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II.—Growth and Development of the Modern Methods of Chemically Detecting Poisons.

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§ 8. The history of the detection of poisons has gone through several phases. The first phase has already been incidentally touched upon—i.e., detection by antecedent and surrounding circumstances, aided sometimes by experiments on animals. If the death was sudden, if the post-mortem decomposition was rapid, poison was indicated: sometimes a portion of the food last eaten, or the suspected thing, would be given to an animal; if the animal also died, such accumulation of proof would render the matter beyond doubt. The modern toxicologists are more sceptical, for even the last test is not of itself satisfactory. It is now known that meat may become filled with bacilli and produce rapid death, and yet no poison, as such, has been added.

In the next phase, the doctors were permitted to dissect, and to familiarise themselves with pathological appearances. This was a great step gained: the apoplexies, heart diseases, perforations of the stomach, and fatal internal hæmorrhages could no longer be ascribed to poison. If popular clamour made a false accusation, there was more chance of a correct judgment. It was not until the end of the eighteenth and the beginning of the present century, however, that chemistry was far enough advanced to test for the more common mineral poisons; the modern phase was then entered on, and toxicology took a new departure.

§ 9. From the treatise of Barthélémy d’Anglais[17] in the thirteenth century (in which he noticed the poisonous properties of quicksilver vapour), up to the end of the fifteenth century, there are numerous treatises upon poison, most of which are mere learned compilations, and scarcely repay perusal. In the sixteenth century, there are a few works, such, for example, as Porta, which partook of the general advancement of science, and left behind the stereotyped doctrine of the old classical schools.[18]

[17] De Rerum Proprietaribus.

[18] In the sixteenth century it was not considered proper to write upon poisons. Jerôme Cardan declared a poisoner worse than a brigand, “and that is why I have refused not only to teach or experiment on such things, but even to know them.”—J. Cardan: De Subtilitate. Basel, 1558.

In the seventeenth century the Honourable Robert Boyle made some shrewd observations, bearing on toxicology, in his work on “The usefulness of Natural Philosophy,” &c.: Oxford, 1664. Nicolas L’Emery also wrote a Cours de Chimie—quite an epitome of the chemical science of the time.[19]

[19] Cours de Chimie, contenant la manière de faire les opérations qui sont en usage dans la Médecine. Paris, 1675.

In the eighteenth century still further advances were made. Richard Mead published his ingenious Mechanical Theory of Poisons. Great chemists arose—Stahl, Marggraf, Brandt, Bergmann, Scheele, Berthollet, Priestley, and lastly, Lavoisier—and chemistry, as a science, was born. Of the chemists quoted, Scheele, in relation to toxicology, stands chief. It was Scheele who discovered prussic acid,[20] without, however, noting its poisonous properties; the same chemist separated oxalic acid from sorrel,[21] and made the important discovery that arsenic united with hydrogen, forming a fœtid gas, and, moreover, that this gas could be decomposed by heat.[22] From this observation, a delicate test for arsenic was afterwards elaborated, which for the first time rendered the most tasteless and easily administered poison in the whole world at once the easiest of detection. The further history of what is now called “Marsh’s Test” is as follows:—

[20] Opuscula Chemica, vol. ii. pp. 148–174.

[21] De Terra Rhubarbi et Acido Acetosellæ. Nova Acta Acad. Veg. Sued. Anni, 1784. Opuscula Chemica, vol. ii. pp. 187–195.

Bergmann first described oxalic acid as obtained by the oxidation of saccharine bodies; but Scheele recognised its identity with the acid contained in sorrel.

[22] Mémoires de Scheele, t. i., 1775.

