PART II. I. Definition of Poison.

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§ 14. The term “Poison” may be considered first in its legal, as distinct from its scientific, aspect.

The legal definition of “poison” is to be gathered from the various statute-books of civilised nations.

The English law enacts that: “Whoever shall administer, or cause to be administered to, or taken by any person, any poison or other destructive thing, with intent to commit murder, shall be guilty of felony.”

Further, by the Criminal Consolidation Act, 1861: “Whosoever shall, by any other means other than those specified in any of the preceding sections of this Act, attempt to commit murder, shall be guilty of felony.”

It is therefore evident that, by implication, the English law defines a poison to be a destructive thing administered to, or taken by, a person, and it must necessarily include, not only poisons which act on account of their inherent chemical and other properties after absorption into the blood, but mechanical irritants, and also specifically-tainted fluids. Should, for example, a person give to another milk, or other fluid, knowing, at the same time, that such fluid is contaminated by the specific poison of scarlet fever, typhoid, or any serious malady capable of being thus conveyed, I believe that such an offence could be brought under the first of the sections quoted. In fine, the words “destructive thing” are widely applicable, and may be extended to any substance, gaseous, liquid, or solid, living or dead, which, if capable at all of being taken within the body, may injure or destroy life. According to this view, the legal idea of “poison” would include such matters as boiling water, molten lead, specifically-infected fluids, the flesh of animals dying of diseases which may be communicable to man, powdered glass, diamond dust, &c. Evidence must, however, be given of guilty intent.

The words, “administered to or taken by,” imply obviously that the framers of the older statute considered the mouth as the only portal of entrance for criminal poisoning, but the present law effectually guards against any attempt to commit murder, no matter by what means. There is thus ample provision for all the strange ways by which poison has been introduced into the system, whether it be by the ear, nose, brain, rectum, vagina, or any other conceivable way, so that, to borrow the words of Mr. Greaves (Notes on Criminal Law Consolidation), “the malicious may rest satisfied that every attempt to murder which their perverted ingenuity may devise, or their fiendish malignity suggest, will fall within some clause of this Act, and may be visited with penal servitude for life.”

Since poison is often exhibited, not for the purpose of taking life, but from various motives, and to accomplish various ends—as, for example, to narcotise the robber’s victim (this especially in the East), to quiet children, to create love in the opposite sex (love philters), to detect the secret sipper by suitably preparing the wine, to expel the inconvenient fruit of illicit affection, to cure inebriety by polluting the drunkard’s drink with antimony, and, finally, to satisfy an aimless spirit of mere wantonness and wickedness, the English law enacts “that whosoever shall unlawfully or maliciously administer to, or cause to be taken by, any other person, any poison or other destructive or noxious thing, so as thereby to endanger the life of such person, or so as thereby to inflict upon such person any grievous bodily harm, shall be guilty of felony.”

There is also a special provision, framed, evidently, with reference to volatile and stupefying poisons, such as chloroform, tetrachloride of carbon, &c.:

“Whoever shall unlawfully apply, or administer to, or cause to be taken by any person, any chloroform, laudanum, or other stupefying or overpowering drug, matter, or thing, with intent, in any such case, thereby to enable himself or any other person to commit, or with intent, &c., to assist any other person in committing, any indictable offence, shall be guilty of felony.”§ 15. The German statute, as with successive amendments it now stands, enacts as follows:[27]


[27] “Wer vorsÄtzlich einem Andern, um dessen Gesundheit zu beschÄdigen, Gift oder andere Stoffe beibringt, welche die Gesundheit zu zerstÖren geeignet sind, wird mit Zuchthaus von zwei bis zu zehn Jahren bestraft.

“Ist durch die Handlung eine schwere KÖrperverletzung verursacht worden, so ist auf Zuchthaus nicht unter fÜnf Jahren, und wenn durch die Handlung der Tod verursacht worden, auf Zuchthaus nicht unter zehn Jahren oder auf lebenslÄngliches Zuchthaus zu erkennen.

“Ist die vorsÄtzliche rechtswidrige Handlung des Gift—&c.,—Beibringens auf das ‘TÖdten’ gerichtet, soll also durch dieselbe gewollter Weise der Tod eines Anderen herbeigefÜhrt werden, so kommt in betracht: Wer vorsÄtzlich einen Menschen tÖdtet, wird, wenn er die TÖdtung mit Ueberlegung ausgefÜhrt hat, wegen Mordes mit dem Tode bestraft.”


“Whoever wilfully administers (beibringt) to a person, for the purpose of injuring health, poison, or any other substance having the property of injuring health, will be punished by from two to ten years’ imprisonment.

“If by such act a serious bodily injury is caused, the imprisonment is not to be less than five years; if death is the result, the imprisonment is to be not under ten years or for life.

“If the death is wilfully caused by poison, it comes under the general law: ‘Whoever wilfully kills a man, and if the killing is premeditated, is on account of murder punishable with death.’”

The French law runs thus (Art. 301, Penal Code):—“Every attempt on the life of a person, by the effect of substances which may cause death, more or less suddenly, in whatever manner these substances may have been employed or administered, and whatever may have been the results, is called poisoning.”[28]


[28] “Est qualifiÉ empoisonnement—tout attentat À la vie d’une personne par l’effet de substances qui peuvent donner la mort plus ou moins promptement, de quelque maniÈre que ces substances aient ÉtÉ employÉes ou administrÉes, et quelles qu’en aient ÉtÉ les suites.”—Art. 301, Penal Code.


There is also a penalty provided against any one who “shall have occasioned the illness or incapacity for personal work of another, by the voluntary administration, in any manner whatever, of substances which, without being of a nature to cause death, are injurious to health.”[29]


[29] “Celui qui aura occasionnÉ À autrui une maladie ou incapacitÉ de travail personnel en lui administrant volontairement, de quelque maniÈre que ce soit, des substances qui, sans Être de nature À donner la mort, sont nuisibles À la santÉ.”—Art. 317, Penal Code.


§ 16. Scientific Definition of a Poison.—A true scientific definition of a poison must exclude all those substances which act mechanically,—the physical influences of heat, light, and electricity; and parasitic diseases, whether caused by the growth of fungus, or the invasion of an organism by animal parasites, as, for example, “trichinosis,” which are not, so far as we know, associated with any poisonous product excreted by the parasite;—on the other hand, it is now recognised that pathogenic micro-organisms develop poisons, and the symptoms of all true infections are but the effects of “toxines.” The definition of poison, in a scientific sense, should be broad enough to comprehend not only the human race, but the dual world of life, both animal and vegetable.

Husemann and Kobert are almost the only writers on poisons who have attempted, with more or less success, to define poison by a generalisation, keeping in view the exclusion of the matters enumerated. Husemann says—“We define poisons as such inorganic, or organic substances as are in part capable of artificial preparation, in part existing, ready-formed, in the animal or vegetable kingdom, which, without being able to reproduce themselves, through the chemical nature of their molecules under certain conditions, change in the healthy organism the form and general relationship of the organic parts, and, through annihilation of organs, or destruction of their functions, injure health, or, under certain conditions, destroy life.” Kobert says:—“Poisons are organic or inorganic unorganised substances originating in the organism itself, or introduced into the organism, either artificially prepared, or ready formed in nature, which through their chemical properties, under certain conditions, so influence the organs of living beings, that the health of these beings is seriously influenced temporarily or permanently.”

In the first edition of this work I made an attempt to define a poison thus:—A substance of definite chemical composition, whether mineral or organic, may be called a poison, if it is capable of being taken into any living organism, and causes, by its own inherent chemical nature, impairment or destruction of function. I prefer this definition to Kobert’s, and believe that it fairly agrees with what we know of poisons.


II.—Classification of Poisons.

§ 17. At some future time, with a more intimate knowledge of the way in which each poison acts upon the various forms of animal and vegetable life, it may be possible to give a truly scientific and philosophical classification of poisons—one based neither upon symptoms, upon local effects, nor upon chemical structure, but upon a collation and comparison of all the properties of a poison, whether chemical, physical, or physiological. No perfect systematic arrangement is at present attainable: we are either compelled to omit all classification, or else to arrange poisons with a view to practical utility merely.

From the latter point of view, an arrangement simply according to the most prominent symptoms is a good one, and, without doubt, an assistance to the medical man summoned in haste to a case of real or suspected poisoning. Indeed, under such circumstances, a scheme somewhat similar to the following, probably occurs to every one versed in toxicology:

A. Poisons causing Death immediately, or in a few minutes.

There are but few poisons which destroy life in a few minutes. Omitting the strong mineral acids, carbon monoxide, carbon dioxide, with the irrespirable gases,—Prussic acid, the cyanides, oxalic acid, and occasionally strychnine, are the chief poisons coming under this head.

B. Irritant Poisons (symptoms mainly pain, vomiting, and purging).

Arsenic, antimony, phosphorus, cantharides, savin, ergot, digitalis, colchicum, zinc, mercury, lead, copper, silver, iron, baryta, chrome, yew, laburnum, and putrid animal substances.

C. Irritant and Narcotic Poisons (symptoms those of an irritant nature, with the addition of more or less pronounced cerebral indications).

To this class more especially belong oxalic acid and the oxalates, with several poisons belonging to the purely narcotic class, but which produce occasionally irritant effects.

D. Poisons more especially affecting the Nervous System.

1. Narcotics (chief symptom insensibility, which may be preceded by more or less cerebral excitement): Opium, Chloral, Chloroform.

2. Deliriants (delirium for the most part a prominent symptom): Belladonna, hyoscyamus, stramonium, with others of the SolanaceÆ, to which may be added—poisonous fungi, Indian hemp, lolium temulentum, oenanthe crocata, and camphor.

3. Convulsives.—Almost every poison has been known to produce convulsive effects, but the only true convulsive poisons are the alkaloids of the strychnos class.

4. Complex Nervous Phenomena: Aconite, digitalis, hemlock, calabar bean, tobacco, lobelia inflata, and curara.


§ 18. Kobert’s Classification.—The latest authority on poisons—Kobert—has classified poisons according to the following scheme:

I. POISONS WHICH CAUSE COARSE ANATOMICAL CHANGES OF THE ORGANS.

A. Those which specially irritate the part to which they are applied.

1. Acids.

2. Caustic alkalies.

3. Caustic salts, especially those of the heavy metals.

4. Locally irritating organic substances which neither can be classified as corrosive acids nor alkalies, nor as corrosive salts; such are:—cantharidine, phrynine, and others in the animal kingdom, croton oil and savin in the vegetable kingdom. Locally irritating colours, such as the aniline dyes.

5. Gases and vapours which cause local irritation when breathed, such as ammonia, chlorine, iodine, bromine, and sulphur dioxide.

B. Those which have but little effect locally, but change anatomically other parts of the body; such as lead, phosphorus, and others.

II. BLOOD POISONS.

1. Blood poisons interfering with the circulation in a purely physical manner, such as peroxide of hydrogen, ricine, abrine.

2. Poisons which have the property of dissolving the red blood corpuscle, such as the saponins.

3. Poisons which, with or without primary solution of the red blood corpuscles, produce in the blood methÆmoglobin; such as potassic chlorate, hydrazine, nitrobenzene, aniline, picric acid, carbon disulphide.

4. Poisons having a peculiar action on the colouring matter of the blood, or on its decomposition products, such as hydric sulphide, hydric cyanide, and the cyanides and carbon monoxide.

III. POISONS WHICH KILL WITHOUT THE PRODUCTION OF COARSE ANATOMICAL CHANGE.

1. Poisons affecting the cerebro-spinal system; such as chloroform, ether, nitrous oxide, alcohol, chloral, cocaine, atropine, morphine, nicotine, coniine, aconitine, strychnine, curarine, and others.

2. Heart Poisons; such as, digitalis, helleborin, muscarine.

IV. POISONOUS PRODUCTS OF TISSUE CHANGE.

1. Poisonous albumin.

2. Poisons developed in food.

3. Auto-poisoning, e.g. urÆmia, glycosuria, oxaluria.

4. The more important products of tissue change; such as, fatty acids, oxyacids, amido-fatty acids, amines, diamines, and ptomaines.


