CHAPTER IV

METALLIC IRRITANTS

ARSENIC

Arsenic is found as metallic arsenic, as arsenious acid, in the form of two sulphides--realgar and orpiment, and as a constituent of several ores--iron, copper, &c.

Metallic arsenic is of a steel-grey colour, brittle, and sublimes at a temperature a little below 400° F., without, however, previously fusing. The vapour of the metal has a peculiar garlic-like odour, which is not possessed by any of its compounds.

Arsenious Acid

Arsenious anhydride--white arsenic--the most important of all the compounds of arsenic, is colourless, odourless, and almost devoid of taste. As found in commerce, it occurs under two forms--as a white powder, and as a solid cake, which is at first nearly transparent, but soon becomes opaque, and then resembles white enamel. At a temperature of about 380° F. it sublimes, but is again deposited on cool surfaces in the form of octahedral crystals. It is but slightly soluble in cold water, only about half a grain to a grain being taken up by an ounce of water. Stirred in boiling water, and then allowed to cool, from a grain to a grain and a quarter is dissolved in the same quantity of water; but when it is boiled for an hour, about twelve grains are dissolved in the ounce of water. This solubility is, however, diminished by the presence of any organic matter in the liquid. It is therefore less soluble in infusions of tea or coffee than in pure water. A teaspoonful of powdered arsenic is said to weigh 150 grains, and a pinch 17 grains.

Arsenious acid is used in the arts in the manufacture of certain green colours, in dyeing, and in calico printing. A weak solution is employed in medicine in the treatment of certain diseases of the skin, in ague, and in other diseases.

It has been proposed to use arsenious acid, on account of its caustic properties, as an application for cancerous tumours. The employment of this substance for this purpose is by no means new; but its use has been revived from time to time by the charlatan. In the year 1844, a man was tried at the Chester Winter Sessions (R. _v._ Port) for the murder of a woman whom he pretended to cure of a cancer by the use of an arsenical plaster. In another case, recorded by M. Flandin, where death occurred, the quack declared that he had not applied more than _four_ or _five_ grains to the woman‘s breast. The powder used for this purpose is generally composed of arsenious acid, realgar, and oxide of iron. The above cases, to which many more might be added, attest to the danger which attends the application of arsenic to the surface of the body; it should, therefore, never be used, especially as a more safe and potent caustic for this purpose is found in the chloride of zinc. Some years ago, in London, several cases of severe arsenical poisoning were due to the presence of arsenic in some cheap violet powder. In one case the navel and scrotum of a baby were fearfully excoriated, due to the use of this powder.

Farmers employ arsenious acid (white arsenic) for destroying vermin: for steeping corn in order to destroy any spores of fungi; and it also forms an ingredient in the wash for sheep. Injurious effects have followed the accidental use of the corn thus treated, and those employed in washing the sheep have suffered more or less severely.

By an Act of Parliament (14 Vict. cap. xiii. sec. 3), it is ordered that if sold in small quantities, it must be mixed with the sixteenth part of its weight of soot, or the thirty-second part of its weight of indigo, ten pounds being the smallest quantity allowed to be sold unmixed.

The presence of this admixture must be remembered, as a medical man may be led into an error when the vomited matters are coloured blue, black, or green, from the mixture of bile with the indigo. Arsenic is not, as a rule, a corrosive poison. One case is, however, on record where it acted as a corrosive, but the purity of the arsenic in that case has been questioned. Its action is that of an irritant, causing inflammation in the stomach and bowels of those who have taken it; and it appears that fatal effects are produced whether the poison be swallowed or introduced into the system in any other way--_e.g._ by injection into the rectum or vagina, or applied to the surface of the body.

Some observers hold that arsenic cannot be considered in the light of an accumulative poison, others that it is so to a certain extent, and that its elimination is not so rapid as was previously thought. Given in medicinal doses, it is eliminated in from fifteen to twenty days. Hence, in cases which have survived the immediate action of the drug, no arsenic may be found in the body fifteen days after its fatal administration. This is a fact of considerable importance. In the case of Pierre Emile L‘Angelier, for whose murder Madeline Smith was tried, Dr. Penny found 88 grains in the stomach, although the deceased survived eight or ten hours after the probable period of taking the poison, and vomited repeatedly during that time. At the above trial, the question was suddenly raised, that if such a large quantity was found after death in the stomach, it was scarcely possible to infer the administration of a much larger quantity; and thus, that the quantity must have been larger than another party could have secretly administered, or naturally would attempt to administer. Drs. Mackinlay and Wylie, of Paisley, obtained 60 grains, and Sir R. Christison 30 grains more, from the stomach of a man poisoned by arsenic administered in whisky-punch sweetened, the arsenic being kept in suspension by constant stirring.

Symptoms of Arsenical Poisoning

_Acute._--The rapidity and virulence of the symptoms are more or less modified by the form (_e.g._ solution) and the dose taken. From half an hour to an hour is the usual time which elapses before the symptoms of poisoning present themselves. In one case, in which the poison was in solution, the symptoms came on immediately after it was swallowed; in another, after the lapse of ten hours. The patient first complains of a feeling of faintness and depression, followed by intense burning pain in the stomach, increased by the slightest pressure. Nausea and vomiting, the latter increased by the act of swallowing, now occur. The vomited matters may be dark brown, black, or bilious; or they may be greenish from the indigo mixed with the arsenic coming in contact with the yellow colouring matter of the bile. Blood may also be vomited. Purging, accompanied with straining at stool, and cramps in the calves of the legs may occur--the purging, like the vomiting, being incessant, and affording no relief to the sufferer; the stools may contain blood, or resemble those of cholera. The thirst is intense, and there may be a feeling of throat irritation, the pulse feeble and irregular, and the skin cold and clammy. The urine may or may not be suppressed. As a rule, the symptoms in this form of poisoning are _continuous_; but cases occur in which there are distinct _remissions_, and even _intermissions_. Coma, paralysis, or tetanic convulsions may supervene before death closes the scene.

_Certain anomalies may occur._--The pain may be absent or but slight. Vomiting and purging do not occur in all cases, nor is thirst, a most common and persistent symptom, always present. In some cases the symptoms resemble those which accompany an attack of cholera. In others, signs of collapse first make their appearance, from which the patient may rally, or he may die outright. These variations in the symptoms do not appear to be due to the _form_ or _quantity_ of the poison taken. It should also be remembered that arsenic may produce symptoms closely resembling those the result of _narcotic poisoning_.

_Chronic._--In whatever way the poison be exhibited in small and repeated doses, there follows a peculiar and characteristic train of symptoms, associated with (_a_) the general nutrition of the body, (_b_) the facial appearance, (_c_) irritative disturbance of the alimentary canal, (_d_) skin eruptions, and (_e_) implication of the nervous system.

(_a_) The nutrition of the body is altered, there is gradual loss of flesh with ragged growth of the finger-nails and falling out of the hair. There may be œdema and jaundice in some cases.

(_b_) The face presents a peculiar appearance, the eyes are inflamed and watery, the conjunctivæ reddened and congested, there is excessive secretion from the nose resembling coryza.

(_c_) The disturbance of the digestive organs is revealed by the dryness of the mouth and occasional excoriation of the tongue, which may be reddened or covered with white fur and silvery in appearance; salivation may be present instead of dryness of the mouth; there may also be irritation of the throat; symptoms of gastro-enteritis, _e.g._ nausea and vomiting, anorexia, diarrhœa, or alternating diarrhœa and constipation.

(_d_) The skin eruptions are of various kinds, and comprise eczema, herpes, urticaria, erythema, keratosis, marked pigmentation and exfoliation.

(_e_) The nervous symptoms are those of peripheral neuritis, numbness, formication, hyperæsthesia, and tenderness, especially of the soles of the feet, the latter presenting appearances of erythro-melalgia; there is some amount of paresis, in some cases amounting to absolute paralysis of the limbs affected. The hands may be anæsthetic, while the feet are hyperæsthetic and hyperalgesic, and the perspiration much increased. Mental symptoms are not common, but there may be hebetude, or delusions.

In the Maybrick case, tried at the Liverpool Assizes in 1889, the following symptoms arose from repeated administration of arsenic during a period of probably about fourteen days. On April 27 Mr. Maybrick was seized with vomiting after taking tea. On the next day the vomiting continued, with foulness of the tongue, and he complained of stiffness in the lower limbs. On May 1 he complained of feeling unwell after taking luncheon, and he was sick on the following three days, and complained of a tickling sensation in the throat, with retching. On May 7 he was still suffering from vomiting, diarrhœa had commenced, and the throat was very dry and inflamed. On May 8 the diarrhœa was accompanied by tenesmus. On May 9 the tenesmus was distressing, and he died on May 11.

Dr. Prosper de Pietra Santa describes a disease to which workers in manufactories of paper coloured with Schweinfurt-green are liable, characterised by the appearance of vesicles, pustules, _plaques muqueuses_, and ulcerations on the exposed parts of the body, fingers, toes, and scrotum. Arsenical poisoning has been mistaken for nettle-rash, scarlet fever, and Addison‘s disease. In cases of slow poisoning the symptoms resemble very much those of gastritis and ulcer of the stomach, and death due to the action of arsenic has been referred to “spontaneous inflammation of the bowels.”

It must be remembered that in some cases of acute arsenical poisoning, when the acute symptoms have passed away, the nervous system exhibits its effects at a later period; in one case paresis came on on the fifth day, in another at the end of a week, and in a case recorded by Seeligmüller four weeks elapsed before the onset of nervous symptoms.

_Post-mortem Appearances._--The appearances found after death depend upon the quantity of the dose and the length of time which supervenes between the taking of the poison and death. Inflammation of the stomach is a marked effect of the action of this substance on the system; and this condition is in most cases present whether the poison be swallowed, sprinkled on an ulcerated surface, or rubbed into the skin. The inflammatory redness, which may assume the appearance of _crimson velvet_, may be found in cases where death has taken place in _two_ hours. It is sometimes found spreading over the entire surface of the stomach; at others, at the cardiac end only. The red colour is increased on exposing the stomach to the air. When the poison has been swallowed, the stomach may be found covered with white patches of arsenic, embedded in dark-coloured thick mucus, mixed with blood. Dr. Paterson thus describes the condition of a stomach he examined: Its lining membrane was generally very red and injected; but in addition there were very numerous stellated patches of vivid red, leading to a darker tint; in the centre of some of them was noticed a minute clot of blood; in others, an exceedingly rough particle of a crystalline substance, which was afterwards found to be arsenious acid. Perforation of the stomach is extremely rare, if it has ever occurred, but ulceration of the same organ has been observed in a person who died from the effects of arsenic in _five_ hours (Christison, on _Poisons_, p. 340). In opposition to all the statements just made it has been shown that arsenic may prove fatal without leaving any sign of inflammatory action (R. _v._ M‘Cracken; R. _v._ Newton).

The mouth, pharynx, and gullet are generally found free from any inflammatory action. The small intestines may or may not be affected: in most cases the duodenum alone shows any signs of irritation. The rectum is that part of the large intestine most prone to inflammation. I have seen marked ulceration of the colon after death from inhalation of arseniuretted hydrogen. The other internal organs--the liver, spleen, and kidneys--do not appear to be appreciably affected by arsenic.

Due probably to the antiseptic properties of arsenic, the stomach and intestines retain for a long period after death the appearances of irritant poisoning. In two cases, this was so well marked as to be visible--in the one case, _twelve_ months, and in the other, _nineteen_ months after interment. In suspected cases portions of the liver should always be preserved and examined for arsenic.

=The Period after Death when Arsenic may be Detected=

Arsenic is an indestructible poison, and may be found in the body after many years. In one case it was detected after the lapse of fourteen years. Arsenic has the power, to a certain extent, of arresting putrefactive changes; the stomach may, therefore, be found well preserved, and with the signs of inflammatory action present after the lapse of many months, and after putrefaction has far advanced in other parts of the body. When a person is suspected of having been poisoned with arsenic, and nothing but the skeleton is left for investigation, the arsenic should be looked for specially in the bones of the pelvis and the neighbouring vertebræ (_Watt‘s Dictionary of Chemistry_, Sup.).