§ 10. Proust[23] observed that a very fœtid hydrogen gas was disengaged when arsenical tin was dissolved in hydrochloric acid, and that arsenic was deposited from the inflamed gas on cold surfaces which the flame touched. Trommsdorff next announced, in 1803, that when arsenical zinc was introduced into an ordinary flask with water and sulphuric acid, an arsenical hydrogen was disengaged; and if the tube was sufficiently long, arsenic was deposited on its walls.[24] Stromeyer, Gay-Lussac, Thénard, Gehlen, and Davy later studied this gas, and Serullas in 1821 proposed this reaction as a toxicological test. Lastly, in 1836, Marsh published his Memoir.[25] He elaborated a special apparatus of great simplicity, developed hydrogen by means of zinc and sulphuric acid, inflamed the issuing gas, and obtained any arsenic present as a metal, which could be afterwards converted into arsenious acid, &c.

[23] Proust, Annales de Chimie, t. xxviii., 1798.

[24] Nicholson’s Journal, vol. vi.

[25] “Description of a New Process of Separating Small Quantities of Arsenic from Substances with which it is mixed.” Ed. New. Phil. Journal, 1836.

This brief history of the so-called “Marsh’s Test” amply shows that Marsh was not the discoverer of the test. Like many other useful processes, it seems to have been evolved by a combination of many minds. It may, however, be truly said that Marsh was the first who perfected the test and brought it prominently forward.

§ 11. Matthieu Joseph Bonaventura Orfila must be considered the father of modern toxicology. His great work, Traité de Toxicologie, was first published in 1814, and went through many editions. Orfila’s chief merit was the discovery that poisons were absorbed and accumulated in certain tissues—a discovery which bore immediate fruit, and greatly extended the means of seeking poisons. Before the time of Orfila, a chemist not finding anything in the stomach would not have troubled to examine the liver, the kidney, the brain, or the blood. The immense number of experiments which Orfila undertook is simply marvellous. Some are of little value, and teach nothing accurately as to the action of poisons—as, for example, many of those in which he tied the gullet in order to prevent vomiting, for such are experiments under entirely unnatural conditions; but there are still a large number which form the very basis of our pathological knowledge.

Orfila’s method of experiment was usually to take weighed or measured quantities of poison, to administer them to animals, and then after death—first carefully noting the changes in the tissues and organs—to attempt to recover by chemical means the poison administered. In this way he detected and recovered nearly all the organic and inorganic poisons then known; and most of his processes are, with modifications and improvements, in use at the present time.[26]

[26] Orfila’s chief works are as follows:— Traité de Toxicologie. 2 vols. 8vo. Paris, 1814. Leçons de Chimie, appliquées à la Méd. Pratique. 16mo. Brussels, 1836. Mémoire sur la Nicotine et la Conicine. Paris, 1851. Leçons de la Méd. Légale. 8vo. Paris, 1821. Traité des Exhumations Juridiques, et Considérations sur les Changemens Physiques que les Cadavres éprouvent en se pourrissant. 2 tom. Paris, 1831.

§ 12. The discovery of the alkaloids at the commencement of this century certainly gave the poisoner new weapons; yet the same processes (slightly modified) which separated the alkaloids from plants also served to separate them from the human body. In 1803 Derosne discovered narcotine and morphine, but he neither recognised the difference between these two substances, nor their basic properties. Sertürner from 1805 devoted himself to the study of opium, and made a series of discoveries. Robiquet, in 1807, recognised the basic characters of narcotine. In 1818 Pelletier and Caventou separated strychnine; in 1819 brucine; and in the same year delphinine was discovered simultaneously by Brande, Lassaigne, and Feneuille. Coniine was recognised by Giesecke in 1827, and in the following year, 1828, nicotine was separated by Reimann and Posselt. In 1832 Robiquet discovered codeine; and in 1833 atropine, aconitine, and hyoscyamine were distinguished by Geiger and Hesse. Since then, every year has been marked by the separation of some new alkaloid, from either animal or vegetable substances. So many workers in different countries now began to study and improve toxicology, that it would exceed the limits and be foreign to the scope of this treatise to give even a brief résumé of their labours. It may, notwithstanding, be useful to append a short bibliography of the chief works on toxicology of the present century.