§ 19. I have preferred an arrangement which, as far as possible, follows the order in which a chemical expert would search for an unknown poison—hence an arrangement partly chemical and partly symptomatic. First the chief gases which figure in the mortality statistics are treated, and then follow in order other poisons.

A chemist, given a liquid to examine, would naturally test first its reaction, and, if strongly alkaline or strongly acid, would at once direct his attention to the mineral acids or to the alkalies. In other cases, he would proceed to separate volatile matters from those that were fixed, lest substances such as prussic acid, chloroform, alcohol, and phosphorus be dissipated or destroyed by his subsequent operations.

Distillation over, the alkaloids, glucosides, and their allies would next be naturally sought, since they can be extracted by alcoholic and ethereal solvents in such a manner as in no way to interfere with an after-search for metals.

The metals are last in the list, because by suitable treatment, after all organic substances are destroyed, either by actual fire or powerful chemical agencies, even the volatile metals may be recovered. The metals are arranged very nearly in the same order as that in which they would be separated from a solution—viz., according to their behaviour to hydric and ammoniac sulphides.

There are a few poisons, of course, such as the oxalates of the alkalies, which might be overlooked, unless sought for specially; but it is hoped that this is no valid objection to the arrangement suggested, which, in greater detail, is as follows:

A.—POISONOUS GASES.

  1. Carbon monoxide.
  2. Chlorine.
  3. Hydric sulphide.

B.—ACIDS AND ALKALIES.

  1. Sulphuric acid.
  2. Hydrochloric acid.
  3. Nitric acid.
  4. Potash.
  5. Soda.
  6. Ammonia.
  7. Neutral sodium, potassium, and ammonium salts.

In nearly all cases of death from any of the above, the analyst, from the symptoms observed during life, from the surrounding circumstances, and from the pathological appearances and evident chemical reactions of the fluids submitted, is put at once on the right track, and has no difficulty in obtaining decided results.

C.—POISONOUS SUBSTANCES CAPABLE OF BEING SEPARATED BY DISTILLATION FROM EITHER NEUTRAL OR ACID LIQUIDS.

  1. Hydrocarbons.
  2. Camphor.
  3. Alcohols.
  4. Amyl-nitrite.
  5. Chloroform and other anÆsthetics.
  6. Carbon disulphide.
  7. Carbolic acid.
  8. Nitro-benzene.
  9. Prussic acid.
  10. Phosphorus.

The volatile alkaloids, which may also be readily distilled by strongly alkalising the fluid, because they admit of a rather different mode of treatment, are not included in this class.

D.—ALKALOIDS AND POISONOUS VEGETABLE PRINCIPLES SEPARATED FOR THE MOST PART BY ALCOHOLIC SOLVENTS.

DIVISION I.—Vegetable Alkaloids.

  1. Liquid volatile alkaloids, alkaloids of hemlock, nicotine, piturie, sparteine, aniline.
  2. The opium group of alkaloids.
  3. The strychnine or tetanic group of alkaloids—strychnine, brucine, igasurine.
  4. The aconite group of alkaloids.
  5. The mydriatic group of alkaloids—atropine, hyoscyamine, solanin, cytisine.
  6. The alkaloids of the veratrines.
  7. Physostigmine.
  8. Pilocarpine.
  9. Taxine.
  10. Curarine.
  11. Colchicin.
  12. Muscarine and the active principles of certain fungi.

There would, perhaps, have been an advantage in arranging several of the individual members somewhat differently—e.g., a group might be made of poisons which, like pilocarpine and muscarine, are antagonistic to atropine; and another group suggests itself, the physiological action of which is the opposite of the strychnos class; solanin (although classed as a mydriatic, and put near to atropine) has much of the nature of a glucoside, and the same may be said of colchicin; so that, if the classification were made solely on chemical grounds, solanin would have followed colchicin, and thus have marked the transition from the alkaloids to the glucosides.

DIVISION II.—Glucosides.

  1. The digitalis group.
  2. Other poisonous glucosides acting on the heart.
  3. Saponin.

The glucosides, when fairly pure, are easily recognised; they are destitute of nitrogen, neutral in reaction, and split up into sugar and other compounds when submitted to the action of saponifying agents, such as boiling with dilute mineral acids.

DIVISION III.—Certain Poisonous Anhydrides of the Organic Acids.

  1. Santonin.
  2. Mezereon.

It is probable that this class will in a few years be extended, for several other organic anitrogenous poisons exist, which, when better known, will most likely prove to be anhydrides.

DIVISION IV.—Various Vegetable Poisonous Principles not admitting of Classification under the previous Three Divisions.

Ergot, picrotoxin, the poison of Illicium religiosum, cicutoxin, Æthusa cynapium, Œnanthe crocata, croton oil, savin oil, the toxalbumins of castor oil and Abrus.

The above division groups together various miscellaneous toxic principles, none of which can at present be satisfactorily classified.

E.—POISONS DERIVED FROM LIVING OR DEAD ANIMAL SUBSTANCES.

DIVISION I.—Poisons Secreted by the Living.

  1. Poisonous amphibia.
  2. Poison of the scorpion.
  3. Poisonous fish.
  4. Poisonous insects—spiders, wasps, bees, beetles, &c.
  5. Snake poison.

DIVISION II.—Poisons formed in Dead Animal Matters.

  1. Ptomaines.
  2. Poisoning by putrid or changed foods—sausage poisoning.

F.—THE OXALIC ACID GROUP.

G.—INORGANIC POISONS.

DIVISION I.—Precipitated from a Hydrochloric Acid Solution by Hydric Sulphide—Precipitate, Yellow or Orange.

  • Arsenic, antimony, cadmium.

DIVISION II.—Precipitated by Hydric Sulphide in Hydrochloric acid Solution—Black.

  • Lead, copper, bismuth, silver, mercury.

DIVISION III.—Precipitated from a Neutral Solution by Hydric Sulphide.

  • Zinc, nickel, cobalt.

DIVISION IV.—Precipitated by Ammonia Sulphide.

  • Iron, chromium, thallium, aluminium.

DIVISION V.—Alkaline Earths.

  • Barium.

III.—Statistics.

§ 20. The number of deaths from poison (whether accidental, suicidal, or homicidal), as compared with other forms of violent, as well as natural deaths, possesses no small interest; and this is more especially true when the statistics are studied in a comparative manner, and town be compared with town, country with country.

The greater the development of commercial industries (especially those necessitating the use or manufacture of powerful chemical agencies), the more likely are accidents from poisons to occur. It may also be stated, further, that the higher the mental development of a nation, the more likely are its homicides to be caused by subtle poison—its suicides by the euthanasia of chloral, morphine, or hemlock.

Other influences causing local diversity in the kind and frequency of poisoning, are those of race, of religion, of age and sex, and the mental stress concomitant with sudden political and social changes.

In the ten years from 1883-1892, there appear to have died from poison, in England and Wales, 6616 persons, as shown in the following tables:

DEATHS FROM POISON IN ENGLAND AND WALES DURING THE TEN YEARS 1883-92.

Accident or
Negligence.
Suicide. Murder. Total.
M. F. M. F. M. F. M. F.
Metals.
Arsenic, 37 14 37 20 1 1 75 35
Antimony, 3 ... 1 2 ... ... 4 2
Copper, 4 1 2 1 ... ... 6 2
Lead, 831 209 1 2 ... ... 832 211
Silver Nitrate, 1 ... ... ... ... ... 1 ...
Zinc Chloride (or Sulphate), 7 ... 4 ... ... ... 11 ...
Mercury, 22 11 16 8 2 1 40 20
Chromic Acid, 1 ... ... ... ... ... 1 ...
Iron Perchloride, ... ... ... 1 ... ... ... 1
Alkaline Earths.
Lime, 2 ... ... 1 ... ... 2 1
Barium Chloride, 1 ... ... ... ... ... 1 ...
The Alkalies and their Salts.
Ammonia, 39 25 18 16 ... ... 57 41
Caustic Soda, 3 4 ... 1 ... ... 3 5
Cautic Potash, 8 10 1 ... ... ... 9 10
Potassic Chlorate, 1 ... ... ... ... ... 1 ...
Potssic Bichromate, 2 2 7 3 ... ... 9 5
Potssic Bromide, 1 ... ... ... ... ... 1 ...
Potssic Binoxalate (Sorrel), 1 3 1 4 ... ... 2 7
Acids.
Sulphuric Acid, 30 9 29 24 1 ... 60 33
Nitric 18 7 18 9 ... ... 36 16
Hydrochloric 48 18 83 55 ... ... 131 73
Oxalic 17 6 114 86 ... ... 131 92
Tartaric ... 1 ... ... ... ... ... 1
Acetic 4 3 ... 2 ... ... 4 5
Carbolic 169 101 219 271 ... 1 388 373
Hydrofluoric ... ... ... 1 ... ... ... 1
Phosphorus (including Lucifer matches), 24 47 28 56 ... ... 52 103
Iodine, 6 7 1 1 ... ... 7 8
Volatile Liquids.
Paraffin (Petroleum), 9 2 1 ... ... ... 10 2
Benzoline, 3 2 ... 1 ... ... 3 3
Naphtha, 1 ... ... ... ... ... 1 ...
Carbon Bisulphide, ... ... 1 ... ... ... 1 ...
Turpentine, 5 1 ... 3 ... ... 5 4
Methylated Spirit, ... 2 1 2 ... ... 1 4
Alcohol, 81 24 1 2 ... ... 82 26
Chloroform, 57 41 9 5 1 ... 67 46
Ether, 5 2 ... ... ... ... 5 2
Spt. Etheris Nitrosi, 1 ... ... ... ... ... 1 ...
AnÆsthetic (kind not stated), 4 3 ... ... ... ... 4 3
Oil of Juniper, 1 ... ... ... ... ... 1 ...
Opiates and Narcotics.
Opium, Laudanum—Morphia, 503 373 330 167 4 2 837 542
Soothing Syrup, Paregoric, &c. 18 22 2 3 ... ... 20 25
Chlorodyne, 56 30 8 8 ... ... 64 38
Chloral, 89 22 14 1 1 ... 104 23
Cyanides.
Prussic Acid, and Oil of Almonds, 17 11 203 19 2 8 222 38
Potassium Cyanide, 19 21 100 22 3 1 122 44
Alkaloids.
Strychnine and Nux Vomica, 22 21 65 85 4 4 91 110
Vermin-Killer, 2 6 49 69 1 ... 52 75
Atropine, 2 ... 1 ... ... ... 3 ...
Belladonna, 36 20 11 9 ... ... 47 29
Aconite, 19 21 9 10 ... ... 28 31
Ipecacuanha, 1 1 ... ... ... ... 1 1
Cocaine, 3 ... ... ... ... ... 3 ...
Miscellaneous.
Antipyrine, 1 ... ... ... ... ... 1 ...
Cantharides, 1 ... ... 1 ... ... 1 1
Camphorated Oil, 1 ... ... ... ... ... 1 ...
Croton Oil, 1 ... ... ... ... ... 1 ...
Cayenne Pepper, 1 ... ... ... ... ... 1 ...
Syrup of Rhubarb, 1 ... ... ... ... ... 1 ...
Colchicum, 2 ... ... ... ... ... 2 ...
Hemlock, 3 1 ... ... ... ... 3 1
Water Hemlock, 5 6 ... ... ... ... 5 6
Colocynth, ... 2 ... ... ... ... ... 2
Castor Oil Seeds, 1 1 ... ... ... ... 1 1
Laburnum Seeds, 2 1 ... ... ... ... 2 1
Thorn Apple, 1 ... ... ... ... ... 1 ...
Yew Leaves or Berries, 3 2 ... ... ... ... 3 2
Crow-foot, ... 1 ... ... ... ... ... 1
Whin-flower, 1 ... ... ... ... ... 1 ...
Pennyroyal, ... 1 ... ... ... ... ... 1
Meadow Crow-foot, ... 1 ... ... ... ... ... 1
Arum Seeds, ... 1 ... ... ... ... ... 1
Bitter Aloes, ... 1 ... 1 ... ... ... 2
Cocculus Indicus, ... ... 1 ... ... ... 1 ...
Horse Chestnut, ... 1 ... ... ... ... ... 1
Creosote, 1 ... ... ... ... ... 1 ...
Spirits of Tar (Oil of Tar), 2 1 ... ... ... ... 2 1
Nitro-Glycerine, 1 ... ... ... ... ... 1 ...
Camphor, ... 1 ... ... ... ... ... 1
Tobacco, 4 ... 1 ... ... ... 5 ...
Lobelia, 1 ... ... ... ... ... 1 ...
Fungi, 13 10 ... ... ... ... 13 10
Poisonous Weeds, 2 ... ... ... ... ... 2 ...
Hellebores, ... ... 1 1 ... ... 1 1
Kind not stated, 216 158 256 167 3 1 475 326
2498 1292 1644 1140 23 19 4165 2551
3790 2784 42 6616