In reference to the preservative action of arsenic upon the tissues of those poisoned by it, the appearances of the bodies of the victims of Flannagan and Higgins, recorded by Whitford (_B. M. J._, 1884, vol. i. p. 504), are interesting. Arsenical poisoning having been established in one of three victims, the bodies of two others, Mary Higgins, aged ten years, and John Flannagan, aged twenty-four years, were exhumed and examined. The abdominal viscera of Mary Higgins yielded one grain of arsenious acid, and although the body had been interred for about thirteen and a half months, it was well preserved. A remarkable state of preservation obtained in the body of John Flannagan, who had been interred for thirty-seven and a half months; the face and body generally could be easily identified. Three and a half grains of arsenious acid were found in the abdominal viscera. In these cases a peculiar appearance was found in the stomach and intestines, consisting of a golden-yellow pigment or coating of the mucous membrane of the parts. It was thought by some observers to be composed of arsenic sulphide, but Campbell-Brown, and Davies of Liverpool, as a result of their analysis of it, found that it did not contain any appreciable amount of arsenic, but consisted mainly of bile pigment.

In trials for arsenical poisoning, where an exhumation has been made, the question may arise whether the arsenic found in the body has been carried into it from the earth surrounding the coffin.

In reply, the following points must be kept in mind:

1. Arsenic may occur in certain calcareous and ochrey soils.

2. In these soils no arsenical compound _soluble in water_ has been found.

3. The arsenic of these soils is dissolved out by hydrochloric acid, proving their previous insolubility.

4. The arsenic is, therefore, probably in the form of an arsenite or arseniate of iron, lime, &c.

5. Careful experiments have rendered it evident that even “under the most favourable circumstances the dead human body does not acquire an impregnation of arsenic from contact with arsenical earth” (Taylor).

6. It has been suggested that the arsenical compound in the soil may be rendered soluble by the ammonia formed during putrefaction.

This last suggestion is negatived by the following facts:

1. The production of ammonia ceases before the body arrives at that stage of decomposition when it is at all likely to be exposed to the

## action of the soil of the cemetery.

2. The production of hydrosulphuret of ammonia during decomposition would tend to the production of sulphuret of arsenic forming yellow patches in the substance of the organs, thus rather fixing the arsenic on particular parts than allowing it to percolate through the tissues of the body from external application.

_Analysis of the Suspected Earth._--About two pounds of the earth should be boiled for some time in water; supernatant liquid should then be poured off from the insoluble residue, and filtered. The filtered liquid, after concentration, may then be examined by the tests about to be described. If no arsenic be found, the earth may now be boiled with dilute hydrochloric acid, filtered, concentrated, and then tested as before. The first process shows that no compound of arsenic soluble in water is present; the second shows that the arsenic is in a state of combination, and therefore not likely to impregnate the body.

=The Detection of Arsenic=

_General Directions._--In cases of suspected poisoning by arsenic or antimony, the contents of the stomach should be mixed with distilled water acidulated with hydrochloric acid and filtered, and the filtrate placed in a stoppered bottle lettered or numbered “A” or “1.” The liver should be cut into pieces, some of which should be bruised in a mortar with distilled water acidulated as above mentioned, pressed and filtered, and the filtrate placed in a bottle marked “B” or “2.”

The kidneys and portions of the other solid organs may also be treated as above. Each solution so obtained may be then tested by the processes about to be described. By these means the amount of poison in each organ may be estimated.

Before subjecting the organic mixture to Marsh‘s or Reinsch‘s processes, Brande and Taylor strongly recommend a modified course of procedure.

The contents of the stomach, vomited matters, &c., and the solid organs, finely divided, must each be separated and _thoroughly_ dried in a water bath, then mixed with an excess of _strong_ hydrochloric acid in a flask, and slowly distilled by means of a sand bath, the distillate carried into a receiver containing a little pure distilled water, and the process continued nearly to dryness.

If arsenic be present, the distillate contains the arsenic as chloride, and can be at once subjected with great facility to the usual tests for the presence of that metal. This mode of proceeding both facilitates and expedites the ordinary methods of testing, as it separates the arsenic present from the complex organic mixtures with which it is associated, and presents it in a comparatively pure form for identification. The process also admits of the residue left in the retort being examined for lead and the other metallic poisons.

Before the following processes are applied, some of the sediment from the contents of the stomach, or the vomited matters, may be collected and well washed. If this is boiled in distilled water and filtered, the following tests, known as “the liquid tests for arsenic,” may be applied to the filtrate:

1. _Ammonia Nitrate of Silver_, prepared by adding a weak solution of ammonia to a strong solution of nitrate of silver, gives with arsenic a yellow precipitate of _arsenite of silver_ soluble in nitric, citric, acetic, and tartaric acids, and ammonia.

2. _Ammonia-Sulphate of Copper_, prepared by adding ammonia to a dilute solution of sulphate of copper, gives with arsenic a green precipitate of _arsenite of copper_. This precipitate is soluble in the mineral and vegetable acids and ammonia, but is not affected by soda or potash. The precipitate, dried and heated in a reduction tube, yields octahedral crystals of arsenious acid.

3. _Sulphuretted Hydrogen._--The suspected liquid should be first slightly acidulated with _pure_ hydrochloric acid _before_ the sulphuretted hydrogen gas is passed into it, when, if arsenic be present, a yellow precipitate is formed, known to be such by the following tests:

(1) Insoluble in water, ether, alcohol, the vegetable acids, and dilute hydrochloric acid, but decomposed by strong nitric and nitro-hydrochloric acids.

(2) Dissolved, if no organic matter present, forming a colourless solution, when potash, soda, or ammonia is added.

(3) The yellow precipitate dried and heated with soda and cyanide of potassium yields a sublimate of metallic arsenic.

_N.B._--None of the above tests should be applied in the presence of organic matter. The soluble salts of cadmium and per-salts of tin give yellow-coloured precipitates with sulphuretted hydrogen.

(4) If stannous chloride dissolved in strong hydrochloric acid be added to a solution of arsenic in hydrochloric acid, metallic arsenic is thrown down as a precipitate. This is a fairly delicate test.

The following Table gives the differences between the Yellow Precipitates formed with Sulphuretted Hydrogen and Arsenic, Cadmium, and Per-Salts of Tin:

+------------------+-----------------+------------+--------------+ | | | | Per-Salts | | | Arsenic. | Cadmium. | of Tin. | +------------------+-----------------+------------+--------------+ |Colour. |Yellow. |Yellow. | Dirty yellow.| | | | | | |Action of ammonia.|Soluble. |Insoluble. | Insoluble. | | | | | | |Action of |Insoluble. |Soluble. | | |hydrochloric acid.| | | | | | | | | |With cyanide |Sublimes as |Sublimes as | No sublimate.| |flux. |metallic arsenic.|brown oxide.| | +------------------+-----------------+------------+--------------+

_Marsh‘s Process._--This method for the detection of arsenic is founded on the fact that the several compounds of arsenic, except the sulphide and metallic arsenic itself, form a gaseous compound with nascent hydrogen, from which it may be readily separated by appropriate treatment. The solution to be tested should, therefore, be prepared as proposed by Brande and Taylor, given on a preceding page.

_Precautions._--(1) Absolute purity of reagents. (2) The sulphuric acid should be diluted with five times its weight of water, and allowed to cool. (3) The suspected fluid should be added gradually. (4) Generate the gas regularly. (5) If no stain be at once produced, keep a portion of the exit tube red-hot for at least one hour.

The usual form of the apparatus is that of a =U=-shaped glass tube, about one inch in diameter and eight inches high, supported in a vertical position on a wooden stand. One end of the tube is fitted with a tap, and terminates in a glass tube drawn to a fine point; the other end is closed with a cork.

The apparatus is used as follows: A piece of pure zinc is dropped into the tube, and shaken into such a position that it occupies the bottom of that limb of the tube which is furnished with the tap. Water is then added, and subsequently sufficient pure sulphuric acid to cause a moderately brisk evolution of hydrogen. The production of hydrogen gas from pure zinc and pure sulphuric acid is sometimes slow, and may be facilitated by adding a few drops of platinic chloride solution to the contents of the flask previous to the addition of the sulphuric acid. The gas being allowed to accumulate for a short time, the tap is then partially turned on, and the gas ignited; if, on depressing a piece of white porcelain momentarily in the flame, no deposit or discoloration occur, the reagents used may be taken as pure. By the use of Thorpe‘s apparatus for Marsh‘s test, in which the hydrogen is obtained by the electrolysis of water, the absence of arsenic in the reagents and apparatus is ensured. The tap is now connected with a tube of thin, hard glass, drawn out to a fine point at the end and having a constriction in the middle. The liquid to be tested being now placed in the apparatus, the gas is again ignited, and a piece of white porcelain momentarily depressed in the flame, when, if arsenic be present, a black, circular, metallic-looking stain will appear, which has the following composition. In the centre is the unoxidised metal, round this is a mixed deposit, and outside this the zone of arsenious acid. While the gas is passing, the exit tube should be heated to redness a little behind the constricted part, when a dark ring will appear if arsenic be present. The black deposit on the porcelain may be either arsenic or antimony, but may be distinguished as follows:

--------------------+---------------------------+-------------------- | Arsenic. | Antimony. --------------------+---------------------------+-------------------- Nature of the stain.|Metallic brilliancy. |Absence of metallic | |lustre. | | Effect of heat. |Volatile. |Non-volatile. | | Heated with a little|Dissolves. |Oxidises to a white nitric acid. | |insoluble powder. | | Warmed with a strong|Dissolves immediately. |Slowly dissolved. solution of chloride| | of lime. | | | | Treated with |Detached but not dissolved,|Soluble: on bisulphide |but if heated |evaporation, of ammonium. |to drive off ammonia |_orange-yellow_ |_yellow sulphide_ |sulphide formed. |formed. | | | The nitric acid |A brick-red precipitate |No reaction, but if solution |soluble in ammonia. |ammonia and potash evaporated to | |are added, a black dryness gives with | |precipitate is nitrate of silver. | |ultimately formed. --------------------+---------------------------+--------------------

The portion of the tube on which the dark ring has been deposited is now cut off, broken into fragments, and heated in a small, hard glass tube--when, if arsenic be present, a white sublimate will be obtained of well-defined octahedral crystals. If the sublimate be treated with sulphide of ammonium, it is detached but not perfectly dissolved, and on evaporation of the solution to dryness, a residue of the yellow sulphide of arsenic will remain, which, if heated with strong nitric acid, and evaporated again to dryness, will give a brick-red precipitate with nitrate of silver solution, soluble in ammonia. The process of Marsh may be used quantitatively by passing the issuing gas through a glass tube, dipping into a strong solution of argentic nitrate. A portion of the tube is kept at a red heat, when, if arsenic be present, it is deposited in the metallic form in the cool portion. The glass tube containing the stain is cut with a file and weighed. The stain is then removed by strong nitric acid, the tube dried and weighed: the difference in weight equals the amount of metallic arsenic. The nitrate of silver solution is now treated with pure hydrochloric acid, filtered, and the filtrate neutralised with sodium carbonate, titrated with standard solution of iodine. By dipping the end of the issuing tube into a fresh solution of argentic nitrate, the absence of colour will show that all the arsenic has been obtained.

Instead of the =U=-shaped tube a Wolff‘s bottle or Erlenmeyer‘s flask may be used, and the exit tube carrying off the gas bent twice upon itself and connected with a glass bulb containing calcium chloride. From this bulb the long, hard glass tube proceeds, pointed at the end to form a gas jet; the gas is lighted at the end, and if a Bunsen flame be applied at a short distance from the end, a deposit of the arsenic, if present, will form on the distal side of the point at which the flame is applied.

