, stands between the other two. If taken, in not too small a quantity, for a long time, the functional activity of the muscular and nervous systems is influenced injuriously, the development of the animal cells is inhibited, the number of the red blood corpuscles decreased, and therefore the oxidising process and metabolism are likewise diminished, leading ultimately to a condition of marked cachexia. . . . From a toxic point of view, the three metals named also stand near each other, and their compounds differ from other metals injurious to the organism in this, that they do not produce notable changes of the tissues or coarse functional disturbances leading to death as other poisonous metals, and therefore are not to be considered poisons in the same sense as lead, mercury, arsenic, antimony, phosphorus are considered poisons; for, on stopping the entry of the poison, any injurious effect is completely recovered from and the functions again become normal.”