Although so large a number of substances destroy life by accident or design, yet there are in the list only about 21 which kill about 2 persons or above each year: the 21 substances arranged in the order of their fatality are as follows:

Actual deaths
in ten years
ending 1892.
Caustic potash 19
Poisonous fungi 23
Aconite 59
Mercury 60
Belladonna 76
Sulphuric acid 93
Ammonia 98
Chlorodyne 102
Alcohol 108
Arsenic 110
Chloroform 113
Vermin-killer 127
Chloral 127
Phosphorus 155
Cyanide of potassium 166
Strychnine 201
Nitric acid 204
Prussic acid 260
Carbolic acid 762
Lead 1043
Opiates 1324

In each decade there are changes in the position on the list. The most significant difference between the statistics now given and the statistics for the ten years ending 1880, published in the last edition of this work, is that in the former decade carbolic acid occupied a comparatively insignificant place; whereas in the ten years ending 1892, deaths from carbolic acid poisoning are the most frequent form of fatal poisoning save lead and opiates.§ 21. The following table gives some German statistics of poisoning:

TABLE SHOWING THE ADMISSIONS INTO VARIOUS MEDICAL INSTITUTIONS[30] IN BERLIN OF PERSONS SUFFERING FROM THE EFFECTS OF POISON DURING THE THREE YEARS 1876, 1877, 1878.


[30] Viz., the KÖnigl. CharitÉ, Allg. StÄdtisches Krankenhaus, StÄdtisches Baracken-Lazareth, Bethanien, St. HelwÖg’s-Lazarus, Elisabethen-Krankenhaus, Augusta Hospital, and the Institut fÜr Staatsarzneikunde.


Males. Females. Total.
Charcoal Vapour, 77 78 155
Sulphuric Acid, 24 54 - 93
Hydrochloric Acid, 4 4
Nitric Acid, and Aqua Regia, 7 ...
Phosphorus, 13 28 41
Cyanide of Potassium, 29 3 - 38
Prussic Acid, 5 1
Oxalic Acid, and Oxalate of Potash, 11 8 19
Alcohol, 12 2 14
Arsenic, 7 5 12
Morphine, 8 1 - 12
Opium, 2 1
Potash or Soda Lye, 2 6 8
Chloral, 3 4 7
Chloroform, 4 2 6
Sewer Gas, 5 ... 5
Strychnine, ... 4 4
Atropine, 1 2 3
Copper Sulphate, 1 2 3
Nitrobenzol, 2 ... 2
Carbolic Acid, ... 2 2
Chromic Acid, 1 1 2
Burnt Alum, ... 1 1
Ammonium Sulphide, 1 ... 1
Datura Stramonium, ... 1 1
Petroleum, ... 1 1
Benzine, 1 ... 1
Ether, 1 ... 1
Prussic Acid and Morphine, 1 ... 1
Prussic Acid and Chloral, 1 ... 1
Turpentine and Sal Ammoniac, ... 1 1
223 212 435

Suicidal Poisoning.—Poisons which kill more than one person suicidally each year are only 19 in number, as follows:

Deaths from suicide
during the ten
years ending 1892.
Potassic bichromate 10
Chloroform 14
Chloral 15
Chlorodyne 16
Aconite 19
Belladonna 20
Mercury 24
Nitric acid 27
Ammonia 34
Sulphuric acid 53
Arsenic 77
Phosphorus 84
Vermin-killer 118
Prussic acid 122
Hydrochloric acid 138
Strychnine 150
Oxalic acid 200
Prussic acid 222
Opiates 281
Phenol 290

In the ten years ending 1880, suicidal deaths from vermin-killers, from prussic acid, from cyanide of potassium, and from opiates were all more numerous than deaths from phenol, whereas at present phenol appears to be the poison most likely to be chosen by a suicidal person.


Criminal Poisoning.

§ 22. Some useful statistics of criminal poisoning have been given by Tardieu[31] for the 21 years 1851-1871, which may be summarised as follows:


[31] Étude MÉdico-LÉgale sur l’Empoisonnement, Paris, 1875.


Total accusations of Poisoning in the 21 years, 793
Results of the Poisoning:—
Death, 280 - 872
Illness, 346
Negative, 246
Accused:—
Men, 304 - 703
Women, 399
Nature of Poison Employed:—
Arsenic, 287
Phosphorus, 267
Copper - Sulphate, 120 - 159
Acetate (Verdigris), 39
Acids - Sulphuric Acid, 36 - 47
Hydrochloric Acid, 8
Nitric Acid, 3
Cantharides, 30
Nux Vomica, 5 - 12
Strychnine, 7
Opiates - Opium, 6 - 10
Laudanum, 3
Sedative Water, 1
Salts of Mercury, 8
Sulphate of Iron, 6
Preparations of Antimony, 5
Ammonia, 4
Cyanides - Prussic Acid, 2 - 4
Cyanide of Potassium, 2
Hellebore, 3
Datura Stramonium, 3
Powdered Glass, 3
Digitalin, 2
Potash, 2
Sulphate of Zinc, 2
Eau de Javelle (a solution of Hypochlorite of Potash), 1
Tincture of Iodine, 1
Croton Oil, 1
Nicotine, 1
Belladonna, 1
“Baume Fiovarenti,” 1
Euphorbia, 1
Acetate of Lead, 1
Carbonic Acid Gas, 1
Laburnum Seeds, 1
Colchicum, 1
Mushrooms, 1
Sulphuric Ether, 1
Total, 867

It hence may be concluded, according to these statistics of criminal poisoning, that of 1000 attempts in France, either to injure or to destroy human life by poison, the following is the most probable selective order:

Arsenic, 331
Phosphorus, 301
Preparations of Copper, 183
The Mineral Acids, 54
Cantharides, 35
Strychnine, 14
Opiates, 12
Mercurial preparations, 9
Antimonial preparations, 6
Cyanides (that is, Prussic Acid and Potassic Cyanide), 5
Preparations of Iron, 5

This list accounts for 955 poisonings, and the remaining 45 will be distributed among the less used drugs and chemicals.


IV.—The Connection between Toxic Action and Chemical Composition.

§ 23. Considerable advance has been made of late years in the study of the connection which exists between the chemical structure of the molecule of organic substances and physiological effect. The results obtained, though important, are as yet too fragmentary to justify any great generalisation; the problem is a complicated one, and as Lauder Brunton justly observes:

“The physiological action of a drug does not depend entirely on its chemical composition nor yet on its chemical structure, so far as that can be indicated even by graphic formula, but upon conditions of solubility, instability, and molecular relations, which we may hope to discover in the future, but with which we are as yet imperfectly acquainted.”[32]


[32] Introduction to Modern Therapeutics, Lond., 1892. 136.


The occurrence of hydroxyl, whether the substance belong to the simpler chain carbon series or to the aromatic carbon compounds, appears to usually endow the substance with more or less active and frequently poisonous properties, as, for example, in the alcohols, and as in hydroxylamine. It is also found that among the aromatic bodies the toxic action is likely to increase with the number of hydroxyls: thus phenol has one hydroxyl, resorcin two, and phloroglucin three; and the toxic power is strictly in the same order, for, of the three, phenol is least and phloroglucin most poisonous.

Replacing hydrogen by a halogen, especially by chlorine, in the fatty acids mostly produces substances of narcotic properties, as, for instance, monochloracetic acid. In the sulphur compounds, the entrance of chlorine modifies the physiological action and intensifies toxicity: thus ethyl sulphide (C2H5)2S is a weak poison, monochlorethyl sulphide C2H5C2H4ClS a strong poison, and dichlorethyl sulphide C4H8Cl2S a very strong poison: the vapour kills rabbits within a short time, and a trace of the oil applied to the ear produces intense inflammation of both the eyes and the ear.[33]


[33] V. Meyer, Ber. d. Chem. Ges., XX., 1725.


The weight of the molecule has an influence in the alcohols and acids of the fatty series; for instance, ethyl, propyl, butyl, and amyl alcohols show as they increase in carbon a regular increase in toxic power; the narcotic actions of sodium propionate, butyrate, and valerianate also increase with the rising carbon. Nitrogen in the triad condition in the amines is far less poisonous than in the pentad condition.

Bamberger[34] distinguishes two classes of hydrogenised bases derived from a and naphthylamine, by the terms “acylic” and “aromatic.” The acylic contains the four added hydrogens in the amidogen nucleus, the aromatic in the other nucleus, thus


[34] Ber., xxii. 777-778.


a Naphthylamine.

Naphthylamine.

Acylic tetrahydro-a Naphthylamine.

Aromatic tetrahydro- Naphthylamine.

a Naphthylamine.

Naphthylamine.

Acylic tetrahydro-a Naphthylamine.

Aromatic tetrahydro- Naphthylamine.

The acylic tetrahydro-naphthylamine, the tetrahydroethylnaphthylamine, and the tetrahydromethylnaphthylamine all cause dilatation of the pupil and produce symptoms of excitation of the cervical sympathetic nerve; the other members of the group are inactive.§ 24. The result of replacing hydrogen by alkyls in aromatic bodies has been studied by Schmiedeberg and others; replacing the hydrogen of the amidogen by ethyl or methyl, usually results in a body having a more or less pronounced narcotic action. The rule is that methyl is stronger than ethyl, but it does not always hold good; ortho-amido-phenol is not in itself poisonous, but when two hydrogens of the amidogen group are replaced by two methyls thus

the resulting body has a weak narcotic action.

It would naturally be inferred that the replacement of the H in the hydroxyl by a third methyl would increase this narcotic action, but this is not so: on the other hand, if there are three ethyl groups in the same situation a decidedly narcotic body is produced.

The influence of position of an alkyl in the aromatic bodies is well shown in ortho-, para- and meta-derivatives. Thus the author proved some years ago that with regard to disinfecting properties, ortho-cresol was more powerful than meta-; meta-cresol more powerful than para-; so again ortho-aceto-toluid is poisonous, causing acute nephritis; meta-aceto-toluid has but feeble toxic actions but is useful as an antipyretic; and para-aceto-toluid is inactive.

In the trioxybenzenes, in which there are three hydroxyls, the toxic action is greater when the hydroxyls are consecutive, as in pyrogallol, than when they are symmetrical, as in phloroglucin.

Pyrogallol.

Phloroglucin.

Pyrogallol.

Phloroglucin.

The introduction of methyl into the complicated molecule of an alkaloid often gives curious results: thus methyl strychnine and methyl brucine instead of producing tetanus have an action on voluntary muscle like curare.

Benzoyl-ecgonine has no local anÆsthetic action, but the introduction of methyl into the molecule endows it with a power of deadening the sensation of the skin locally; on the other hand, cocethyl produces no effect of this kind.

Drs. Crum Brown and Fraser[35] have suggested that there is some relation between toxicity and the saturated or non-saturated condition of the molecule.


[35] Journ. Anat. and Phys., vol. ii. 224.


Hinsberg and Treupel have studied the physiological effect of substituting various alkyls for the hydrogen of the hydroxyl group in para-acetamido-phenol.

Para-aceto-amido-phenol when given to dogs in doses of 0.5 grm. for every kilogr. of body weight causes slight narcotic symptoms, with slight paralysis; there is cyanosis and in the blood much methÆmoglobin.

In men doses of half a gramme (7·7 grains) act as an antipyretic, relieve neuralgia and have weak narcotic effects.

The following is the result of substituting certain alkyls for H in the HO group.

(1) Methyl.—The narcotic action is strengthened and the antipyretic action unaffected. The methÆmoglobin in the blood is somewhat less.