_Reinsch‘s Process._--First obtain a clear solution by filtration or otherwise, and then proceed as follows: Strongly acidify the liquid with hydrochloric acid, introduce some pieces of copper foil, and heat to near the boiling-point of the liquid. Both the acid and metal must be previously tested to ensure their freedom from arsenic. Any arsenic present will then be deposited on the copper in the metallic state, either in the form of a black lustrous deposit when the arsenic is present in any quantity, or else as a steel-grey coating when a minute quantity only is present. In either case, the copper foil, after remaining for some time in the suspected fluid, is taken out, cut into small pieces, introduced into the bottom of a hard glass tube, and heated to low redness, when the arsenic will sublime as arsenious acid in octahedral crystals, forming a ring in the cooler portion of the tube. The deposit is identified as arsenious acid by the form of the crystals, and by its deportment with the various reagents, as in the treatment of similar sublimates mentioned under _Marsh‘s Process_. Two precautions have to be taken in applying this test: do not use too large a portion of copper foil at first, and do not remove the copper too quickly from the boiling fluid. A solution containing arsenic acid or an alkaline arsenite, mixed with sulphuric acid, does not produce any deposit on metallic copper even after long boiling, unless the quantity of the arsenic present be considerable; the deposition may, however, be ensured by adding sulphurous acid or a sulphite, whereby the arsenic is reduced to arsenious acid (G. Werther, _J. Pr. Chem._, lxxxii. 286; _Jahresb._, 1861, p. 851).

_Objections to Reinsch‘s Process._--The chief objection to Reinsch‘s process is the possible impurity of the reagents used--both these reagents, even when supplied as pure, being liable to contain traces of arsenic. As met with in commerce, both hydrochloric acid and metallic copper invariably contain minute quantities of arsenic, the former generally containing the larger quantity of that impurity. Although, by purchasing the purest possible reagents, specially prepared for analysis, it may be possible to ensure their freedom from arsenic, yet in all cases they should be tested before using them. Some of the hydrochloric acid should be diluted with distilled water, and gently heated with the copper foil. If no tarnishing or deposit of any kind occur on the metal after a lapse of several hours, the reagents may be taken as pure and the trial of the suspected substance at once made.

Professor Abel has proposed the following process to ensure the purity of the copper and acid: Boil together equal portions of strong hydrochloric acid and a solution of perchloride of iron. While the mixture is boiling immerse the copper foil, which, if pure, will be merely brightened in colour; if impure, a black deposit on the metal is formed.

[Illustration: Fig. 30.--Photo-micrograph of sublimate of arsenious acid obtained by Reinsch‘s process, × 250. (R. J. M. Buchanan.)]

_Bloxam‘s Method for the Detection of Arsenic._--The late Professor Bloxam suggested an admirable and delicate process for the detection of small quantities of arsenic. The method is, like that of Marsh, founded on the property possessed by nascent hydrogen of forming a gaseous compound with arsenic; but, instead of the hydrogen being generated by the action of dilute sulphuric acid on zinc, Bloxam generates the gas by an electric current.

The wires from the extremities of a battery terminate in small plates of platinum foil, which are plunged into the liquid to be tested, the apparatus being so arranged that the hydrogen gas evolved from the negative pole is collected. The issuing gas is tested in a similar manner to that obtained in Marsh‘s process.

This method of Bloxam‘s is exceedingly delicate, and possesses one great advantage, that no zinc being used, there is no danger of contamination by the use of impure metal; while, as nothing foreign is introduced during the process of testing, the liquid under examination is left pure for the application of other tests if necessary.

[Illustration: Fig. 31.--Dowzard‘s apparatus for Gutzeit‘s test for arsenic. A and B indicate glass cells or traps which contain solutions of lead acetate and copper chloride for the purpose of fixing H₂S and PH₃ which otherwise would react upon the mercuric chloride spot on the filter-cap. The cells are fitted into one another, as shown in the figure.]

_Gutzeit‘s Test._--This test is more sensitive to the presence of minute quantities of arsenic than that of either Reinsch or Marsh. The apparatus devised by Dowzard should be used (_Journ. Chem. Soc._, vols. lxxix. and lxxx. 463, p. 715), which consists of an Erlenmeyer‘s flask fitted with superimposed cells, containing solutions which will wash or neutralise those gases which would interfere with the accuracy of the result. The following is Dowzard‘s description of the method of using the apparatus:

“A weighed or measured portion of the sample is mixed with 5 c.c. of pure HCl (if the sample is alkaline it must be neutralised first), four drops of a 15 per cent. solution of cuprous chloride in hydrochloric acid are then added, and the mixture made up to 30 c.c. with water; if it is not convenient to work with such a small bulk as 30 c.c. this quantity may be doubled or trebled, but the same proportion of acid should be used. A rod of pure zinc, 3 cm. long and 5 mm. in diameter, is first placed in the flask, the above mixture is then introduced and the first cell placed in position; lead acetate solution 5 per cent. is now poured into the cell until it is about half full. The second and third cells are filled in a similar manner; a small tuft of cotton wool is introduced into the neck of the top cell, and its mouth capped with mercuric chloride paper, which may be held in position by an elastic band or a glass collar made from a piece of glass tubing. After forty minutes or more the cap is removed and examined in full daylight. A minute trace of arsenic is indicated by a lemon-yellow spot, which varies in tint according to the amount present; and a heavy trace by an orange-brown spot. The mercuric chloride paper is prepared as follows: one drop of a 5 per cent. solution of mercuric chloride is allowed to fall on the centre of a piece (4 cm. square) of thin Swedish filtering paper, such as Muncktell‘s No. 1 F.; the paper is dried before using.” The lead acetate in the cells absorbs any H₂S gas given off, and if additional cells contain a 15 per cent. solution of cuprous chloride in hydrochloric acid, PH₃ is also prevented from passing and causing a stain. By this method arsenic can be detected in the presence of 2500 times its weight of antimony. The presence of selenium and tellurium compounds does not interfere with the usefulness of this method.

_Fleitmann‘s Test._--Detects arsenic in the presence of antimony, but does not detect arsenic as arsenic acid. When zinc or aluminium is heated with excess of potassium or sodium hydroxide in a mixture containing arsenious anhydride, arseniuretted hydrogen is evolved. The gas may be led into 4 per cent. nitrate of silver solution, or a test tube the top of which is covered with filter paper wet with nitrate of silver. The gas reduces the silver salt, and a black precipitate is produced in the solution, or a black spot on the paper.

_Fatal Dose._--Two grains in solution have been known to cause death. Recoveries have, however, occurred after an ounce or more of the poison has been taken. Much will depend upon the fulness or emptiness of the stomach at the time the poison is taken, and also upon the vehicle in which the poison is administered. Vomiting and purging are more urgent when the dose is large, probably assisting to get rid of the arsenic before its fatal action is produced.

_Fatal Period._--From twenty minutes to two or three weeks, and even later from the secondary effects of the poison. Any thick medium, cocoa or soup, will of course delay the action of the poison.

_Treatment._--Vomiting should be promoted, and diluent drinks largely given. The stomach pump, if it can be procured without much delay, should also be employed to empty the stomach. Emetics of sulphate of zinc should be given without delay--followed by the administration of milk, lime-water, and albumen. Symptoms as they occur must be treated on general principles.

The hydrated sesquioxide of iron, the hydrated oxide of magnesia, and animal charcoal have been proposed and used as antidotes. The sesquioxide of iron can be prepared ready to hand by saturating the tincture _ferri perchloridi_ with ammonia or washing soda. It should be given freely. Drachm doses of dialysed iron in water may be administered. Reputed antidotes are useless when the poison is in the solid state. The diarrhœa, tenesmus, collapse, pain, and nervous symptoms should be treated on general principles.

=Other Poisonous Compounds of Arsenic=

=Arsenical Vapour.=--The vapour from the flues of the copper and arsenic smelting-works in Cornwall, escaping into the air, may cause death to cattle, and the destruction of vegetation. The workmen in these works not infrequently suffer from eruptions on the skin, and from great constitutional derangement; but, on the whole, taking into consideration the dangerous nature of their employment, the men appear to enjoy average health. Actions for damage and nuisance have resulted from the escape of this vapour from the factories.

=Arsenite of Potash.=--A solution of arsenite of potash, mixed with the tincture of red lavender (the solution contains four grains of arsenious acid in one ounce)--better known as Fowler‘s Solution, or as Fowler‘s Mineral Solution or Tasteless Ague Drop. It is probably a solution of arsenious acid in carbonate of potash, and not a true arsenite of potash. This preparation has been much used as a domestic remedy for ague in the Fens of Cambridgeshire. Death from its use is rare; but it is, nevertheless, too dangerous a medicine to be used recklessly. Idiosyncrasy has much to do with the action of the drug, some persons taking even large doses with impunity, whilst, in others, the smallest medicinal dose has produced alarming symptoms. It is stated that the Styrian arsenic-eating peasant is capable of taking without injury five grains of arsenious acid for a dose; and in one case of suspected murder in Styria, the prisoner was acquitted as the deceased was known to be an arsenic-eater.

_Donovan‘s Solution._--A solution of hydriodate of arsenic and mercury. Now officinal, and much used by many practitioners.

_Sheep Dip._--The mixture used for washing sheep, composed of tar-water, soft soap, and arsenic, has caused death in twenty-four hours. The men engaged in dipping the sheep may suffer both locally and constitutionally from the effects of the arsenic in the solution.

_Treatment._--As before described.

_Analysis._--See p. 280 _et seq._

=Arsenite of Copper.=--Scheele‘s green, and the aceto-arsenite of copper, Schweinfurt-green, are met with in commerce and the arts as green pigments. Among workmen they are familiarly known as emerald-green, Brunswick-green, or Vienna-green. In France, the term _vert Anglais_ or English green has been given to them. Scheele‘s green contains about 55 per cent. of pure arsenious acid; the other, Schweinfurt-green, about 58 per cent.

These colours are employed for various purposes, among which the following may be mentioned:

1. Artificial flowers and other articles of dress. 2. Confectionery, pastry ornaments, and toys. 3. As green paint for the insides of houses. 4. In the green colour for wall-papers. 5. In the green-coloured paper lining boxes, &c. 6. Green-coloured tapers used for artificial lighting.

The employment of emerald-green in the colouring of wall-papers is so extensive, that in the year 1860 an English paper-stainer stated that he used two tons of arsenic weekly. In 1862 the amount of this colour manufactured during the year was from 500 to 700 tons. Numerous cases of chronic arsenical poisoning have resulted from the presence of arsenic in the form of Scheele‘s green and Schweinfurt-green in wall-papers and other articles. As the colour is only loosely applied to the surface by means of a weak solution of size, it is easily brushed off, and may so impregnate the air of a room as to produce injurious effects on those who inhabit the apartment. By fermentation of the starch paste used for fastening the paper to the walls, nascent hydrogen is liberated, and, combining with the arsenic to form arseniuretted hydrogen, passes into the air of the room and is inhaled. This gas is extremely poisonous, and small quantities suffice to produce serious results. Certain moulds are endowed with the power of living in materials containing arsenic, and of decomposing arsenious acid or its salts into the gaseous form known as _diethylarsine_; there are altogether ten such moulds, and the most active is the _Penicillium brevicaule_.

In the case of ladies‘ dresses, the following method is adopted:

The colouring material is made by thoroughly stirring together a mixture containing, in definite proportions, the green pigment, cold water, starch, and gum arabic, or some similar substance which shall give the colour consistence and adhesiveness. Not infrequently in this process the hand and forearm are freely used in the liquid to expedite the work. Of this mixture, properly prepared, the workman takes a quantity in his fingers and roughly spreads it over the muslin or fine calico. The fabric is then beaten and kneaded between the hands until it is uniformly coloured. The longer this process is continued, the more perfect is the result. The cloth is now fastened to a frame for drying. In all this process of colouring, the hands, forearms, and frequently also the face of the operative must become soiled with the green colour. It will be also observed that the colour is but loosely applied, _no mordant being used_, as in calico printing, to fix the pigment in the texture of the cloth.

_Symptoms._--All the effects produced by arsenic may result from the use of articles coloured with these pigments. Chronic inflammation of the stomach and bowels, and irritation of the eyes, accompanied in some cases with extreme nervous debility and prostration, are by no means uncommon in those employed in the manufacture of this “cheerful,” but poisonous colour. The skin of the hands, arms, and scalp is often attacked by a vesicular eruption or an erythema. When it is borne in mind that, according to the analysis of Hoffman, a single twig of twelve artificial leaves may contain as much as ten grains of pure arsenic, it is not to be wondered at that the most serious results have occurred from the reckless use of these colours. In Prussia and France the use of the arsenical colours is prohibited.

_Analysis._--Scheele‘s green is insoluble in water, but is soluble in ammonia, the solution having a blue colour, from the separation of the arsenious acid from the oxide of copper. If a few drops of the blue ammoniacal solution be poured on some crystals of nitrate of silver, the yellow arsenite of silver is formed. The blue ammoniacal solution, if acidified with HCl and boiled with pure copper foil, deposits arsenic on the copper, which, if cut into strips and placed in a small reduction tube and heated, sublimes and is deposited in octahedral crystals on the cold portion of the tube. The tests before described are applicable for the detection of this substance.

=Orpiment=

Orpiment, or yellow arsenic, one of the sulphurets of arsenic, has been used occasionally as a poison. It is also largely employed in the arts for paper-staining and for colouring toys. In cases of arsenical poisoning, it is this compound that is commonly found adhering to the stomach and intestines. It is formed by the sulphuretted hydrogen, the result of decomposition, acting on the white arsenic swallowed.

=Realgar=

Realgar, or red arsenic, is another of the sulphurets of arsenic, and, like orpiment, is largely used in the arts as a colour. It is also employed, like orpiment, as a depilatory, fatal results having followed its use for this purpose. The colour of this substance prohibits its frequent use as a poison.

Both of these compounds owe their poisonous properties to the amount of free arsenious acid which they contain, and which may be as much as 30 per cent.

_Symptoms._--The symptoms produced by these substances are similar to those caused by arsenic. The fatal dose will depend on the amount of free arsenious acid which they may each contain.

_Treatment._--Emetics and demulcent drinks.

=Metallic Arsenic, &c.=

Metallic arsenic, fly powder, arsenic acid, largely used in the manufacture of magenta, aniline red, or fuchsine, and the arseniates of potash and soda, are all poisonous. The _papier moure_ of the shops consists of blotting-paper steeped in a solution of arseniate of potash. Macquer‘s neutral arsenical salt is the binarsenate of potash.

_Symptoms._--The symptoms are those of arsenical poisoning.

_Treatment._--When metallic arsenic has been taken, vomiting must be promoted by the use of proper emetics. Tartar emetic should never be used. In the treatment for poisoning with arsenic acid, or of the arseniates of potash and soda, the hydrated oxide of iron, or of the acetate of iron, should be used, as the arseniates are precipitated by the iron.

=Arsenic Acid=

No case of poisoning by this substance has been recorded, for, although poisonous, it is better known in the laboratory than in the shops. It differs from arsenious acid in being only partially volatilised by heat, in its solubility in water, and in being precipitated of a brick-red colour by nitrate of silver. With sulphuretted hydrogen a yellow precipitate is slowly formed, insoluble in hydrochloric acid.

=Arseniuretted Hydrogen=

This gas has proved fatal in several cases. It is generated in the process known as Marsh‘s process for arsenic, and is so poisonous that a very small quantity, not sufficient to be detected by its odour, has caused death. In most cases death has been the result of accident.

_Symptoms._--Giddiness, fainting, constant vomiting, pain in stomach, and suppression of urine, with rapid destruction of the red blood corpuscles, associated with hæmorrhages from all the mucous membranes and jaundice, are among the most prominent symptoms.

The _post-mortem_ appearances are inflammation of the stomach, with softening of its coats. The liver and kidneys are also more or less affected, and have been found of a deep indigo colour.

_Analysis._--This has been described when speaking of Marsh‘s process for arsenic.

=Cacodylic Acid=

Cacodylic acid and the cacodylates are poisonous. The acid dissolves easily in water and alcohol, and it unites with many metals and organic substances to form salts. Although it is held by some to be non-poisonous, Murrell asserts that the administration of cacodylate of sodium produces symptoms “far more severe than those which follow the exhibition of arsenic in its ordinary forms” (_B. M. J._, 1900, vol. ii. p. 1823; 1901, vol. i. p. 120).

Professor Fraser of Edinburgh, on the other hand, from clinical observation and chemical tests, affirms that cacodylic acid and the cacodylates are extremely stable bodies, and the arsenic in them is with such great difficulty set free that it passes through the body in combination as an inert substance (_B. M. J._, 1902, vol. i. p. 713).

=Arsenical Contamination of Food Stuffs=

Arsenic is found associated with many other substances in nature,

## particularly copper and pyrites. Arsenic is commonly present in

commercial sulphuric acid manufactured from pyrites containing the metal, and when such acid is used with common salt for the production of hydrochloric acid, the latter also becomes contaminated. It may be safely stated that commercial sulphuric acid, hydrochloric acid, copper and zinc, free from arsenic, do not exist in the market. Hence in the detection of arsenic by the toxicologist the absolute purity of these reagents, which he uses, must be established.

In the manufacture of glucose, arseniferous sulphuric acid has been the means of contaminating it. Ritter and Blyth pointed out the danger, by this means, of conveying arsenic into beer, confectionery, syrup, and other food stuffs. Glucose made with such acid, and used in the manufacture of beer, was the cause, in the year 1900, of a widespread and serious epidemic of arsenical poisoning in Manchester and Liverpool, in which several thousand persons suffered. Arsenic may also contaminate grain during malting by the use of anthracite coal or sulphur bar in the kilns.

Recapitulation of the Leading Facts with regard to Poisoning with Arsenic --------------------------+------------------------------------------ ACUTE POISONING.--SYMPTOMS, ETC. --------------------------+------------------------------------------

## Action on alimentary | Intense irritation of the stomach, upper

canal | part of small intestine, and lower part | of the large. The inflamed condition of | the stomach occurs even if arsenic be | absorbed by the skin. Not present in | all cases. | Circulation | The heart weakened, with a consequent | reduction in force and frequency of | pulse. | The brain and nervous | In some cases the action upon the brain system. | is that of a narcotic, and the | paralysis sometimes seen appears to be | due to a direct action of the drug on | the cord. | The urinary organs | Arrest of the action of the kidneys is | not uncommon. Stranguary. | Fatal dose | Two grains. | Average period of the | From half an hour to an hour after the commencement | poison is taken. of the symptoms. | | Average period before | Ten to twenty-four hours. death. | --------------------------+------------------------------------------ CHRONIC POISONING.--SYMPTOMS, ETC. --------------------------+------------------------------------------ The eyes, nose, and mouth| Irritation and redness of the eyes and | nostrils. Dryness of the mouth and | throat. | The stomach and bowels | Loss of appetite, colicky pains, cramps, | irritability of bowels, mucous | discharges. | Nervous system | Depression and irritability of spirits, | sleeplessness, giddiness, convulsions, | vertigo, paralysis, etc. | Cutaneous surface | Brown pigment deposit in the skin of the | face. “Eczema arsenicale,” etc. | Means of diagnosis in | Examine the urine unostentatiously. suspected cases. | Remove patient from present abode. | Examine wall-paper, etc., for arsenic. | The probable | Signs of irritation, slight or absent, _post-mortem_ | in stomach and bowels. if death is due | to this poison. | | Organs most important to | Liver, stomach, kidney. secure for analysis. | | Circumstances under | Green wall-papers, coloured toys and which it may occur | sweets, green tarlatan dresses, etc. independently of | criminal administration.| --------------------------+------------------------------------------

ANTIMONY

Antimony, the Stibium of the ancients, is obtained from the native sulphide. Metallic antimony is of a bluish-white colour, crystalline and brittle. It melts at about 840° F., and is slowly volatilised at a white heat.

Two compounds of antimony--tartar emetic and chloride of antimony--are alone of any toxicological interest.

[Illustration: Fig. 32.--Photo-micrograph of crystals of tartarated antimony, × 50.

(R. J. M. Buchanan.)]

=Tartar Emetic=

=Antimonium Tartaratum.     Tartarated Antimony=

Tartar emetic occurs as a white powder; sometimes, however, with a yellowish tint. It is soluble in about three parts of boiling water and fifteen of cold, and insoluble in alcohol.

The _vinum antimoniale_ of the Pharmacopœia contains two grains of the salt in an ounce of wine.

Before 1856 poisoning by antimony was of rare occurrence, but since that year several cases of chronic poisoning have occurred, giving to this substance considerable importance.

Symptoms of Antimonial Poisoning

_Acute._--Tartar emetic is an irritant poison, but possesses slight corrosive properties. When taken in large doses, two or three drachms, it gives rise to a metallic taste in the mouth, which is not easily removed. In most cases, violent vomiting follows immediately after the poison is swallowed, the vomiting continuing even after the stomach is emptied of its contents. In a few cases, however, even when a large dose has been taken, vomiting may be absent. Burning pain is felt at the pit of the stomach, accompanied with cramps in the belly and purging. There is considerable difficulty in swallowing, and the patient complains of tightness and constriction in the throat. The mouth and throat in some cases are excoriated, or covered with whitish aphthous-looking spots, which ultimately become brown or black. In some cases the thirst is intense; in others, absent or nearly so. Cramps in the lower extremities, almost amounting in some cases to tetanic spasms, followed by extreme depression, are generally the precursor of a fatal termination. The urine may be suppressed, as is the case in arsenical poisoning; in some cases it has even been increased. On this point, however, the statements of observers differ. Trousseau says that the urine is suppressed; Huseman that it is _never_ suppressed. The skin is in some cases covered by a pustular eruption, not unlike that of smallpox. Dobie has recorded a case of poisoning by tartar emetic in which a comatose condition was present. In antimonial poisoning, even in the most desperate cases, there is always greater hope of recovery than in arsenical poisoning.

[Illustration: Fig. 33.--Photo-micrograph of crystals of tartarated antimony, × 50.

(R. J. M. Buchanan.)]

_Chronic._--The symptoms which mark the chronic form of poisoning differ chiefly in being less intense and less rapid than in the acute. Chronic poisoning by small repeated doses is that form of poisoning which appears most in vogue of late years--as certain diseases, enteritis, etc., can be simulated by the administration of repeated small doses. The unfortunate victim complains of constant nausea and retching, with great depression. Food is objected to, as it only increases the vomiting. The matters vomited are at first merely mucus, but after a time they become mixed with bile. Each time the poison is repeated, the symptoms become aggravated. Emaciation gradually sets in, and the person dies from complete exhaustion, or from the effects of a larger dose than usual. Chronic poisoning has given rise to several errors in diagnosis, and the histories of recorded cases should put medical men on their guard. In all doubtful cases examine the urine.

_Post-mortem Appearances._--The mucous membrane of the throat, gullet, and stomach is inflamed, and in some places softened and corroded. Aphthous-looking spots are not infrequently found on the mucous membrane of the stomach, and these may also be observed on the throat and on the small intestines. The liver has been found in some cases of chronic poisoning, where the fatal termination has been for some time retarded, enlarged, and its structure so soft as to be easily broken down. Fatty degeneration of the internal organs has been found after protracted fatal administration of the drug. It is stated that in Brunswick the fatty livers of the geese are produced by the judicious administration of antimony. The appearances above detailed may be more or less absent or present, according to the time that may have elapsed from the swallowing of the poison to the time at which death has occurred.

At the _post-mortem_ examination on the body of Mr. Bravo, poisoned with tartar emetic in 1876, the mucous surfaces of the stomach and duodenum were found pale and yellowish. Ulcers were present in the cæcum, and the rest of the large intestine blood-stained, but not ulcerated. Stevenson records the _post-mortem_ appearances of the bodies of three women poisoned by tartar emetic (_B. M. J._, 1903, vol. i. p. 873). They are of peculiar interest in reference to the preservative action of antimony upon the bodies of those poisoned by it. In the case of M. E. Marsh, upon whose body the examination was made eight days after death, there was no odour of putrefaction, the bowels were in a condition of acute catarrh and streaky congestion without ulceration.