(2) Ethyl.—Action very similar, but much less methÆmoglobin is produced.

(3) Propyl.—Antipyretic action a little weaker. MethÆmoglobin in the blood smaller than in para-acetamido-phenol, but more than when the methyl or ethyl compound is administered.

(4) Amyl.—Antipyretic action decreased.

The smallest amount of toxicity is in the ethyl substitution; while the maximum antipyretic and antineuralgic action belongs to the methyl substitution.

Next substitution was tried in the Imid group. It was found that substituting ethyl for H in the imid group annihilated the narcotic and antipyretic properties. No methÆmoglobin could be recognised in the blood.

Lastly, simultaneous substitution of the H of the HO group by ethyl and the substitution of an alkyl for the H in the NH group gave the following results:

Methyl.—In dogs the narcotic action was strengthened, the methÆmoglobin in the blood diminished. In men the narcotic action was also more marked as well as the anti-neural action. The stomach and kidneys were also stimulated.

Ethyl.—In dogs the narcotic action was much strengthened, while the methÆmoglobin was diminished. In men the antipyretic and anti-neural actions were unaffected.

Propyl.—In dogs the narcotic action was feebler than with methyl or ethyl, and in men there was diminished antipyretic action.

Amyl.—In dogs the narcotic action was much smaller.

From this latter series the conclusion is drawn that the maximum of narcotic action is obtained by the introduction of methyl and the maximum antipyretic action by the introduction of methyl or ethyl. The ethyl substitution is, as before, the less toxic.[36]


[36] Ueber die physiologische Wirkung des p-amido-phenol u. einiger Derivate desselben. O. Hinsberg u. G. Treupel, Archiv f. Exp. Pathol. u. Pharm., B. 33, S. 216.


The effect of the entrance of an alkyl into the molecule of a substance is not constant; sometimes the action of the poison is weakened, sometimes strengthened. Thus, according to Stolnikow, dimethyl resorcin, C6H4(OCH3)2, is more poisonous than resorcin C6H4(OH)2. Anisol C6H5OCH3, according to Loew, is more poisonous to algÆ, bacteria, and infusoria than phenol C6H5OH. On the other hand, the replacement by methyl of an atom of hydrogen in the aromatic oxyacids weakens their action; methyl salicylic acid is weaker than salicylic acid .

Arsen-methyl chloride, As(CH3)Cl2, is strongly poisonous, but the introduction of a second methyl As(CH3)2Cl makes a comparatively weak poison.§ 25. In some cases the increase of CO groups weakens the action of a poison; thus, in allantoin there are three carbonyl (CO) groups; this substance does not produce excitation of the spinal cord, but it heightens muscular irritability and causes, like xanthin, muscular rigidity; alloxantin, with a similar structure but containing six carbonyl groups, does not possess this action.

Allantoin.

Alloxantin.

Allantoin.

Alloxantin.

§ 26. A theory of general application has been put forward and supported with great ability by Oscar Loew[37] which explains the action of poisons by presuming that living has a different composition to dead albumin; the albumin of the chemist is a dead body of a definite composition and has a stable character; living albumin, such as circulates in the blood or forms the protoplasm of the tissues, is not “stable” but “labile”; Loew says:—“If the old idea is accepted that living albumin is chemically the same substance as that which is dead, numerous toxic phenomena are inexplicable. It is impossible, for instance, to explain how it is that diamide N2H4 and hydroxylamine NH2OH are toxic, even with great dilution, on all living animals; whilst neither of those substances have the smallest action on dead plasma or the ordinary dissolved passive albumin, there must therefore be present in the albumin of the living plasma a grouping of atoms in a “labile” condition (Atomgruppirungen labiler Art) which are capable of entering into reactions; such, according to our present knowledge, can only be the aldehyde and the ketone groups. The first mentioned groups are more labile and react in far greater dilution than the latter groups.”


[37] Ein natÜrliches System der Gift-Wirkungen, MÜnchen, 1893.


Loew considers that all substances which enter into combination with aldehyde or ketone groups must be poisonous to life generally. For instance, hydroxylamine, diamide and its derivatives, phenylhydrazine, free ammonia, phenol, prussic acid, hydric sulphide, sulphur dioxide and the acid sulphites all enter into combination with aldehyde.

So again the formation of imide groups in the aromatic ring increases any poisonous properties the original substance possesses, because the imide group easily enters into combination with aldehyde; thus piperidine (CH2)5NH is more poisonous than pyridine (CH)5N; coniine NH(CH2)4CH-CH2-CH2CH3, is more poisonous than collidine N(CH)4C-CH-(CH3)2; pyrrol (CH)4NH than pyridine (CH)5N; and amarin,[38] , than hydrobenzamide .


[38] Th. Weyl (Lehrbuch der organischen Chemie) states (p. 385) that amarin is not poisonous, but Baccheti (Jahr. d. Chemie, 1855) has shown that 250 mgrms. of the acetate will kill a dog, 80 mgrms. a guinea-pig; and that it is poisonous to fishes, birds, and frogs: hydrobenzamide in the same doses has no effect.


If the theory is true, then substances with “labile” amido groups, on the one hand, must increase in toxic activity if a second amido group is introduced; and, on the other, their toxic qualities must be diminished if the amido group is changed into an imido group by the substitution of an atom of hydrogen for an alkyl.

Observation has shown that both of these requirements are satisfied; phenylenediamine is more poisonous than aniline; toluylenediamine more poisonous than toluidine. Again, if an atom of hydrogen in the amido (NH2) group in aniline be replaced by an alkyl, e.g. methyl or ethyl, the resulting substance does not produce muscular spasm; but if the same alkyl is substituted for an atom of hydrogen in the benzene nucleus the convulsive action remains unaffected.

If an acidyl, as for example the radical of acetic acid, enter into the amido group, then the toxic action is notably weakened; thus, acetanilide is weaker than aniline, and acetylphenylhydrazine is weaker than phenylhydrazine. If the hydrogen of the imido group be replaced by an alkyl or an acid radical, and therefore tertiary bound nitrogen restored, the poisonous action is also weakened.

In xanthin there are three imido groups; the hydrogen of two of these groups is replaced by methyl in theobromin; and in caffein the three hydrogens of the three imido groups are replaced by three methyls, thus:

Xanthin.

Theobromin.

Xanthin.

Theobromin.

Caffein.

and experiment has shown that theobromin is weaker than xanthin, and caffein still weaker than theobromin.

Loew[39] makes the following generalisations:


[39] Ein natÜrliches System der Gift-Wirkungen, MÜnchen, 1893.


1. Entrance of the carboxyl or sulpho groups weakens toxic action.

2. Entrance of a chlorine atom exalts the toxic character of the catalytic poisons (Loew’s catalytic poisons are alcohols, ether, chloroform, chloral, carbon tetrachloride, methylal, carbon disulphide and volatile hydrocarbons).

3. Entrance of hydroxyl groups in the catalytic poisons of the fatty series weakens toxic character; on the other hand, it exalts the toxicity of the substituting poisons. (Examples of Loew’s class of “substituting” poisons are hydroxylamine, phenylhydrazine, hydric cyanide, hydric sulphide, aldehyde, and the phenols.)

4. A substance increases in poisonous character through every influence which increases its power of reaction with aldehyde or amido groups. If, for example, an amido or imido group in the poison molecule be made more “labile,” or if thrice linked nitrogen is converted into nitrogen connected by two bands, whether through addition of water or transposition (umlagerung) or if a second amido group enters, the poisonous quality is increased. Presence of a negative group may modify the action.

5. Entrance of a nitro group strengthens the poisonous character. If a carboxyl or a sulpho group is present in the molecule, or if, in passing through the animal body, negative groups combine with the poison molecule, or carboxyl groups are formed in the said molecule; in such cases the poisonous character of the nitro group may not be apparent.

6. Substances with double carbon linkings are more poisonous than the corresponding saturated substances. Thus neurine with the double linking of the carbon of CH2 is more poisonous than choline; vinylamine than ethylamine.

Neurine.

Choline.

Neurine.

Choline.

Vinylamine.

Ethylamine.

Vinylamine.

Ethylamine.

§ 27. M. Ch. Michet[40] has investigated the comparative toxicity of the metals by experiments on fish, using species of Serranus, Crenolabrus, and Julius. The chloride of the metal was dissolved in water and diluted until just that strength was attained in which the fish would live 48 hours; this, when expressed in grammes per litre, he called “the limit of toxicity.”


[40]De la ToxicitÉ comparÉe des diffÉrents MÉtaux.Note de M. Ch. Michet. Compt. Rend., t. xciii., 1881, p. 649.


The following is the main result of the inquiry, by which it will be seen that there was found no relation between “the limit of toxicity” and the atomic weight.

TABLE SHOWING THE RESULTS OF EXPERIMENTS ON FISH.

No. of
Experiments.
Metal. Limit of
Toxicity.
20. Mercury, ·00029
7. Copper, ·0033
20. Zinc, ·0084
10. Iron, ·014
7. Cadmium, ·017
6. Ammonium, ·064
7. Potassium, ·10
10. Nickel, ·126
9. Cobalt, ·126
11. Lithium, ·3
20. Manganese ·30
6. Barium, ·78
4. Magnesium, 1 ·5
20. Strontium, 2 ·2
5. Calcium, 2 ·4
6. Sodium, 24 ·17

V.—Life-Tests; or the Identification of Poison by Experiments on Animals.

§ 28. A philosophical investigation of poisons demands a complete methodical examination into their action on every life form, from the lowest to the highest. Our knowledge is more definite with regard to the action of poisons on man, dogs, cats, rabbits, and frogs than on any other species. It may be convenient here to make a few general remarks as to the action of poisons on infusoria, the cephalopoda, and insects.

Infusoria.—The infusoria are extremely sensitive to the poisonous alkaloids and other chemical agents. Strong doses of the alkaloids cause a contraction of the cell contents, and somewhat rapid disintegration of the whole body; moderate doses at first quicken the movements, then the body gets perceptibly larger, and finally, as in the first case, there is disintegration of the animal substance.

Rossbach[41] gives the following intimations of the proportion of the toxic principle necessary to cause death:—Strychnine 1 part dissolved in 1500 of water; veratrine 1 in 8000; quinine 1 in 5000; atropine 1 in 1000; the mineral acids 1 in 400-600; salts 1 in 200-300.


[41] N. J. Rossbach, Pharm. Zeitschr. fÜr Russland, xix. 628.


The extraordinary sensitiveness of the infusoria, and the small amount of material used in such experiments, would be practically useful if there were any decided difference in the symptoms produced by different poisons. But no one could be at all certain of even the class to which the poison belongs were he to watch, without a previous knowledge of what had been added to the water, the motions of poisoned infusoria. Hence the fact is more curious than useful.

Cephalopoda.—The action of a few poisons on the cephalopoda has been investigated by M. E. Yung.[42] Curara placed on the skin had no effect, but on the branchiÆ led to general paralysis. If given in even fifteen times a greater dose than necessary to kill a rabbit, it was not always fatal. Strychnine, dissolved in sea-water, in the proportion of 1 to 30,000, causes most marked symptoms. The first sign is relaxation of the chromataphore muscle and the closing of the chromataphores; the animal pales, the respiratory movements become more powerful, and at the end of a notable augmentation in their number, they fall rapidly from the normal number of 25 to 5 a minute. Then tetanus commences after a time, varying with the dose of the poison; the arm stiffens and extends in fan-like form, the entire body is convulsed, the respiration is in jerks, the animal empties his pouch, and at the end of a few minutes is dead, in a state of great muscular rigidity. If at this moment it is opened, the venous heart is found still beating. Nicotine and other poisons were experimented with, and the cephalopoda were found to be generally sensitive to the active alkaloids, and to exhibit more or less marked symptoms.


[42] Compt. Rend., t. xci. p. 306.


Insects.—The author devoted considerable time, in the autumn of 1882, to observations on the effect of certain alkaloids on the common blow-fly, thinking it possible that the insect would exhibit a sufficient series of symptoms of physiological phenomena to enable it to be used by the toxicologist as a living reagent. If so, the cheapness and ubiquity of the tiny life during a considerable portion of the year would recommend it for the purpose. Provided two blow-flies are caught and placed beneath glass shades—the one poisoned, the other not—it is surprising what a variety of symptoms can, with a little practice, be distinguished. Nevertheless, the absence of pupils, and the want of respiratory and cardiac movements, are, in an experimental point of view, defects for which no amount or variety of merely muscular symptoms can compensate.