The body of Bessie Taylor had been buried for twenty-one months; ordinary putrefactive changes were absent, and with the exception of the integuments, it was in a remarkably good state of preservation. The alimentary canal showed acute non-ulcerative gastro-enteritis, the stomach and duodenum were of a cinnabar-red colour, the jejunum also in patches. The ileum was covered with orange-red mucus in its lower portion, and there was an orange-coloured patch twelve inches above the ileo-cæcal valve. The patch on analysis was proved to contain antimonious sulphide. Similar orange patches were present in the colon and upper portion of the rectum. There were no ulcerations, but the mucous membrane of the intestines was of a dull cinnabar-red colour.

The body of Mary J. Spink was exhumed five years after burial, and presented a life-like aspect; there was no putrefactive odour, and no larvæ present. The stomach and intestines were of a cinnabar-red colour; there were no ulcerations; the intestines contained orange-coloured mucus.

Elimination of Antimony from the System

Antimony, taken in a large dose, or in small doses frequently repeated, appears to be rapidly absorbed, and then eliminated from the system by the kidneys. Dating from the time at which the poison was swallowed, it will be found in the organs of the body in the following order:--

1. Stomach and bowels, but slightly in the liver.

2. Absent from the stomach, but present in the liver, spleen, and kidneys--traces in the blood.

3. Present in the fat and bones, with traces in the liver, fæces, and urine.

4. The period required for its complete elimination from the vital organs varies from fifteen to thirty days.

In other words, the presence of antimony in the stomach and intestines points to the recent administration of the poison; and its absence from those organs, and presence in the others above mentioned, to a more remote period of administration. It has been suggested that in some cases the poison may be eliminated by the mucous membrane of the stomach. This assumption has been proved to be correct, for it has been shown that antimony may be found in the stomach after the inhalation of antimoniuretted hydrogen.

_Fatal Dose._--It is impossible to state with certainty the exact amount of antimony--tartar emetic--which may prove fatal, as recoveries have taken place even after an ounce had been taken. Large doses are uncertain in their effects, as the severe vomiting which they produce generally helps to get rid of the poison. In small doses, death may result from the depressing action which it exerts over the heart.

_Fatal Period._--From a few hours to several weeks, and even months.

_Treatment._--Promote vomiting by the administration of warm water, or warm greasy water, or the stomach may be washed out with a syphon tube, unless the chloride of antimony is the poison, and then give tannic acid in drachm doses in warm water, or any vegetable infusion containing tannin--viz., tea, oak bark, or cinchona bark. Demulcent drinks may be administered, and warmth applied. Opium may be given to relieve pain, and stimulants for the depression.

The Detection of Antimony

Prepare the solutions of the liver and other solid organs, and also the contents of the stomach, as described under the detection of arsenic, using tartaric acid instead of hydrochloric acid. Through a portion of one of the solutions, obtained by filtration or dialysis, pass a current of sulphuretted hydrogen, which will produce, if antimony be present, an orange-coloured precipitate of the sulphide of antimony. The precipitated sulphide is dissolved by hot hydrochloric acid with the evolution of sulphuretted hydrogen; and if the resulting solution be poured into water, a white precipitate is formed of oxychloride of antimony, soluble in tartaric acid. Chloride of bismuth is precipitated when poured into water, but the precipitate is turned black by sulphide of ammonium, the antimonial orange-red; the precipitate of bismuth is not soluble in tartaric acid, the antimonial is soluble.

Marsh‘s and Reinsch‘s processes may also be used for the detection of antimony. The former is, however, open to the objection that antimony, when present in any quantity, rapidly precipitates on the zinc in the form of a flocculent black deposit, while the issuing gas is found to contain only traces of the metal.

Reinsch‘s process is, however, very delicate, and its application is in every respect similar to that in use for the detection of arsenic. The acid liquid should, however, be boiled down to a small bulk with the copper, before a conclusion is drawn as to the entire absence of the metal.

Table giving the Characteristic Reactions of Antimonial and Arsenical Deposits on Copper.

--------------------+----------------------------+---------------- | Antimony. | Arsenic. --------------------+----------------------------+---------------- The colour of the | Lustrous, with a violet | Dark steel-grey deposit on copper| hue. | colour, and by Reinsch‘s | | lustrous. process is-- | | | | The coated copper | No effect, or only a | Well-marked heated in the end| trifling white sublimate,| sublimate of of a small tube. | non-crystalline, | octahedral | non-volatile. If the | crystals; is | sublimate be dissolved | readily | in solution of tartaric | volatile. | acid and sulphuretted | | hydrogen passed | | through the solution, | | the orange antimonious | | sulphide is thrown | | down. | --------------------+----------------------------+----------------

It may be noted that mercury likewise yields a deposit on copper with Reinsch‘s process; but the coating is in this case either of a grey colour or white, and silvery on the application of friction. When the coated copper is heated in a glass tube, there is a sublimate of metallic mercury readily aggregating into globules on being rubbed with a glass rod. If the deposit is trifling in quantity, a magnifying-glass should be used to identify the metallic globules. This test at once distinguishes a deposit on copper due to mercury from that produced under similar conditions by arsenic or antimony.

_Quantitative Analysis._--Take a measured quantity of the suspected liquid and precipitate thoroughly with sulphuretted hydrogen. Wash, dry, and weigh precipitate. One hundred parts equal 202.78 parts of crystallised tartar emetic.

Recapitulation of the Leading Facts with regard to Poisoning with Antimony. --------------------------------------------------------------------- ACUTE POISONING.--SYMPTOMS, ETC. -------------------------+-------------------------------------------

## Action on alimentary | Intense irritation of the stomach and

canal. | bowels, constant vomiting, and | frequently purging. Eliminated by the | stomach when absorbed by the skin, or as | antimoniuretted hydrogen by the lungs. | Presence, in some cases absence, of | signs of inflammation in intestinal | canal. | Circulation | The cardiac contractions are lessened in | frequency and force, the heart being | finally arrested in diastole. | Brain and nervous | Sometimes delirium, paralysis of sensation system. | and motion, and diminution of reflex | action. | Urinary organs | Secretion of the kidneys, as a rule, not | arrested; sometimes increased. | Fatal dose | Two grains. | Average period of | A very short time after the poison is commencement of | taken. Almost immediately. symptoms. | | Average period before | Various. Ten to twenty hours. death. | -------------------------+------------------------------------------- CHRONIC POISONING.--SYMPTOMS, ETC. -------------------------+------------------------------------------- Mouth | Aphthous spots on mouth, metallic taste. | The stomach and bowels | Constant irritation, nausea, sinking at | the stomach, symptoms of enteritis or | cholera, purging, tenesmus, etc. | Nervous system | Malaise, low spirits, giddiness, delirium. | Cutaneous surface | Pustular eruption like smallpox, sweating, | decrease in temperature. | Means of diagnosis in | Same as for arsenic. suspected cases. | | The probable post-mortem| Much the same as in arsenic poisoning. if death is due to | this poison. | | Organs most important to| Liver, stomach, and kidneys. secure for analysis. | -------------------------+-------------------------------------------

MERCURY

Metallic mercury possesses no toxicological interest, as it appears to be almost inert, even in very large doses. If applied to the skin in a finely-divided state, as in mercurial ointment, or internally, as blue pill, its toxic effects may be produced. The vapour given off from the metal is highly poisonous, producing salivation, emaciation, and death. A singular accident of poisoning by mercurial vapour occurred on board H.M.S. _Triumph_ in 1810, owing to the bursting of bladders containing large quantities of the metal; in three weeks 200 men were affected with salivation, etc., nearly all the cattle on board died, as well as the mice, a dog, and a canary-bird.

[Illustration: Fig. 34.--Photo-micrograph of crystals of corrosive sublimate, × 50. (R. J. M. Buchanan.)]

Corrosive Sublimate

This is the most important of the preparations of mercury. It occurs either in crystalline masses of prismatic crystals or as a white powder. It is now known among chemists as the perchloride, though it is frequently spoken of as the bichloride, chloride, and oxymuriate of mercury. It has a powerful metallic and styptic taste, and is soluble in about sixteen parts of cold water and three of boiling water. Alcohol and ether readily dissolve it, the _latter having the power of abstracting it from its solution in water_. This property of ether is of importance as a means of separating corrosive sublimate from its solution in other liquids. It is important to remember that corrosive sublimate is soluble in alcohol (R. _v._ Walsh). The liquor hydrargyri perchloridi of the Pharmacopœia contains half a grain of the salt to a fluid ounce of water. Half a grain of the muriate of ammonia is added to increase the solubility of the mercurial salt. Applied externally to the unbroken skin, corrosive sublimate has caused death in several cases, the symptoms being almost identical with those which follow the entrance of the poison into the stomach. Toxic symptoms have followed intra-uterine or vaginal injections of solution of perchloride of mercury, also when it has been used to wash out abscess cavities. Acute poisoning, in some cases fatal, has resulted from the external application of corrosive sublimate to ulcers and tumours.

Symptoms of Poisoning by Corrosive Sublimate

_Acute._--The symptoms come on almost immediately the poison is swallowed. A strong metallic coppery taste in the mouth is experienced, and a choking sensation in the throat. Pain of a burning character is felt, extending from the mouth to the stomach, followed by nausea and vomiting of stringent mucus, more or less tinged with blood, and violent purging, the evacuations being also mixed with blood and mucus. The pulse is feeble, quick, and irregular; the countenance flushed or pale, and the tongue white and shrivelled. This appearance of the tongue is not present in all cases. Broncho pneumonia may occur. The skin is cold and clammy, and the functions of the kidneys are altered and albuminuria present, there being in many cases complete suppression of urine. As is the case with other irritant poisons, the symptoms and effects produced admit of considerable variation. Thus, there may be no pain in the stomach, and no purging. Salivation is present in some cases, but chiefly in those in whom the fatal termination is somewhat prolonged. This sign is not infrequently absent. Poisoning with corrosive sublimate differs from arsenical poisoning in the following

## particulars:--Corrosive sublimate has a distinct metallic taste,

arsenic is almost tasteless; the symptoms in the former supervene immediately the poison is swallowed, in the latter there is a short delay. The discharges in corrosive sublimate are more frequently bloody than in arsenic poisoning.

_Chronic._--The symptoms present in this form of poisoning are modified by the size of the dose, and the interval allowed to elapse between each dose. Nausea, followed by occasional vomiting, and pains in the stomach, are complained of by the patient. There is general constitutional disturbance, with anæmia and cachexia, and consequent mental depression. Salivation, as might be expected, is a more prominent symptom than in acute poisoning; but the salivation may be intermittent--that is, it may cease and then reappear, even after the lapse of months, without an additional dose of mercury having been given in the interval. Salivation may also come on in the course of certain diseases, attacking the salivary glands, and it may also be produced by other causes--pregnancy, etc. The glands of the mouth become swollen and painful, the gums tender, and the teeth loosened fall out of the mouth. Periostitis of the jaw may occur. The breath has a peculiar, offensive smell, the bowels are irritable, and diarrhœa is not infrequently present. It must be borne in mind that in certain diseases--granular disease of the kidney--the smallest dose of any mercurial preparation may produce profuse ptyalism. And the toxicologist must be careful not to mistake the affection known as _cancrum oris_, or “the canker,” most common in delicate, ill-fed children and adults, for the effects of mercury. The nervous system is more or less affected, neuralgic pains and mercurial tremors being present in many cases. The tremors commence in the tongue and face and spread to the arms and legs--they are similar to those of paralysis agitans; at first they are invoked by exertion, finally they become continuous; they cease during sleep. Paralysis may also occur, especially in those exposed to the vapour of mercury. Habit appears to exert some influence on the action of corrosive sublimate, if we may accept the story of the old man of Constantinople, who for thirty years took large doses till his daily allowance was a drachm, and then died at the respectable age of one hundred years.

_Post-mortem Appearances._--The morbid appearances are chiefly confined, as is the case with arsenic, to the stomach and bowels; but the corrosive action of the mercurial sublimate is more marked. Inflammation more or less intense is always present in the stomach, the mucous membrane of which may be found of a slate-grey colour, corroded, and so soft as to scarcely admit of the removal of the organ without tearing it. The cæcum and rectum are also sometimes found inflamed, and the mucous membrane softened. Perforation of the stomach is very rare, only one case having been recorded in which this was present. The mouth, throat, and gullet may also present signs of the action of the poison similar to those just described as seen in the stomach. Patches of pneumonia are present in the lungs of some cases, and the kidneys show coagulative and desquamative nephritis.

_Fatal Dose._--The smallest dose was _two grains_ in the case of a child, but the exact amount to cause death in an adult has not been accurately determined. Recovery has taken place after one hundred grains has been taken.

_Fatal Period._--From half an hour to five days. No exact time can be stated. In one case death took place on the twelfth day after swallowing seventy grains of the perchloride.

_Treatment._--Vomiting, if present, must be encouraged; if absent, it must be produced by emetics--zinc sulphate or cupric sulphate, followed by copious draughts of warm water. The hypodermic injection of ¹/₂₀ to ⅒ grain of apomorphine may also be used to produce vomiting. Albumen, the white of egg, or vegetable gluten produced from flour by washing it in a muslin bag, should be given. The albuminate of mercury so formed should be quickly removed by an emetic or lavage by means of a soft tube and funnel in mild cases, as it is soluble in excess of albumen, and may be digested or absorbed. The rapid removal of the poison from the stomach, however, is the end to which all our exertions must tend. The forcible use of the stomach pump should not be employed if it can possibly be avoided, as it may greatly injure the softened mucous membrane of the gullet and stomach. Opium may be given to relieve pain, and opium enemata to relieve purging and tenesmus.

=Calomel=

Calomel, or the subchloride of mercury, is not used as a poison. In large doses it may act as an irritant poison, and death has not infrequently occurred even from comparatively small doses. Profuse salivation and gangrene of the mouth have resulted from its use, and cases are recorded of death resulting from these. In many cases idiosyncrasy appears to modify, more or less, the action of this preparation of mercury. The poisonous effect of calomel has been attributed to--(1) Adulteration with corrosive sublimate. (2) Conversion of the calomel into corrosive sublimate by the action of the hydrochloric acid of the gastric juice.

_N.B._--The free acid of the gastric juice is probably in too small a quantity to materially alter the composition of the calomel.

=Ammonio-Chloride of Mercury=

White precipitate may, if taken in large doses, produce alarming effects, but it cannot be regarded as an active poison. Pavy‘s experiments on rabbits indicate that it is a more powerful poison than was formerly thought to be the case. Its action is that of an irritant, accompanied with, in some cases, severe salivation.

=Red Precipitate=

Red oxide of mercury possesses poisonous properties, but it is seldom employed as a poison. The symptoms most frequently present are vomiting, coldness of the surface of the body, stupor, pain in the abdomen, and cramps of the muscles of the lower extremities. The vomited matters are generally mixed with some of the red oxide.

=Cinnabar. Vermilion=

A compound of sulphur and mercury in the form of a dark red crystalline mass is known as cinnabar; and to the same substance reduced to a fine powder the name vermilion has been given. It is used as a red pigment. It can scarcely be considered as a poison, Orfila asserting that it is not poisonous. The vapour of this substance appears, however, to be capable of producing severe symptoms, and in one case, profuse salivation resulted from the application of the vapour to the body.

=Cyanide of Mercury=

This substance, though an active poison little inferior to corrosive sublimate, is seldom used as such, probably from its being better known to chemists than to the general public. It differs from corrosive sublimate in having no local corrosive action. It has been supposed, but proof is wanting, that its injurious effects are due to its decomposition by the acids of the stomach and the formation of prussic acid. Death has occurred in nine days from a dose of ten grains. It acts as an irritant. The sulphocyanide of mercury is used in the manufacture of the toy known as Pharaoh‘s serpents.

=Turbith Mineral=

A powerful irritant poison, but seldom used. A drachm has caused death in a boy sixteen years of age. Coldness of the surface, burning pain in the stomach and bowels, with other symptoms of irritant poisoning, were present. After death, the mucous membranes of the throat, stomach, and bowels were found considerably inflamed.

=Nitrates of Mercury=

These substances--the nitrate and sub-nitrate--are used in the arts for various purposes. They act as powerful irritant poisons, with symptoms and _post-mortem_ appearances not unlike those before described when speaking of corrosive sublimate and other irritants.

_Chemical Analysis_:

Table showing the Reaction of Mercuric and Mercurous Salts with Reagents

-------------------------------+------------------------------------ Mercuric Salts -------------------------------+------------------------------------ 1. With solution of iodide of | 1. Bright scarlet precipitate, potassium. | soluble in excess. | 2. With potash solution. | 2. Bright yellow precipitate. | 3. With hydrosulphuret of | 3. First a yellowish and then a ammonia. | black precipitate is produced. | 4. Heated in a reduction tube.| 4. It melts, boils, is volatilised, | and forms a white crystalline | sublimate. | 5. With ether. | 5. It is freely soluble in ether; | and the ethereal solution, when | allowed to evaporate | spontaneously, deposits the salt | in white prismatic crystals. | 6. Heated with carbonate of | 6. Globules of metallic mercury soda in a reduction tube. | are produced. -------------------------------+------------------------------------ Mercurous Salts -------------------------------+------------------------------------ 1. Hydrochloric acid. | 1. A white precipitate of calomel, | blackened on addition of ammonia. | 2. Potassium iodide solution. | 2. Green precipitate. | 3. Caustic potash or soda | 3. Black precipitate of mercurous solution. | oxide. -------------------------------+------------------------------------

=Detection of Mercury in the Tissues and in the Contents of the Stomach.=

Mercury is particularly liable to be absorbed by the tissues; it also readily combines with various organic substances, gelatine, albumin, &c.

[Illustration: Fig. 35.--Photo-micrograph of globules of mercury obtained by Reinsch‘s process, × 50. (R. J. M. Buchanan.)]

_A._--If the contents of the stomach are under examination, they should be diluted with distilled water, filtered, and the residue pressed and reserved for further examination.

The liquid thus obtained may be concentrated, and, while still warm, slightly acidified with hydrochloric acid. A slip of zinc foil, with a piece of gold foil twisted round it, is then introduced. If mercury be present, the gold will, sooner or later, lose its yellow colour, and its surface become white and silvery, while the zinc is wholly or

## partially dissolved. The gold being removed, separated from the zinc,

washed first with water and then with ether, is divided into two equal parts. One half may be heated in a reduction tube, when it will yield a sublimate of metallic mercury, identified by the spherical form of the globules under a magnifying-glass, and their metallic reflection and complete opacity. The other half of the gold may be treated with nitric acid and heated, which will dissolve off the mercury. The resulting solution, after expelling the excess of acid by evaporation, will give a scarlet precipitate with iodide of potassium soluble in excess; and, with protochloride of tin, a black precipitate of metallic mercury.

_B._--For the detection of mercury in the insoluble form, the residue from _A_ is dried; or, if the tissues are under examination, they should be finely divided, and freed from superfluous moisture. In either case, the substance is boiled in moderately strong nitric or hydrochloric acid (about one part of acid to four of water). After digestion for some time, the liquid is filtered, concentrated, and tested as in _A_. When there is reason to infer the presence of corrosive sublimate in considerable quantity in an organic liquid, advantage may be taken of the solubility of the salt in ether, and the power possessed by this liquid of abstracting it from its aqueous solutions. The liquid is agitated with an equal volume of ether, the ethereal solution poured off and allowed to spontaneously evaporate, when the corrosive sublimate will be left in white silky prisms, yielding all the characteristic reactions of the salt. In obscure cases of salivation, the saliva should be examined as follows: Take about two drachms of the saliva, acidulate with pure hydrochloric acid, and immerse in the mixture a very small piece of copper gauze attached to a platinum wire, and set aside in a warm place for some hours. If mercury be present, the copper will be covered with a white coating; this should be washed and heated in a reduction tube, when globules of mercury will be formed, and examined with a lens.

_C._--Mercury in solution may be detected by Reinsch‘s process. On boiling with pure copper foil after acidifying the solution with hydrochloric acid, the mercury is deposited on the copper in the metallic state, as a whitish silvery film, which can be polished to a silvery mirror surface. On washing the film in water, ether, and absolute alcohol and allowing it to dry, then subliming it in a reduction tube by the aid of heat, the mercury deposits on the cool part of the tube in the form of minute globules, which may be easily recognised through the microscope. If a small crystal of iodine be now placed in the tube and gently warmed so as to volatilise it, but not the mercury, and the tube be left to stand for a short time, the iodine combines with the mercury to form the scarlet iodide, the colour of which renders it easy of recognition.

According to Bonnewyn, the presence of an extremely small quantity of corrosive sublimate (¹/₅₀₀₀₀) in calomel may be detected by immersing a clean knife blade, moistened with alcohol or ether, in the suspected calomel. A black spot is formed on the steel very difficult of removal. No spot is formed when the calomel is pure.

LEAD

Metallic lead is not poisonous; but it appears probable that when it is acted upon by the acids of the intestinal secretions, it may become so changed as to produce unpleasant symptoms. Any salt of lead is poisonous when in a condition to be absorbed into the system.

Sugar of lead and white lead are alone important, and will therefore be briefly considered.

=Sugar of Lead=

Acetate of Lead.   Subacetate.   Goulard‘s Extract

_General Character._--The acetate of lead, better known as sugar of lead, is not unlike loaf-sugar in its general appearance. It is usually met with in the form of solid crystalline masses of a white or brownish-white colour. To the taste it is sweet, a metallic astringent taste being left in the mouth. Acetate of lead is soluble in water and in alcohol. The subacetate is a more active poison than the neutral acetate. Sugar of lead is popularly considered as an active poison, but this does not appear to be the case. Sir R. Christison gave eighteen grains daily in divided doses for eight or ten days with no other unpleasant symptoms than slight colicky pains in the abdomen. Lead is probably eliminated from the system by the urine, and also by the milk; but there is reason to believe that when once deposited in the body, some considerable time is required for its complete elimination. Dr. Wilson is of opinion that in chronic lead poisoning the lead is more largely deposited in the spleen than in any other organ of the body. This organ should therefore always be carefully examined in suspected cases of poisoning by this metal.

_Goulard‘s Extract_ is a solution of the subacetate of lead. It may be of a reddish colour, from the employment of common vinegar in the place of pure acetic acid in the manufacture.

_Goulard‘s Lotion_ is the extract diluted with water.

=White Lead=

White lead, carbonate of lead, ceruse, or kremser white, is used as a pigment. It is generally in the form of white, heavy chalky masses, insoluble in water, and, when taken in large doses, poisonous. It is this substance which, in the majority of cases, causes chronic lead poisoning, or _painter‘s colic_.

The _chloride_ and _nitrate_, the oxides, _litharge_ and _red lead_, are all poisonous; but the _sulphate_, due probably to its insolubility, appears to be inert.

Lead poisoning may result from--

1. Constant contact with lead and its salts in manufactories.

2. Its use in the arts and as a pigment. The injurious effects of this substance are strikingly seen among painters, the makers of glazed cards, and the workmen engaged in preparing Brussels lace--this material being whitened by beating white lead into it. All thus employed are liable to suffer more or less from chronic poisoning.

3. Its application to the surface of the body in the form of ointment, plasters, cosmetics, and hair-dyes.

4. Drinking water impregnated with lead, from being stored in leaden cisterns or conveyed in leaden pipes.

“The action of water upon lead is much modified by the presence of saline substances. It is increased by chlorides and nitrates, and diminished by carbonates, sulphates, and phosphates, and especially by carbonate of lime, which, held in solution by excess of carbonic acid, is a frequent ingredient of spring and river water. But water highly charged with carbonic acid may become dangerously impregnated with lead, in the absence of any protecting salt, in consequence of its solvent power over carbonate of lead. In general, water which is not discoloured by sulphuretted hydrogen may be considered as free from lead; but there are few waters which have passed through leaden pipes, or have been retained in leaden cisterns, in which a minute analysis will not detect a trace of the metal; and were it not for the great convenience of lead, iron pipes and slate cisterns would, from a sanitary point of view, be in all cases preferable.

“Another case of contamination by lead may arise from electric action, as where iron, copper, or tin is in contact with or soldered into lead; and in these cases, owing to the action of alkaline bases as well as of acids upon the lead, danger may occur when it is thrown into an electro-negative as well as into an electro-positive state.