From the nature of the case, we can only distinguish in the poisoned fly dulness or vivacity of movement, loss of power in walking on smooth surfaces, irritation of the integument, disorderly movements of the limbs, protrusion of the fleshy proboscis, and paralysis, whether of legs or wings. My experiments were chiefly made by smearing the extracts or neutral solutions of poisons on the head of the fly. In this way some of it is invariably taken into the system, partly by direct absorption, and partly by the insect’s efforts to free itself from the foreign substance, in which it uses its legs and proboscis. For the symptoms witnessed after the application of saponin, digitalin, and aconitine, the reader is referred to the articles on those substances.

In poisoning by sausages, bad meat, curarine, and in obscure cases generally, in the present state of science, experiments on living animals are absolutely necessary. In this, and in this way only, in very many instances, can the expert prove the presence of zymotic, or show the absence of chemical poison.

The Vivisection Act, however, effectually precludes the use of life-tests in England save in licensed institutions. Hence the “methods” of applying life-tests described in former editions will be omitted.

§ 29. Effect of poisons on the heart of Cold-blooded Animals.—The Vivisection Act does not, however, interfere with the use of certain living tests, such, for instance, as the testing of the action of poisons upon the recently extirpated hearts of cold-blooded animals.

Williams’ Apparatus.

The heart of the frog, of the turtle, of the tortoise, and of the shark will beat regularly for a long time after removal from the body, if supplied with a regular stream of nutrient fluid. The fluids used for this purpose are the blood of the herbivora diluted with common salt solution, or a serum albumin solution, or a 2 per cent. solution of gum arabic in which red blood corpuscles are suspended. The simplest apparatus to use is that known as “Williams’.” Williams’ apparatus consists of two glass bulbs (see diagram), the one, P, containing nutrient fluid to which a known quantity of the poison has been added; the other, N, containing the same fluid but to which no poison has been added; these bulbs are connected by caoutchouc tubing to a three-way tube, T, and each piece of caoutchouc tubing has a pressure screw clip, V1 and V; the three-way tube is connected with a wider tube containing a valve float, F, which gives free passage of fluid in one direction only, that is, in the direction of the arrow; this last wide tube is connected with a Y piece of tubing, which again is connected with the aorta of the heart under examination, the other leg of the Y tube is connected with another wide tube, X, having a float valve, F²: the float containing a drop of mercury and permitting (like the float valve F) passage in one direction only of fluid, it is obvious that if the clip communicating with N is opened and the clip communicating with P is closed, the normal fluid will circulate alone through the heart; if, on the other hand, the P clip is open and the N clip closed, the poisoned blood will alone feed the heart. It is also clear that by raising or depressing the bulbs, the circulating fluid can be delivered at any pressure, high or low. Should a bubble of air get into the tubes, it can be got rid of by removing the cork at S and bringing the fluid up to the level of the top of the aperture. The observation is made by first ascertaining the number and character of the beats when the normal fluid is circulating, and then afterwards when the normal is replaced by the poisoned fluid. A simpler but less accurate process is to pith two frogs, excise their respective hearts, and place the hearts in watch-glasses containing either serum or a solution of common salt (strength 0·75 per cent.); to the one heart is now added a solution of the poison under examination, and the difference in the behaviour and character of the beats noted.

The phenomena to be specially looked for are the following:

  1. The heart at the height of the poisoning is arrested in diastole.
  2. The heart at the height of the poisoning is arrested in systole.

Arrest in diastole.—The arrest may be preceded by the contractions becoming weaker and weaker, or after the so-called heart peristalsis; or it may be preceded by a condition in which the auricle shows a different frequency to the ventricle.

The final diastole may be the diastole of paralysis or the diastole of irritation.

The diastole of irritation is produced by a stimulus of the inhibitory ganglia, and only occurs after poisoning by the muscarine group of poisons. This condition may be recognised by the fact that contraction may be excited by mechanical and electrical stimuli or by the application of atropine solution; the latter paralyses the inhibitory nervous centres, and therefore sets the mechanism going again. The diastole of paralysis is the most frequent form of death. It may readily be distinguished from the muscarine diastole; for, in muscarine diastole, the heart is full of blood and larger than normal; but in the paralytic form the heart is not fully extended, besides which, although, if normal blood replace that which is poisoned, the beats may be restored for a short time, the response is incomplete, and the end is the same; besides which, atropine does not restore the beats. The diastole of paralysis may depend on paralysis of the so-called excito-motor ganglia (as with iodal), or from paralysis of the muscular structure (as with copper).§ 30. The effect of poisons on the iris.—Several poisons affect the pupil, causing either contraction or dilatation. The most suitable animal is the cat; the pupil of the cat readily showing either state.

Toxic myosis, or toxic contraction of the pupil.—There are two forms of toxic myosis, one of which is central in its origin. In this form, should the poison be applied to the eye itself, no marked contraction follows; the poison must be swallowed or injected subcutaneously to produce an effect. The contraction remains until death.

The contraction in such a case is considered to be due to a paralysis of the dilatation centre; it is a “myosis paralytica centralis;” the best example of this is the contraction of the pupil caused by morphine.

In the second case the poison, whether applied direct to the eye or entering the circulation by subcutaneous injection, contracts the pupil; the contraction persists if the eye is extirpated, but in all cases the contraction may be changed into dilatation by the use of atropine. An example of this kind of myosis is the action of muscarine. It is dependent on the stimulation of the ends of the nerves which contract the pupil, especially the ends of the nervus oculomotorius supplying the sphincter iridis; this form of myosis is called myosis spastica periphera. A variety of this form is the myosis spastica muscularis, depending on stimulation of the musc. sphincter iridis, seen in poisoning by physostigmine. This causes strong contraction of the pupil when locally applied; the contraction is not influenced by small local applications of atropine, but it may be changed to dilatation by high doses. Subcutaneous injection of small doses of physostigmine does not alter the pupil, but large poisonous doses contracts the pupil in a marked manner.

Toxic mydriasis, or toxic dilatation of the pupil.—The following varieties are to be noticed:

1. Toxic doses taken by the mouth or given by subcutaneous injection give rise to strong dilatation; this vanishes before death, giving place to moderate contraction. This form is due to stimulation of the dilatation centre, later passing into paralysis. An example is found in the action of aconite.

2. After subcutaneous or local application, a dilatation neutralised by physostigmine in moderate doses. This is characteristic of -tetrahydronaphthylamine.

3. After subcutaneous injection, or if applied locally in very small doses, dilatation occurs persisting to death. Large doses of physostigmine neutralise the dilatation, but it is not influenced by muscarine or pilocarpine: this form is characteristic of atropine, and it has been called mydriasis paralytica periphera.

The heart at the height of the poisoning stops in systole.

2. Arrest in systole.—The systole preceding the arrest is far stronger than normal, the ventricle often contracting up into a little lump. Contraction of this kind is specially to be seen in poisoning by digitalis. In poisoning by digitalis the ventricle is arrested before the auricle; in muscarine poisoning the auricle stops before the ventricle. If the reservoir of Williams’ apparatus is raised so as to increase the pressure within the ventricle the beat may be restored for a time, to again cease.

A frog’s heart under the influence of any poison may be finally divided into pieces so as to ascertain if any parts still contract; the significance of this is, that the particular ganglion supplying that portion of the heart has not been affected: the chief ganglia to be looked for are Remak’s, on the boundary of the sinus and auricle; Ludwig’s, on the auricle and the septum of the auricle; Bidder’s, on the atrioventricular border, especially in the valves; and Dogiel’s ganglion, between the muscular fibres. According to Dogiel, poisons acting like muscarine affect every portion of the heart, and atropine restores the contractile power of every portion.


VI.—General Method of Procedure in Searching for Poison.

§ 31. Mineral substances, or liquids containing only inorganic matters, can cause no possible difficulty to any one who is practised in analytical investigation; but the substances which exercise the skill of the expert are organic fluids or solids.

The first thing to be done is to note accurately the manner in which the samples have been packed, whether the seals have been tampered with, whether the vessels or wrappers themselves are likely to have contaminated the articles sent; and then to make a very careful observation of the appearance, smell, colour, and reaction of the matters, not forgetting to take the weight, if solid—the volume, if liquid. All these are obvious precautions, requiring no particular directions.

If the object of research is the stomach and its contents, the contents should be carefully transferred to a tall conical glass; the organ cut open, spread out on a sheet of glass, and examined minutely by a lens, picking out any suspicious-looking substance for closer observation. The mucous membrane should now be well cleansed by the aid of a wash-bottle, and if there is any necessity for destroying the stomach, it may be essential in important cases to have it photographed. The washings having been added to the contents of the stomach, the sediment is separated and submitted to inspection, for it must be remembered that, irrespective of the discovery of poison, a knowledge of the nature of the food last eaten by the deceased may be of extreme value.

If the death has really taken place from disease, and not from poison, or if it has been caused by poison, and yet no definite hint of the particular poison can be obtained either by the symptoms or by the attendant circumstances, the analyst has the difficult task of endeavouring to initiate a process of analysis which will be likely to discover any poison in the animal, vegetable, or mineral kingdom. For this purpose I have devised the following process, which differs from those that have hitherto been published mainly in the prominence given to operations in a high vacuum, and the utilisation of biological experiment as a matter of routine. Taking one of the most difficult cases that can occur—viz., one in which a small quantity only of an organic solid or fluid is available—the best method of procedure is the following:

Mercury pump

A small portion is reserved and examined microscopically, and, if thought desirable, submitted to various “cultivation” experiments. The greater portion is at once examined for volatile matters, and having been placed in a strong flask, and, if neutral or alkaline, feebly acidulated with tartaric acid, connected with a second or receiving flask by glass tubing and caoutchouc corks. The caoutchouc cork of the receiving flask has a double perforation, so as to be able, by a second bit of angle tubing, to be connected with the mercury-pump described in the author’s work on “Foods,” the figure of which is here repeated (see the accompanying figure). With a good water-pump having a sufficient length of fall-tube, a vacuum may be also obtained that for practical purposes is as efficient as one caused by mercury; if the fall-tube delivers outside the laboratory over a drain, no offensive odour is experienced when dealing with putrid, stinking liquids. A vacuum having been obtained, and the receiving-flask surrounded with ice, a distillate for preliminary testing may be generally got without the action of any external heat; but if this is too slow, the flask containing the substances or liquid under examination may be gently heated by a water-bath—water, volatile oils, a variety of volatile substances, such as prussic acid, hydrochloric acid, phosphorus, &c., if present, will distil over. It will be well to free in this way the substance, as much as possible, from volatile matters and water. When no more will come over, the distillate may be carefully examined by redistillation and the various appropriate tests.

The next step is to dry the sample thoroughly. This is best effected also in a vacuum by the use of the same apparatus, only this time the receiving-flask is to be half filled with strong sulphuric acid. By now applying very gentle heat to the first flask, and cooling the sulphuric acid receiver, even such substances as the liver in twenty-four hours may be obtained dry enough to powder.

Ether recovery apparatus

This figure is from “Foods.” B is a bell-jar, which can be adapted by a cork to a condenser; R is made of iron; the rim of the bell-jar is immersed in mercury, which the deep groove receives.

Having by these means obtained a nearly dry friable mass, it is reduced to a coarse powder, and extracted with petroleum ether; the extraction may be effected either in a special apparatus (as, for example, in a large “Soxhlet”), or in a beaker placed in the “Ether recovery apparatus” (see fig.), which is adapted to an upright condenser. The petroleum extract is evaporated and leaves the fatty matter, possibly contaminated by traces of any alkaloid which the substance may have contained; for, although most alkaloids are insoluble in petroleum ether, yet they are taken up in small quantities by oils and fats, and are extracted with the fat by petroleum ether. It is hence necessary always to examine the petroleum extract by shaking it up with water, slightly acidulated with sulphuric acid, which will extract from the fat any trace of alkaloid, and will permit the discovery of such alkaloids by the ordinary “group reagents.”

The substance now being freed for the most part from water and from fat, is digested in the cold with absolute alcohol for some hours; the alcohol is filtered off, and allowed to evaporate spontaneously, or, if speed is an object, it may be distilled in vacuo. The treatment is next with hot alcohol of 90 per cent., and, after filtering, the dry residue is exhausted with ether. The ether and alcohol, having been driven off, leave extracts which may be dissolved in water and tested, both chemically and biologically, for alkaloids, glucosides, and organic acids. It must also be remembered that there are a few metallic compounds (as, for example, corrosive sublimate) which are soluble in alcohol and ethereal solvents, and must not be overlooked.

The residue, after being thus acted upon successively by petroleum, by alcohol, and by ether, is both water-free and fat-free, and also devoid of all organic poisonous bases and principles, and it only remains to treat it for metals. For this purpose, it is placed in a retort, and distilled once or twice to dryness with a known quantity of strong, pure hydrochloric acid.

If arsenic, in the form of arsenious acid, were present, it would distil over as a trichloride, and be detected in the distillate; by raising the heat, the organic matter is carbonised, and most of it destroyed. The distillate is saturated with hydric sulphide, and any precipitate separated and examined. The residue in the retort will contain the fixed metals, such as zinc, copper, lead, &c. It is treated with dilute hydrochloric acid, filtered, the filtrate saturated with SH2 and any precipitate collected. The filtrate is now treated with sufficient sodic acetate to replace the hydric chloride, again saturated with SH2 and any precipitate collected and tested for zinc, nickel, and cobalt. By this treatment, viz.:

  1. Distillation in a vacuum at a low temperature,
  2. Collecting the volatile products,
  3. Dehydrating the organic substances,
  4. Dissolving out from the dry mass fatty matters and alkaloids, glucosides, &c., by ethereal and alcoholic solvents,
  5. Destroying organic matter and searching for metals,

—a very fair and complete analysis may be made from a small amount of material. The process is, however, somewhat faulty in reference to phosphorus, and also to oxalic acid and the oxalates; these poisons, if suspected, should be specially searched for in the manner to be more particularly described in the sections treating of them. In most cases, there is sufficient material to allow of division into three parts—one for organic poisons generally, one for inorganic, and a third for reserve in case of accident. When such is the case, although, for organic principles, the process of vacuum distillation just described still holds good, it will be very much the most convenient way not to use that portion for metals, but to operate on the portion reserved for the inorganic poisons as follows by destruction of the organic matter.

The destruction of organic matter through simple distillation by means of pure hydrochloric acid is at least equal to that by sulphuric acid, chlorate of potash, and the carbonisation methods. The object of the chemist not being to dissolve every fragment of cellular tissue, muscle, and tendon, but simply all mineral ingredients, the less organic matter which goes into solution the better. That hydrochloric acid would fail to dissolve sulphate of baryta and sulphate of lead, and that sulphide of arsenic is also almost insoluble in the acid, is no objection to the process recommended, for it is always open to the analyst to treat the residue specially for these substances. The sulphides precipitated by hydric sulphide from an acid solution are—arsenic, antimony, tin, cadmium, lead, bismuth, mercury, copper, and silver. Those not precipitated are—iron, manganese, zinc, nickel, and cobalt.

As a rule, one poison alone is present; so that if there should be a sulphide, it will belong only exceptionally to more than one metal.

The colour of the precipitate from hydric sulphide is either yellowish or black. The yellow and orange precipitates are sulphur, sulphides of arsenic, antimony, tin, and cadmium. In pure solutions they may be almost distinguished by their different hues, but in solutions contaminated by a little organic matter the colours may not be distinctive. The sulphide of arsenic is of a pale yellow colour; and if the very improbable circumstance should happen that arsenic, antimony, and cadmium occur in the same solution, the sulphide of arsenic may be first separated by ammonia, and the sulphide of antimony by sulphide of sodium, leaving cadmic sulphide insoluble in both processes.

The black precipitates are—lead, bismuth, mercury, copper, and silver. The black sulphide is freed from arsenic, if present, by ammonia, and digested with dilute nitric acid, which will dissolve all the sulphides, save those of mercury and tin, so that if a complete solution is obtained (sulphur flocks excepted), it is evident that both these substances are absent. The presence of copper is betrayed by the blue colour of the nitric acid solution, and through its special reactions; lead, by the deep yellow precipitate which falls by the addition of chromate of potash and acetate of soda to the solution; bismuth, through a white precipitate on dilution with water. If the nitric acid leaves a black insoluble residue, this is probably sulphide of mercury, and should be treated with concentrated hydrochloric acid to separate flocks of sulphur, evaporated to dryness, again dissolved, and tested for mercury by iodide of potassium, copper foil, &c., as described in the article on Mercury. Zinc, nickel, and cobalt are likewise tested for in the filtrate as described in the respective articles on these metals.


AUTENRIETH’S GENERAL PROCESS.

§ 32. A general method of procedure has been published by W. Autenrieth.[43]


[43] Kurze Anleitung zur Auffindung der Gifte, Freiburg, 1892.


He divides poisonous substances, for the purposes of separation and detection, into three classes:

  1. Poisons capable of distillation from an acid aqueous solution.
  2. Organic substances which are not capable of distillation from acid solutions.
  3. Metallic poisons.

Where possible, the fluid or solids submitted to the research are divided into four equal parts, one of the parts to be kept in reserve in case of accident or as a control; one of the remaining three parts to be distilled; a second to be investigated for organic substances; and a third for metals. After the extraction of organic substances from part No. II. the residue may be added to No. III. for the purpose of search after metals; and, if the total quantity is small, the whole of the process may be conducted without division.

I. SUBSTANCES SEPARATED BY DISTILLATION.

The substances are placed in a capacious flask, diluted if necessary with water to the consistence of a thin soup, and tartaric acid added to distinct acid reaction, and distilled.

In this way phosphorus, prussic acid, carbolic acid, chloroform, chloral hydrate, nitrobenzol, aniline,[44] and alcohol may be separated and identified by the reactions given in the sections of this work describing those substances.


[44] Aniline is a weak base, so that, although a solution be acid, some of the aniline distils over on heating.


II. ORGANIC POISONS NOT VOLATILE IN ACID SOLUTION.

Part No. II. is mixed with double its volume of absolute alcohol, tartaric acid added to distinct acid reaction and placed in a flask connected with an inverted Liebig’s condenser; it is then warmed for 15 to 20 minutes on the water-bath. After cooling, the mixture is filtered, the residue well washed with alcohol and evaporated to a thin syrup in a porcelain dish over the water-bath. The dish is then allowed to cool and digested with 100 c.c. of water; fat and resinous matters separate, the watery solution is filtered through Swedish paper previously moistened: if the fluid filtrate is clear it may be at once shaken up with ether, but if not clear, and especially if it is more or less slimy, it is evaporated again on the water-bath to the consistence of an extract: the extract treated with 60 to 80 c.c. of absolute alcohol (which precipitates mucus and dextrin-like substances), the alcohol evaporated off and the residue taken up with from 60 to 80 c.c. of distilled water; it is then shaken up with ether, as in Dragendorff’s process, and such substances as digitalin, picric acid, salicylic acid, antipyrin and others separated in this way and identified.

After this treatment with ether, and the separation of the ether extract, the watery solution is strongly alkalised with caustic soda and shaken up again with ether, which dissolves almost every alkaloid save morphine and apomorphine; the ethereal extract is separated and any alkaloid left identified by suitable tests.

The aqueous solution, now deprived of substances soluble in ether both from acid and from solutions made alkaline by soda, is now investigated for morphine and apomorphine; the apomorphine being separated by first acidifying a portion of the alkaline solution with hydrochloric acid, then alkalising with ammonia and shaking out with ether. The morphine is separated from the same solution by shaking out with warm chloroform.[45]


[45] Hot amyl alcohol would be better (see “Morphine”).


III. METALS.

The substances are placed in a porcelain dish and diluted with a sufficient quantity of water to form a thin soup and 20 to 30 c.c. of pure hydrochloric acid added; the dish is placed on the water-bath and 2 grms. of potassic chlorate added. The contents are stirred from time to time, and successive quantities of potassic chlorate are again added, until the contents are coloured yellow. The heating is continued, with, if necessary, the addition of more acid, until all smell of chlorine has ceased. If there is considerable excess of acid, this is to be evaporated away by diluting with a little water and continuing to heat on the water-bath. The dish with its contents is cooled, a little water added, and the fluid is then filtered.

The metals remaining on the filter are:

  • Silver chloride,
  • Lead sulphate,
  • Barium sulphate;

in the filtrate will be all the other metals.

The filtrate is put in a flask and heated to from 60 to 80 degrees and submitted to a slow stream of hydric sulphide gas; when the fluid is saturated with the gas, the flask is securely corked and allowed to rest for twelve hours; at the end of that time the fluid is filtered and the filter washed with water saturated with hydric sulphide.

The still moist sulphides remaining on the filter are treated with yellow ammonium sulphide containing some free ammonia and washed with sulphide of ammonium water. Now remaining on the filter, if present at all, will be:

  • Mercury sulphide,
  • Lead sulphide,
  • Copper sulphide,
  • Cadmium sulphide;

in the filtrate may be:

  • Arsenic sulphide,
  • Antimony sulphide,
  • Tin sulphide,

and there may also be a small portion of copper sulphide, because the latter is somewhat soluble in a considerable quantity of ammonium sulphide.

The filtrate from the original hydric sulphide precipitate will contain, if present, the sulphides of zinc and chromium in solution.


INVESTIGATION OF THE SULPHIDES SOLUBLE IN AMMONIUM SULPHIDE, VIZ., ARSENIC, ANTIMONY, TIN.

The ammonium sulphide solution is evaporated to dryness in a porcelain dish, strong nitric acid added and again dried. To this residue a little strong caustic soda solution is added, and then it is intimately mixed with three times its weight of a mixture composed of 2 of potassic nitrate to 1 of dry sodium hydrate. This is now cast, bit by bit, into a red-hot porcelain crucible. The whole is heated until it has melted into a colourless fluid.

Presuming the original mass contained arsenic, antimony, and tin, the melt contains sodic arseniate, sodic pyro-antimonate, sodic stannate, and tin oxide; it may also contain a trace of copper oxide.

The melt is cooled, dissolved in a little water, and sodium bicarbonate added so as to change any caustic soda remaining into carbonate, and to decompose the small amount of sodic stannate; the liquid is then filtered.

The filtrate will contain the arsenic as sodic arseniate; while on the filter there will be pyro-antimonate of soda, tin oxide, and, possibly, a little copper oxide.

The recognition of these substances now is not difficult (see the separate articles on Antimony, Tin, Zinc, Arsenic, Copper).


INVESTIGATION OF THE SULPHIDES INSOLUBLE IN SULPHIDE OF AMMONIUM, VIZ., MERCURY, LEAD, COPPER, CADMIUM.

If the precipitate is contaminated with organic matter, it is treated with hydrochloric acid and potassic chlorate in the manner already described, p. 51.

Afterwards it is once more saturated with hydric sulphide, the precipitate is collected on a filter, well washed, and the sulphides treated with moderately concentrated nitric acid (1 vol. nitric acid, 2 vols. water). The sulphides are best treated with this solvent on the filter; all the sulphides mentioned, save mercury sulphide, dissolve and pass into the filtrate. This mercury sulphide may be dissolved by nitro-muriatic acid, the solution evaporated to dryness, the residue dissolved in water acidified with hydrochloric acid and tested for mercury (see “Mercury”).

The filtrate containing, it may be, nitrates of lead, copper and cadmium is evaporated nearly to dryness and taken up in a very little water. The lead is separated as sulphate by the addition of dilute sulphuric acid.

The filtered solution, freed from lead, is treated with ammonia to alkaline reaction; if copper be present, a blue colour is produced, and this may be confirmed by other tests (see “Copper”). To detect cadmium in the presence of copper, potassic cyanide is added to the blue liquid until complete decolorisation, and the liquid treated with SH2; if cadmium be present, it is thrown down as a yellow sulphide, while potassic cupro-cyanide remains in solution.


SEARCH FOR ZINC AND CHROMIUM.