“Cisterns are sometimes corroded and their bottoms are perforated by pieces of mortar having dropped into them, the lime of which has caused the oxidation of the metal and a solution of the oxide.”

5. Lead may also find its way into the system by means of the food. Farinaceous foods, chocolate, and tea may become contaminated if lead wrappers be used; and confectionery from the use of lead chromate as a colouring agent. The use of leaden vessels in the manufacture of cider is attended with danger, and also the keeping of pickles in glazed earthenware jars. The celebrated “Devonshire Colic” was the result of cider-making in leaden vats. Beer may be contaminated with lead if allowed to stand in leaden pipes overnight. Rum has been known to have been dangerously impregnated with lead, leaden worms having been used attached to the stills. Many tobacconists are in the habit of using lead foil to wrap up their tobacco and snuff; this practice has resulted in several cases of chronic lead poisoning. Soda and Seltzer waters may contain lead when kept in syphons with leaden caps or valves.

6. Acute and subacute cases of poisoning occur from the taking of lead in the form of diachylon pills to procure abortion.

=Symptoms of Poisoning by Lead=

_Acute._--A metallic taste in the mouth, accompanied with dryness in the throat and intense thirst, is experienced by the patient soon after the poison is swallowed. In some cases, however, _two or more hours_ may elapse before the effects of the poison begin to show themselves. Vomiting may or may not be present. Twisting colicky pains are felt in the abdomen, relieved in some cases by pressure. The paroxysms of pain may be separated by intervals of ease. The bowels are, as a rule, obstinately confined, and the fæces are of a dark colour, from the formation of the sulphuret of lead. The skin is cold, the pulse quick and weak, and there is considerable prostration of strength. In some cases the patient suffers from cramps of the calves of the legs, and sometimes, in protracted cases, paralysis of one or more of the extremities may supervene. The effect on the nervous system, headache, temporary blindness, is marked by giddiness, and stupor, in some cases delirium even resembling acute mania, terminating in coma, or convulsions and death. Albuminuria may occur.

_Chronic._--This form of poisoning generally occurs among painters, manufacturers of white lead, pewterers, and others. The early symptoms are those of ordinary colic, only more severe. The patient generally complains, in the first instance, of feeling unwell, and of general debility. He then suffers from pain of a twisting, grinding nature, felt in the region of the navel, the abdomen being retracted and hard. The bowels are obstinately confined. The appetite becomes capricious, and may be entirely lost. The mouth is parched, the breath fœtid, the countenance sallow, the skin dry, and general emaciation sets in. A nasty sweetish metallic taste in the mouth is present in most cases. Not infrequently the subjects of lead poisoning experience a peculiar form of paralysis of the upper extremities, well known as “dropped hand.” It appears that this condition is the result of paralysis of the extensor muscles of the wrist, the long supinator escaping. In other cases the muscles of the shoulder girdle or pelvic girdle and legs may be affected. Acute general paralysis has occurred in workers with lead, and may prove fatal. Optic neuritis and optic atrophy occur in some cases. Persistent headache may be present in others. The muscles undergo a form of fatty degeneration. The lead appears to act primarily on the muscles, then on the nerves, and lastly on the nerve centres. The absorption of lead causes marked anæmia with degeneration of the red corpuscles, which show marked punctate basophilia. One other symptom of importance has yet to be noticed. The gums, at their margins where they join the teeth, present a _well-marked blue line, absent where a tooth has been removed_. This is not present in all cases, but it should be looked for. Chronic lead absorption produces cardiovascular changes with arterio-sclerosis, valvular degeneration, cardiac hypertrophy, and chronic renal changes with albuminuria. Closely associated with these conditions are saturnine arthritis and gout. The effects upon the vessels may predispose to cerebral hæmorrhage or lead encephalopathy. Cicconardi suggests as a method of diagnosis in lead poisoning, where the cause of the colic is uncertain, to paint the skin with a 6 per cent. solution of sodium sulphite. If lead be the cause the painted part will become darkened in colour.

_N.B._--The symptoms produced by white lead--carbonate of lead--are those of _colica pictonum_, or _painter‘s colic_, described under the head of Chronic Lead Poisoning.

_Post-mortem Appearances._--In acute poisoning the mucous membrane of the stomach and intestines is inflamed, and is in some cases covered by layers of white or whitish-yellow mucus, more or less impregnated with the salt of lead swallowed. Corrosion of the mucous membrane may occur if the dose be large, and this condition is more frequently present when the neutral salt is taken.

In chronic poisoning there are no constant _post-mortem_ appearances. The muscles of the paralysed extremity are usually found flaccid, of a cream colour, and the subject of fatty degeneration.

_Fatal Dose._--Sugar of lead is not an active poison, recovery having taken place after one ounce had been swallowed.

_Fatal Period._--Uncertain.

_Treatment._--The stomach should be emptied by means of the pump or syphon tube, followed by the free administration of the sulphates of soda and magnesia. The carbonates should not be given, the carbonate of lead being poisonous. Vomiting should be promoted, and a powerful cathartic administered. Albumen and milk should also be given, as these precipitate the oxide. In the chronic form of poisoning, the iodide of potash and aperients, notably the sulphate of magnesia, should be administered. Dixon Mann does not consider that iodide of potash is of any value as an eliminator of lead, as the latter forms a stable compound with the tissues. Sulphur baths are also useful in removing the lead from the system. Lately the galvanic bath has been tried with great success. By way of _prophylaxis_, it has been recommended that all those engaged in lead manufactories, or who are obliged to handle this metal frequently, should partake largely of lemonade made with sulphuric acid, should not take their meals in the factories, or without well washing the hands.

_Chemical Analysis_.--When the solid acetate is heated on platinum foil, it melts, then solidifies, becomes dark in colour, and gives off fumes of acetic acid.

The following are the liquid tests for lead in solution:

1. Dilute sulphuric acid gives a white precipitate of the sulphate, which is insoluble in nitric, but soluble in hydrochloric acid, in excess of caustic potash solution, and in ammonium acetate solution.

2. Solution of potassium iodide gives a yellow precipitate, soluble in boiling water and caustic potash solution.

3. Sulphuretted hydrogen, or ammonium sulphide, gives a black precipitate.

4. Potassium bichromate a yellow precipitate.

=Detection of Lead in Organic Mixtures=

The contents of the stomach or vomited matters must be diluted with water and filtered. The residue left on the filter, washed with distilled water, should be set aside for further examination; the filtrate and washings acidified with nitric acid. A current of sulphuretted hydrogen passed through the solution will then throw down the whole of the lead, should any of that metal be present, in the form of a brownish-black sulphide, which may be collected on a small filter and dried. The sulphide, boiled with dilute nitric acid, is

## partly converted into insoluble sulphate, and in part dissolved as

nitrate. The carefully neutralised solution may be either tested at once or carefully concentrated. In either case, the production of a bright yellow precipitate, with a solution of bichromate of potash, and a similar one with a solution of iodide of potassium, may be taken as conclusive of the presence of lead. The portion of lead deposited as sulphate will be found to be soluble in a solution of pure potash, the resulting liquid giving a brown-black precipitate on the addition of sulphide of ammonium.

The insoluble residue left on the filter should be incinerated in a porcelain crucible, either with or without nitric acid, care being taken not to raise the temperature more than is necessary to produce the desired effect: the carbonised mass boiled with dilute nitric acid evaporated to dryness, extracted with distilled water, and then filtered, the filtrate tested as before mentioned. It is often useful, as a preliminary test for the presence of lead in a soluble form, to dip a piece of bibulous paper into the clear liquid obtained by submitting the contents of the stomach or vomited matters to filtration, and then exposing the paper to the action of a current of sulphuretted hydrogen. If lead be present, blackening of the paper will take place.

To detect the lead in the urine and fæces, Dixon Mann advised the urine to be evaporated to the consistency of gruel, and the fæces to be mixed with distilled water to a similar consistence; the organic matters are then to be destroyed with hydrochloric acid and chlorate of potash with the aid of heat, and the solution filtered. The filtrate is then placed in a cell with a parchment bottom, and this into another cell containing distilled water acidulated with sulphuric acid. Two pieces of platinum foil are now placed in the inner and outer cells, separated by the parchment; that in the inner cell is connected with the cathode, that in the outer with the anode of four Grove cells, and the current closed for several hours. The lead, if present, is deposited on the platinum connected with the cathode.

The magnesium method (Marsden & Abram) is useful. A strip of pure magnesium is placed in the urine, to which has previously been added ammonium oxalate, about 1 gramme to 150 c.c. Lead, if present, is deposited on the magnesium in about half an hour, but it may take some hours. The strip is washed in distilled water and dried--warmed with a crystal of iodine the yellow iodide will form; or the deposit may be dissolved in HNO₃ and tested in the usual way.

Goadby recommends inoculating the urine with bacillus coli, which during its growth produces H₂S; this precipitates any lead as sulphide. After filtering, the filtrate is dissolved in a small quantity of 10 per cent. nitric acid and tested by the usual methods.

Recapitulation of the Leading Facts with regard to Poisoning by Lead --------------------+------------------------------------------- ACUTE POISONING.--SYMPTOMS, ETC. --------------------+-------------------------------------------

## Action on alimentary| Sweet metallic taste in mouth. Vomiting,

canal. | constipation, burning twisting pain in | the belly. Inflammation of canal. | | | Circulation. | The pulse lowered, and tendency to death | from syncope. Anæmia. | Nervous system. | Neuralgic pain, convulsions, cramps, | paralysis, &c. --------------------+------------------------------------------- CHRONIC POISONING.--SYMPTOMS, ETC. --------------------+------------------------------------------- Mouth and alimentary| Sweet metallic taste; blue line at margins canal. | of gums; breath fœtid. Colic, | constipation. | Nervous and muscular| Headache, delirium, stupor, amaurosis, symptoms. | paralysis of the extensor muscles of the | wrist, anæsthesia of the affected part. | Fatty degeneration of the muscles. | Circumstances under | Certain trades, as painters, plumbers, which it may occur. | type-founders, &c. Action of drinking | water on lead. Hair-dyes, food in leaden | utensils, &c. | Prophylaxis | Grinding lead colours in oil or water. | Cleanliness in factories. Slate cisterns | for water. Dilute sulphuric acid | lemonade. | Medical treatment | Epsom salts, iodide of potassium, galvanic | baths, &c. --------------------+-------------------------------------------

COPPER

Metallic copper, like metallic lead, is not poisonous, but its oxides are; it should, therefore, not be swallowed, as it is rapidly acted on by the intestinal secretions and poisonous compounds formed. An alloy of copper is used for ornamenting ginger-bread, &c. All the salts of copper are poisonous. The most important are, however, the _sulphate_, _blue-stone_, or _blue vitriol_, and the _subacetate_ or _verdigris_.

Copper is eliminated to a slight extent by the urine. It has been found in the stomach, liver, and intestines eight months after its administration had been discontinued. It has also been detected more readily in the bronchial secretion than in the urine.

=Symptoms of Poisoning by Copper=

_Acute._--The primary action of the sulphate of copper in from five- to fifteen-grain doses is that of a quick emetic; in larger doses, a powerful irritant; but when absorbed, it appears to act chiefly on the brain and nervous system. Its irritant action is marked by nausea, vomiting, griping pain in the belly, which is greatly distended, and increased flow of saliva. The vomited matters are of a bluish or greenish colour, and the discharges from the bowels greenish and containing blood. The vomited matters become blue on the addition of ammonia. The above-mentioned symptoms usually follow immediately after the poison is swallowed, and rapidly increase in severity. After a time, the remote effects supervene, marked by headache, giddiness, laboured breathing, quick irregular pulse, coma or convulsions, paralysis, and death.

In poisoning by this substance, the convulsions are most violent, and wild incoherent delirium not infrequent.

The subacetate of copper or verdigris produces symptoms not unlike those just described. Jaundice and suppression of urine may result when either this or the sulphate is taken.