The filtrate from the hydric sulphide precipitate is divided into two parts; the one half is used in the search for zinc, the other half is used for chromium.

Search for Zinc.—The liquid is alkalised with ammonia and then ammonium sulphide is added. There will always be a precipitate of a dark colour; the precipitate will contain earthy phosphates, iron and, in some cases, manganese. The liquid with the precipitate is treated with acetic acid to strong acid reaction and allowed to stand for several hours. The portion of the precipitate remaining undissolved is collected on a filter, washed, dried and heated to redness in a porcelain crucible. The residue thus heated is cooled and dissolved in a little dilute sulphuric acid. To the acid solution ammonia is added, and any precipitate formed is treated with acetic acid; should the precipitate not completely dissolve, phosphate of iron is present; this is filtered off, and if SH2 be added to the filtrate, white zinc sulphide will come down (see “Zinc”).

Search for Chromium.—The second part of the SH2 filtrate is evaporated to a thin extract, mixed with double its weight of sodic nitrate, dried and cast, little by little, into a red-hot porcelain crucible. When the whole is fully melted, the crucible is removed from the flame, cooled, and the mass dissolved in water and filtered. Any chromium present will now be in solution in the easily recognised form of potassic chromate (see “Chromium”).

INVESTIGATION OF THE RESIDUE (p. 52) AFTER THE TREATMENT OF THE ORIGINAL SUBSTANCE WITH HYDROCHLORIC ACID AND POTASSIC CHLORATE FOR PRESENCE OF SILVER CHLORIDE, LEAD AND BARIUM SULPHATES.

The residue is dried and intimately mixed with three times its weight of a mixture containing 2 parts of sodic nitrate and 1 part of sodium hydrate, This is added, little by little, into a red-hot porcelain crucible. The melted mass is cooled, dissolved in a little water, a current of CO2 passed through the solution to convert any caustic soda into carbonate, and the solution boiled. The result will be an insoluble portion consisting of carbonates of lead and baryta, and of metallic silver. The mixture is filtered; the insoluble residue on the filter is warmed for some time with dilute nitric acid; the solution of nitrates of silver, lead and barium are concentrated on the water-bath nearly to dryness so as to get rid of any excess of acid, and the nitrates dissolved in water; then the silver is precipitated by hydrochloric acid, the lead by SH2, and the barium by sulphuric acid.


VII.—The Spectroscope as an aid to the Identification of certain Poisons.

§ 33. The spectra of many of the metals, of phosphine, of arsine and of several other inorganic substances are characteristic and easily obtained.

It is, however, from the employment of the micro-spectroscope that the toxicologist is likely to get most assistance.

Spectroscope

Oscar Brasch[46] has within the last few years studied spectroscopy in relation to the alkaloids and organic poisons. Some of these, when mixed with Froehde’s reagent, or with sulphuric acid, or with sulphuric acid and potassic dichromate, or with nitric acid, give characteristic colours, and the resulting solutions, when examined by a spectroscope, for the most part show absorption bands; these bands may, occasionally, assist materially in the identification of a poison. By far the best apparatus is a micro-spectroscope of the Sorby and Browning type, to which is added an apparatus for measuring the position on a scale of the lines and bands. Seibert and Kraft of Wetzlar make an excellent instrument, in which a small bright triangle is projected on the spectrum; this can be moved by a screw, so that the apex may be brought exactly in the centre of any line or band, and its position read on an outside scale. The first thing to be done with such an instrument is to determine the position on the scale of the chief Fraunhofer lines or of the more characteristic lines of the alkalies and alkaline earths,[47] the wave lengths of which are accurately known. If, now, the scale divisions are set out as abscissÆ, and the wave lengths in millionths of a millimetre are made the ordinates of a diagram, and an equable curve plotted out, as fully explained in the author’s work on “Foods,” it is easy to convert the numbers on the scale into wave lengths, and so make the readings applicable to any spectroscope. For the purpose of graphical illustration the curve method is convenient, and is adopted in the preceding diagrams, all taken from Oscar Brasch’s monograph. Where the curve is highest there the absorption band is thickest; where the curve is lowest there the band is weak. The fluid to be examined is simply placed in a watch-glass, the watch-glass resting on the microscope stand.


[46] Ueber Verwendbarkeit der Spectroscopie zur Unterscheidung der Farbenreactionen der Gifte im Interesse der forensischen Chemie, Dorpat, 1890.[47] The alkalies and earths used for this purpose, with their wave lengths, are as follows: KCl, a line in the red ? 770, in the violet ? 404. Lithium chloride, red line, 670·5; sodium chloride, yellow, 589; strontium chloride, line in the blue, 461. It is also useful to measure the green line of thallium chloride = 535.


CURVES INDICATING THE POSITION OF ABSORPTION BANDS ON TREATING CERTAIN ALKALOIDS WITH REAGENTS.

Absorption bands

NOTES TO CURVES INDICATING ABSORPTION BANDS.

  1. Strychnine, treated with sulphuric acid and potassic dichromate (violet).
  2. Brucine, treated with potassic nitrate and sulphuric acid (clear red).
  3. Quebrachine, treated with vanadium sulphate (dark blue).
  4. Quinine, Vogel’s reaction (red).
  5. Caffein, Murexid reaction (violet-red).
  6. Dephinoidin, Froehde’s reagent (cherry-red).
  7. Veratrine, treated with sulphuric acid (straw-yellow).
  8. Verarine, treatewith sulpuric acid(cherry-red).
  9. Verarine, treatewith sulpuric acid(carmine-red).
  10. Veratrine, Furfurol reaction (blue-violet).
  11. Sabadillin, treated with sulphuric acid (red).
  12. Veratroidine,eatedwith sulphric acid (brown-red).
  13. Jervine, Furfurol reaction (blue).
  14. Sabadine, ururol reation (blue).
  15. Sabadine, treated with sulphuric acid (cherry-red).
  16. Physostigmine,edith sulphric acid(grass-green).
  17. Morphine, treated with Froehde’s reagent and sugar (dark-green).
  18. Narcotine, treated with a mixture of sulphuric acid and nitric acid (30 drops of sulphuric to 1 drop of nitric), (red).
  19. Codeine, treated with Froehde’s reagent and sugar (dark violet).
  20. Papaverine, treated with Froehde’s reagent (green-blue).
  21. Sanguinarin, reatd with Froehe’s reagent(violet-red).
  22. Chelidonin,treated with sulphate of vanadium (dark green).
  23. Solanin,in, treated with sulphuric acid and allowed to stand 4 hours (brown-red).
  24. Digitalin,n, treated with Erdmann’s reagent (red).
  25. Aniline, in, treated with sulphuric acid and potassic dichromate (blue).

The wave lengths corresponding to the numbers on the scale in the diagram are as follows:

W.L.
0 732
1 656
2 589 ·2
3 549 ·8
4 510 ·2
5 480 ·0
6 458
7 438

Examination of Blood, or of Blood-Stains.

§ 34. Spots, supposed to be blood—whether on linen, walls, or weapons—should, in any important case, be photographed before any chemical or microscopical examination is undertaken. Blood-spots, according to the nature of the material to which they are adherent, have certain naked eye peculiarities—e.g., blood on fabrics, if dry, has at first a clear carmine-red colour, and part of it soaks into the tissue. If, however, the tissue has been worn some time, or was originally soiled, either from perspiration, grease, or filth, the colour may not be obvious or very distinguishable from other stains; nevertheless, the stains always impart a certain stiffness, as from starch, to the tissue. If the blood has fallen on such substances as wood or metal, the spot is black, has a bright glistening surface, and, if observed by a lens, exhibits radiating fissures and a sort of pattern, which, according to some, is peculiar to each species; so that a skilled observer might identify occasionally, from the pattern alone, the animal whence the blood was derived. The blood is dry and brittle, and can often be detached, or a splinter of it, as it were, obtained. The edges of the splinter, if submitted to transmitted light, are observed to be red. Blood upon iron is frequently very intimately adherent; this is specially the case if the stain is upon rusty iron, for hÆmatin forms a compound with iron oxide. Blood may also have to be recovered from water in which soiled articles have been washed, or from walls, or from the soil, &c. In such cases the spot is scraped off from walls, plaster, or masonry, with as little of the foreign matters as may be. It is also possible to obtain the colouring-matter of blood from its solution in water, and present it for farther examination in a concentrated form, by the use of certain precipitating agents (see p. 61).

In the following scheme for the examination of blood-stains, it is presumed that only a few spots of blood, or, in any case, a small quantity, is at the analyst’s disposal.

(1) The dried spot is submitted to the action of a cold saturated solution of borax. This medium (recommended by Dragendorff)[48] does certainly dissolve out of linen and cloth blood-colouring matter with great facility. The best way to steep the spots in the solution is to scrape the spot off the fabric, and to digest it in about a cubic centimetre of the borax solution, which must not exceed 40°; the coloured solution may be placed in a little glass cell, with parallel walls, ·5 centimetre broad, and ·1 deep, and submitted to spectroscopic examination, either by the ordinary spectroscope or by the micro-spectroscope; if the latter is used, a very minute quantity can be examined, even a single drop. In order to interpret the results of this examination properly, it will be necessary to be intimately acquainted with the spectroscopic appearances of both ancient and fresh blood.


[48] Untersuchungen von Blutspuren in Maschka’s Handbuch, Bd. i. Halfband 2.


§ 35. Spectroscopic Appearances of Blood.—If defibrinated blood[49] be diluted with water until it contains about ·01 per cent. of oxyhÆmoglobin, and be examined by a spectroscope, the layer of liquid being 1 centimetre thick, a single absorption band between the wave lengths 583 and 575 is observed, and, under favourable circumstances, there is also to be seen a very weak band from 550 to 532. With solutions so dilute as this, there is no absorption at either the violet or the red end of the spectrum. A solution containing ·09 per cent. of oxyhÆmoglobin shows very little absorption in the red end, but the violet end is dark up to about the wave length 428. Two absorption bands may now be distinctly seen. A solution containing ·37 per cent. of oxyhÆmoglobin shows absorption of the red end to about W.L. 720; the violet is entirely, the blue partly, absorbed to about 453. The bands are considerably broader, but the centre of the bands occupies the same relative position. A solution containing as much as ·8 per cent. of oxyhÆmoglobin is very dark; the two bands have amalgamated, the red end of the spectrum is absorbed nearly up to Fraunhofer’s line a; the green is just visible between W.L. 498 and 518. Venous blood, or arterial blood, which has been treated with reducing agents, such, for example, as an alkaline sulphide, gives the spectrum of reduced hÆmoglobin. If the solution is equivalent to about ·2 per cent., a single broad band, with the edges very little defined, is seen to occupy the space between W.L. 595 and 538, the band being darkest about 550; both ends of the spectrum are more absorbed than by a solution of oxyhÆmoglobin of the same strength. In the blood of persons or animals poisoned with hydric sulphide—to the spectrum of reduced hÆmoglobin, there is added a weak absorption band in the red, with its centre nearly corresponding with the Fraunhofer line C. Blood which has been exposed to carbon oxide has a distinct spectrum, due, it would seem, to a special combination of this gas with hÆmoglobin; in other words, instead of oxygen, the oxygen of oxyhÆmoglobin has been displaced by carbon oxide, and crystals of carbon oxide-hÆmoglobin, isomorphous with those of oxyhÆmoglobin, may be obtained by suitable treatment. The spectrum of carbon oxide-hÆmoglobin, however, differs so little from that of normal blood, that it is only comparison with the ordinary spectrum, or careful measurements, which will enable any person, not very familiar with the different spectra of blood, to detect it; with careful and painstaking observation the two spectra are seen to be distinct. The difference between the carbon oxide and the normal spectrum essentially consists in a slight moving of the bands nearer to E. According to the measurements of Gamgee, the band a of CO-hÆmoglobin has its centre approximately at W.L. 572, and the band has for its centre W.L. from 534 to 538, according to concentration. If a small quantity of an ammoniacal solution of ferrous tartrate or citrate be added to blood containing carbon oxide, the bands do not wholly fade, but persist more or less distinctly; whereas, if the same solution is added to bright red normal blood, the two bands vanish instantly and coalesce to form the spectrum of reduced hÆmoglobin. When either a solution of hÆmoglobin or blood is exposed to the air for some time, it loses its bright red colour, becomes brownish-red, and presents an acid reaction. On examining the spectrum, the two bands have become faint, or quite extinct; but there is a new band, the centre of which (according to Gamgee) occupies W.L. 632, but (according to Preyer) 634. In solutions of a certain strength, four bands may be seen, but in a strong solution only one. This change in the spectrum is due to the passing of the hÆmoglobin into methÆmoglobin, which may be considered as an intermediate stage of decomposition, prior to the breaking up of the hÆmoglobin into hÆmatin and proteids.