_Chronic._--Constant and troublesome irritation of the stomach and bowels; vomiting and purging, attended with considerable straining at stool; loss of appetite, loss of power, and general emaciation set in. The patient is subject to frequent trembling of the limbs, which may end in paralysis. The mouth is unpleasant, and a coppery, metallic taste is experienced. Cramps or colicky pains in the belly are not infrequently present. Jaundice is sometimes present. The vomited matters are greenish; but the practitioner must not be led away, and thus mistake the colour of the vomited matters which occur in some morbid states of the bile, for the result of poisoning by a salt of copper. A form of chronic poisoning affecting workers in this metal has been described by some French pathologists as “copper-colic.” A cachectic condition of the system, accompanied with one or more of the symptoms already detailed, marks this form of poisoning. _A purple_ line along the margins of the gums is present in some cases.

Copper poisoning may result from--

1. Its introduction into the system by using, for culinary purposes, copper vessels not properly tinned. An interesting account of poisoning from this source may be found in the second volume of the _Medical Observations and Inquiries by a Society of Physicians in London_, published 1764. The cases there recorded occurred on board ship, with most alarming symptoms.

2. By constant application of the metal to the surface of the body, necessitated by certain processes in its manufacture and in its application for industrial purposes. M. Michel Levy, however, says in his work, _Traité d‘Hygiène, Publique et Privée_, that workmen in copper may pass green-coloured urine and yet be as robust and as long-lived as other workmen.

3. The use of certain preparations of this metal as pigment.

4. The use of German silver--an alloy of copper, zinc, and nickel--may be rendered dangerous by the action of acid food upon the compound.

5. The use of a salt of copper to give a green fresh colour to certain tinned vegetables and fruits, peas, &c., now introduced into this country from France.

_Post-mortem Appearances._--The mucous membrane of the stomach is inflamed, the inflammation extending sometimes into the gullet. The intestines may be found perforated. The lining membrane of the whole alimentary canal presents a deep green colour, distinguished from that the result of a morbid condition of the bile by being turned blue on the addition of ammonia.

_Fatal Dose._--Nothing certain is known as to the exact quantity that may prove fatal, as the evidence of the poisonous action of copper is somewhat contradictory. It appears to be more dangerous in small doses than in large ones. Half an ounce of verdigris or subacetate has proved fatal to an adult.

_Fatal Period._--The shortest time on record is four hours.

_Treatment._--Induce vomiting, and assist the emetic action of the copper salts by the free use of warm water, milk, or any demulcent drink. The stomach tube may be used if vomiting does not occur. As an antidote, large quantities of albumen and iron filings have been given, of which the former appears to be most efficacious.

_Chemical Analysis._--The following are the liquid tests for copper in solution:--

1. Ammonia gives a bluish-white precipitate soluble in excess, forming a blue solution.

2. Sulphuretted hydrogen and ammonium sulphide give a chocolate-coloured precipitate.

3. Ferrocyanide of potassium gives a port-wine colour, or reddish-brown precipitate.

4. If a bright steel needle be introduced into an acid solution of copper, the metal is deposited on the needle.

5. If a piece of zinc bound with platinum wire be placed in a solution of a copper salt, the metal is deposited on the platinum; it is turned violet on exposure to the vapour from sulphuric acid mixed with potassium bromide.

=Detection of Copper in Organic Liquids=

_A._--The finely-divided tissue, or the contents of the stomach, diluted with water, are thrown on a filter, and the insoluble portion set aside for further treatment. (See _B._)

The filtrate and washings may now be concentrated, acidified with sulphuric acid, and a polished needle inserted in the liquid; and should no immediate deposition of metallic copper occur, it may be allowed to remain for several hours. The colour of the metallic deposit is highly characteristic of copper. As a corroborative proof, the concentrated liquid may be placed in a platinum capsule with some fragments of zinc, when the copper will be deposited on the platinum capsule at the parts in contact with the zinc; the liquid poured off, and the excess of zinc adhering to the platinum removed by dilute hydrochloric acid. The copper may now be dissolved off the platinum by nitric acid, the excess of acid driven off by heat, and the solution subjected to the wet tests given above.

_B._--The insoluble portion from _A_ is incinerated in a porcelain crucible. The ash thus obtained is digested in hydrochloric acid with the aid of heat, and evaporated nearly to dryness. The residue, dissolved in distilled water, may be tested as under ‘_A_.’

ZINC

The sulphate and the chloride of zinc are alone important. Poisoning by the chloride of zinc has been described (p. 265).

=Sulphate of Zinc=

White vitriol or white copperas.

_Symptoms._--The sulphate of zinc acts as a pure irritant. Violent vomiting, accompanied with pain in the abdomen, and purging, are the symptoms which first make their appearance. These may be followed by symptoms which betoken collapse, viz. coldness of the limbs, paleness of the face, irregular pulse, and fainting.

_Post-mortem Appearances._--Presence of inflammatory action.

_Fatal Dose._--Uncertain.

_Fatal Period._--Death has occurred in four hours.

_Chemical Analysis._--Distinguished from oxalic acid by remaining fixed when heated on platinum foil.

In Solution:

1. _Ammonia_ gives a white precipitate soluble in excess.

2. _Ferrocyanide of Potassium_, a white precipitate.

3. _Sulphuretted Hydrogen or Ammonium Sulphide_, a milky-white precipitate in a neutral pure solution.

4. _Nitrate of Baryta_, a white precipitate showing the presence of sulphuric acid.

5. _Caustic potash_ or _soda_, a white precipitate soluble in excess.

In Organic Mixtures pass sulphuretted hydrogen, collect the sulphuret, and decompose it with boiling hydrochloric acid, then test for zinc.

_Treatment._--Tea, coffee, milk, warm water, albumen, and in some cases enemata of gruel and other emollients.

IRON

The preparations of iron which are of importance are the sulphate and the muriate.

Sulphate of Iron

_Copperas_ or _Green Vitriol_--has been administered as a poison, but more frequently to procure abortion. An ounce has been taken with no other serious effect than the production of violent pain, purging, and vomiting. Constant application of this substance to the body has produced vomiting, pains in the belly and limbs. These symptoms disappear on treatment.

_Chemical Analysis._--(1) Hydrosulphuret of ammonia gives a black precipitate. (2) Ferrocyanide of potassium added to it, in solution, gives rise to a greenish-blue precipitate, becoming dark blue on exposure. (3) Chloride of barium will point to the nature of the acid present.

=Muriate of Iron=

Better known as the _Tincture of Sesquichloride of Iron_, or the _Tinctura Ferri Perchloridi_.--The tincture acts as a corrosive and irritant poison, death having followed in five weeks after an ounce and a half had been swallowed. It is sometimes used as an abortifacient. Recovery has, however, taken place after three ounces had been swallowed. The symptoms present in most cases observed were those of a corrosive and irritant.

_Chemical Analysis._--(1) The addition of nitrate of silver, causing a white precipitate insoluble in nitric acid, points to the presence of chlorine. (2) The peroxide of iron, indicated by the formation of Prussian blue on adding a solution of the ferrocyanide of potassium.

BISMUTH

The preparations of this metal act as irritant poisons, death having occurred from a dose of two drachms of the sub-nitrate. Dr. Trail (_Outlines of Medical Jurisprudence_, p. 116) mentions the ease of a patient of his who took _six drachms_ in three days in divided doses. The symptoms were vomiting, extreme pain in the abdomen and throat, a weak, feeble pulse, and much anxiety about the præcordia. Recovery took place. A case of severe vomiting during pregnancy, ending fatally, was mistaken for arsenic poisoning. The error arose from mistaking a greyish powder on the walls of the stomach for arsenic. It turned out on further inquiry that it was bismuth, given medicinally to prevent the vomiting. Bismuth carbonate mixed with gruel or bread and milk is given in large quantities for the purposes of radiography of the alimentary canal without any untoward effects.

POTASSIUM

=Nitrate of Potash=

This substance is well known as nitre, saltpetre, and sal prunella. In large doses it acts as an irritant, and cases are recorded in which it has been used to poison children. In one case, the presence of crystals of the salt in some of the dried vomited matter on the child‘s shoe, led to an explanation of the cause of death.

_Symptoms._--Those of a pure irritant, to which death must be referred, and not to any constitutional action of the drug. The nervous symptoms, which are sometimes very marked, are, as is well known, common to the

## action of many pure irritants. In some cases there is suppression of

urine.

_Post-mortem Appearances._--Those produced by irritants generally.

_Chemical Analysis._--Separate the poison by dialysis, evaporate, and test the crystals as directed under nitric acid.

_Fatal Dose._--About an ounce.

_Fatal Period._--Two hours.

_Treatment._--The same as for other irritants; demulcent drinks. Promote vomiting.

=Sulphate of Potash=

_Sal Polychrist_, _Sal de Duobus_, or sulphate of potash, acts as an irritant poison, being largely used in France as an abortive. The symptoms and the _post-mortem_ appearances are much the same as those produced by the nitrate. A like treatment may also be adopted. In the detection of this substance, the nitrate of baryta will point to the acid present, and bichloride of platinum to the presence of potash.

=Chlorate of Potash=

This salt acts as a poison when taken in large doses, producing symptoms which might be mistaken for poisoning with arseniuretted hydrogen, or for such diseases as hæmoglobinuric fever.

_Symptoms._--These comprise pain in the stomach and bowels with vomiting, collapse and stupor, cyanosis, jaundice; diminution of the urine, which contains hæmoglobin, casts, and albumen. It is a question whether the jaundice is hæmatogenous or hepatogenous. Chlorate of potash destroys the red corpuscles, the hæmoglobin is dissolved out and is set free in the liquor sanguinis.

_Fatal Dose._--45-50 grains proved fatal to a child three years old. For an adult 390 grains to an ounce and a half.

_Fatal Period._--From five hours to several days.

_Treatment._--The stomach should be washed out through the syphon tube. Venæsection may be useful, with subsequent transfusion of fresh blood. The nephritis and other symptoms must be treated generally.

_Post-mortem Appearances._--The mucous membrane of the stomach may be inflamed and submucous hæmorrhages may be found. The blood is chocolate in colour and gives the spectrum of methæmoglobin. The spleen is enlarged and chocolate-coloured, and the kidneys acutely inflamed.

_Chemical Analysis._--Chlorate of potash may be separated from organic material by dialysis.

1. If to a solution of the salt a few drops of indigo sulphate be added, and then a few drops of strong sulphuric acid, the indigo-blue is bleached.

2. If a small crystal of the chlorate be heated in a test tube with a drop of strong sulphuric acid, it explodes with detonation.

BARIUM

The chloride, nitrate, and carbonate of barium are all irritant poisons. But besides their irritant action, the salts of barium also appear to act on the nervous system and the heart, arresting its action in systole. The symptoms, post-mortem appearances, and treatment are the same as for the other irritant poisons. Sulphate of magnesia, or other soluble sulphate, should be given to form an insoluble sulphate of baryta. Sulphate of barium is also used like bismuth carbonate for radiography.

_Chemical Analysis._--Sulphuric acid or alkaline sulphate gives a white precipitate with solution of chloride of baryta, insoluble in nitric acid. The salts impart to flame a greenish-yellow colour. The chlorine is detected by nitrate of silver. Dissolve the carbonate in hydrochloric acid, and test as above.

CHROMIUM

Two compounds of this metal are largely used in the arts for dyeing purposes--the neutral chromate and the acid bichromate of potash. The bichromate of potash is a powerful poison, and death may occur from its direct action on the nervous system, without the development of any of the signs of irritation; in other cases, however, well-marked irritant symptoms have been present. Applied externally, it produces deep fistulous sores, especially on the mucous membrane of the septum of the nose, in the workmen who are engaged in its manufacture. These sores are prevented to some extent by taking snuff. Dyers not infrequently suffer severely on their arms when using it in the course of their trade. Death has resulted in _four hours_ after its administration.

_Chemical Analysis._--A solution of the bichromate of potash, added to a solution of acetate of lead, gives a yellow precipitate; with nitrate of silver, a red. The salt boiled with hydrochloric or sulphuric acid and alcohol, gives a green liquid.

_Treatment._--Emetics, magnesia, chalk, demulcent drinks, &c.

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