[49] In this brief notice of the spectroscopic appearances of the blood, the measurements in wave lengths are, for the most part, after Gamgee.—Text-Book of Physiological Chemistry, London, 1880.


A spectrum very similar to that of methÆmoglobin is obtained by treating ancient blood-stains with acetic acid—viz., the spectrum of acid hÆmatin, but the band is nearer to its centre, according to Gamgee, corresponding to W.L. 640 (according to Preyer, 656·6). The portion of the band is a little different in alkaline solution, the centre being about 592. HÆmatin is one of the bodies into which hÆmoglobin splits up by the addition of such agents as strong acetic acid, or by the decomposing influence of exposure; the view most generally accepted being that the colouring-matter of the blood is hÆmatin in combination with one or more albuminoid bodies. The hÆmatin obtained by treating blood with acetic acid may be dissolved out by ether, and the ethereal solution then exhibits a remarkable distinctive spectrum. Hence, in the spectroscopic examination of blood, or solutions of blood, for medico-legal purposes, if the blood is fresh, the spectrum likely to be seen is either that of oxyhÆmoglobin or hÆmoglobin; but, if the blood-stain is not recent, then the spectrum of either hÆmatin or methÆmoglobin.

The colouring-matter of cochineal, to which alum, potassic carbonate, and tartrate have been added, gives a spectrum very similar to that of blood (see “Foods,” p. 82); but this is only the case when the solution is fresh. The colour is at once discharged by chlorine, while the colour of blood, although changed in hue, remains. The colouring-matter of certain red feathers, purpurin-sulphuric acid, and a few other reds, have some similarity to either the hÆmatin or the hÆmoglobin spectrum, but the bands do not strictly coincide; besides, no one would trust to a single test, and none of the colouring-matters other than blood yield hÆmatin.

The blood in CO poisoning has also other characteristics. It is of a peculiar florid vermilion colour, a colour that is very persistent, lasting for days and even weeks.

Normal blood mixed with 30 per cent. potash solution forms greenish streaky clots, while blood charged with CO forms red streaky clots.

Normal blood diluted to 50 times its volume of water, and then treated successively with yellow ammonium sulphide in the proportion of 2 to 25 c.c. of blood, followed by three drops of acetic acid, gives a grey colour, while CO blood remains bright red. CO blood shaken with 4 times its volume of lead acetate remains red, but normal blood becomes brown.[50]


[50] M. Rubner, Arch. Hyg., x. 397.


Solutions of platinum chloride or zinc chloride give a bright red colour with CO blood; normal blood is coloured brown or very dark brown.

Phospho-molybdic acid or 5 per cent. phenol gives a carmine-coloured precipitate with CO blood, but a reddish-brown precipitate with normal blood (sensitive to 16 per cent.).

A mixture of 2 c.c. of dilute acetic acid and 15 c.c. of 20 per cent. potassic ferrocyanide solution added to 10 c.c. of CO blood produces an intense bright red; normal blood becomes dark brown.

Four parts of CO blood, diluted with 4 parts of water and shaken with 3 vols. of 1 per cent. tannin solution, become at first bright red with a bluish tinge, and remain so persistently. Normal blood, on the other hand, also strikes bright red at first, but with a yellowish tinge; at the end of 1 hour it becomes brownish, and finally in 24 hours grey. This is stated to be delicate enough to detect 0·0023 per cent. in air.

If blood be diluted with 40 times its volume of water, and 5 drops of phenylhydrazin solution be added, CO blood strikes rose-red; normal blood grey-violet.[51]


[51] A. Welzel, Centr. med. Wiss., xxvii. 732-734.


Gustave Piotrowski[52] has experimented on the length of time blood retains CO. The blood of dogs poisoned by this agent was kept in flasks, and then the gas pumped out by means of a mercury pump on the following dates:


[52] Compt. Rend. Soc. de Biol., v. 433.


Date. Content of
gas in CO.
Jan. 12, 1892, 24·7 per cent.
J 20, 23·5
J 28, 22·2
Feb. 8, 20·3
F 16, 15·5
F 26, 10·2
March 3, 6·3
Ma 14, 4·6
Ma 22, 1·2

The same dog was buried on the 12th of January, and exhumed on March 28th, and the gas pumped out from some of the blood; this gas gave 11·7 per cent. of CO; hence it is clear that burial preserves CO blood from change to a certain extent.

N. GrÉhant[53] treated the poisoned blood of a dog with acetic acid, and found it evolved 14·4 c.c. CO from 100 c.c. of blood.


[53] Compt. Rend., cvi. 289.


Stevenson, in one of the cases detailed at p. 67, found the blood in the right auricle to contain 0·03 per cent. by weight of CO.

(2) Preparation of HÆmatin Crystals—(Teichmann’s crystals).—A portion of the borax solution is diluted with 5 or 6 parts of water, and one or more drops of a 5 or 6 per cent. solution of zinc acetate added, so long as a brownish-coloured precipitate is thrown down. The precipitate is filtered off by means of a miniature filter, and then removed on to a watch-glass. The precipitate may now be dissolved in 1 or 2 c.c. of acetic acid, and examined by the spectroscope it will show the spectrum of hÆmatin. A minute crystal of sodic chloride being then added to the acetic acid solution, it is allowed to evaporate to dryness at the ordinary temperature, and crystals of hÆmatin hydrochlorate result. There are other methods of obtaining the crystals. When a drop of fresh blood is simply boiled with glacial acetic acid, on evaporation, prismatic crystals are obtained.

HÆmatin is insoluble in water, alcohol, chloroform, and in cold dilute acetic and hydrochloric acids. It may, however, be dissolved in an alcoholic solution of potassic carbonate, in solutions of the caustic alkalies, and in boiling acetic and hydrochloric acids. Hoppe-Seyler ascribes to the crystals the formula C68H70N8Fe2O102HCl. Thudichum considers that the pure crystals contain no chlorine, and are therefore those of hÆmatin. It is the resistance of the hÆmatin to decomposition and to ordinary solvents that renders it possible to identify a certain stain to be that of blood, after long periods of time. Dr. Tidy seems to have been able to obtain blood reactions from a stain which was supposed to be 100 years old. The crystals are of a dark-red colour, and present themselves in three forms, of which that of the rhombic prism is the most common (see fig.). But crystals like b, having six sides, also occur, and also crystals similar to c.

HÆmatin crystals

If the spot under examination has been scraped off an iron implement the hÆmatin is not so easily extracted, but Dragendorff states that borax solution at 50° dissolves it, and separates it from the iron. Felletar has also extracted blood in combination with iron rust, by means of warm solution of caustic potash, and, after neutralisation with acetic acid, has precipitated the hÆmin by means of tannin, and obtained from the tannin precipitate, by means of acetic acid, Teichmann’s crystals. A little of the rust may also be placed in a test tube, powdered ammonium chloride added, also a little strong ammonia, and after a time filtered; a small quantity of the filtrate is placed on a slide with a crystal of sodium chloride and evaporated at a gentle heat, then glacial acetic acid added and allowed to cool; in this way hÆmin crystals have been obtained from a crowbar fifty days after having been blood-stained.[54]


[54] Brit. Med. Journ., Feb. 17, 1894.


(3) Guaiacum Test.—This test depends upon the fact that a solution of hÆmoglobin develops a beautiful blue colour, if brought into contact with fresh tincture of guaiacum and peroxide of hydrogen. The simplest way to obtain this reaction is to moisten the suspected stain with distilled water; after allowing sufficient time for the water to dissolve out some of the blood constituents, moisten a bit of filter-paper with the weak solution thus obtained; drop on to the moist space a single drop of tincture of guaiacum which has been prepared by digesting the inner portions of guaiacum resin in alcohol, and which has been already tested on known blood, so as to ascertain that it is really good and efficient for the purpose; and, lastly, a few drops of peroxide of hydrogen. Dragendorff uses his borax solution, and, after a little dilution with water, adds the tincture and then Heunefeld’s turpentine solution, which is composed of equal parts of absolute alcohol, chloroform, and French turpentine, to which one part of acetic acid has been added. The chloroform separates, and, if blood was present, is of a blue colour.§ 36. To prove by chemical and physical methods that a certain stain is that of blood, is often only one step in the inquiry, the next question being whether the blood is that of man or of animals. The blood-corpuscles of man are larger than those of any domestic animal inhabiting Europe. The diameter of the average red blood-corpuscle is about the 1/126 of a millimetre, or 7·9 µ.[55] The corpuscles of man and of mammals, generally speaking, are round, those of birds and reptiles oval, so that there can be no confusion between man and birds, fishes or reptiles; if the corpuscles are circular in shape the blood will be that of a mammal. By careful measurements, Dr. Richardson, of Pennsylvania, affirms that it is quite possible to distinguish human blood from that of all common animals. He maintains, and it is true, that, by using very high magnifying powers and taking much trouble, an expert can satisfactorily identify human blood, if he has some half-dozen drops of blood from different animals—such as the sheep, goat, horse, dog, cat, &c., all fresh at hand for comparison, and if the human blood is normal. However, when we come to the blood of persons suffering from disease, there are changes in the diameter and even the form of the corpuscles which much complicate the matter; while, in blood-stains of any age, the blood-corpuscles, even with the most artfully-contrived solvent, are so distorted in shape that he would be a bold man who should venture on any definite conclusion as to whether the blood was certainly human, more especially if he had to give evidence in a criminal case.


[55] 1/3200 of an inch; the Greek letter µ is the micro-millimetre, or 1000th of a millimetre, ·00003937 inch.


Neumann affirms that the pattern which the fibrin or coagulum of the blood forms is peculiar to each animal, and Dr. Day, of Geelong, has independently confirmed his researches: this very interesting observation perhaps has not received the attention it merits.

When there is sufficient of the blood present to obtain a few milligrms. of ash, there is a means of distinguishing human blood from that of other common mammals, which has been neglected by authorities on the subject, and which may be found of real value. Its principle depends upon the relative amounts of potassium and sodium in the blood of man as compared with that in the blood of domestic animals. In the blood of the cow, sheep, fowl, pig, and horse, the sodium very much exceeds the potassium in the ash; thus the proportion of sodium oxide to that of potassium oxide in the blood of the sheep is as K2O ·1: Na2O ·6; in that of the cow, as 1: 8; in that of the domestic fowl, as 1: 16; while the same substances in human blood are sometimes equal, and vary from 1: 1 to 1: 4 as extremes, the mean numbers being as 1: 2·2. The potassium is greater in quantity in the blood-corpuscles than in the blood serum; but, even in blood serum, the same marked differences between the blood of man and that of many animals is apparent. Thus, the proportion of potash to soda being as 1: 10 in human blood, the proportion in sheep’s blood is 1 to 15·7; in horse’s serum as 1 to 16·4; and in the ox as 1 to 17. Since blood, when burnt, leaves from 6 to 7 per thousand of ash, it follows that a quantitative analysis of the relative amounts of potassium and sodium can only be satisfactorily effected when sufficient of the blood is at the analyst’s disposal to give a weighable quantity of mineral matter. On the other hand, much work requires to be done before this method of determining that the blood is either human, or, at all events, not that of an herbivorous animal, can be relied on. We know but little as to the effect of the ingestion of sodium or potassium salts on either man or animals, and it is possible—nay, probable—that a more or less entire substitution of the one for the other may, on certain diets, take place. Bunge seems in some experiments to have found no sodium in the blood of either the cat or the dog.

The source from which the blood has emanated may, in a few cases, be conjectured from the discovery, by microscopical examination, of hair or of buccal, nasal, or vaginal epithelium, &c., mixed with the blood-stain.

                                                                                                                                                                                                                                                                                                           

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