§ 13.—BIBLIOGRAPHY OF THE CHIEF WORKS ON TOXICOLOGY (NINETEENTH CENTURY).

Anglada, Jos.—“Traité de Toxicologie Générale, &c.” Montpellier et Paris, 1835.

Autenrieth.—“Kurze Anleitung zur Auffindung der Gifte.” Freiburg, 1892.

Bandlin, O.—“Die Gifte.” Basel, 1869–1873.

Baumert, G.—“Lehrbuch der gerichtl. Chemie.” Braunschweig, 1889–92.

Bayard, Henri.—“Manuel Pratique de Médecine Légale.” Paris, 1843.

Bellini, Ranieri.—“Manuel de Tossicologia.” Pisa, 1878.

Berlin, N. J.—“Nachricht, die gewöhnlichen Gifte chemisch zu entdecken.” Stockholm, 1845.

Bernard, C.—“Leçons sur les Effets des Substances Toxiques et Médicamenteuses.” Paris, 1857.

Bertrand, C. A. R. A.—“Manuel Médico-Légale des Poisons introduits dans l’Estomac, et les Moyens Thérapeutiques qui leur conviennent: suivi d’un Plan d’Organisation Médico-Judiciaire, et d’un Tableau de la Classification Générale des Empoisonnemens.” Paris, 1818.

Binz, C.—“Intoxicationen” in Gerhardt’s “Handbuch der Kinderkrankheiten.” iii. Heft. Tübingen, 1878.

Blyth, A. Wynter.—“A Manual of Practical Chemistry: The Analysis of Foods and the Detection of Poisons.” London, 1879.

Bocker, Frieder. Wilhelm.—“Die Vergiftungen in forensischer u. klinischer Beziehung.” Iserlohn, 1857.

Böhm, R., Naunyn, B., und Von Boeck, H.—“Handbuch der Intoxicationen.” (Bd. 15 of the German edition of Ziemssen’s Cyclopædia.)

Brandt, Phöbus, und Ratzeburg.—“Deutschlands Giftgewächse.” Berlin, 1834–38 (2 vols. with 56 coloured plates).

Briand, J., et Chaude, Ern.—“Manuel Complet de Médecine Légale.” (The latest edition, 1879.) The chemical portion is by J. Bouis.

Buchner, E.—“Lehrbuch der gerichtlichen Medicin für Aerzte u. Juristen.” 3rd ed. München, 1872.

Casper, J. L.—“Handbuch der gerichtlichen Medicin.” 7th ed. Berlin, 1881.

Chevallier, A.—“Traité de Toxicologie et de Chimie Judiciaire.” Paris, 1868.

Chiaje, Stef.—“Enchiridis di Tossicologia teorico-pratica.” 3rd ed. Napoli, 1858.

Christison, Robert.—“A Treatise on Poisons.” Edinburgh, 1830. (A third edition appeared in 1836.)

Cornevin, C.—“Des Plantes Vénéneuses.” Paris, 1887.

Devergie, Alphonse.—“Médecine Légale, Théorique, et Pratique.” 3rd ed. Paris, 1852.

Dragendorff, Jean Georges.—“Die gerichtlich-chemische Ermittelung von Giften in Nahrungsmitteln, Luftgemischen, Speiseresten, Körpertheilen.” &c. St. Petersburg, 1868. 3rd ed. Göttingen, 1888.

—— “Untersuchungen aus dem Pharmaceutischen Institute in Dorpat. Beiträge zur gerichtlichen Chemie einzelner organischer Gifte.” Erstes Heft. St. Petersburg, 1871.

—— “Jahresbericht über die Fortschritte der Pharmacognosie, Pharmacie, und Toxicologie.” Herausgegeben von Dr. Dragendorff. 1876.

Duflos, A.—“Handbuch der angewandten gerichtlich-chemischen Analyse der chemischen Gifte, ihre Erkennung in reinem Zustande u. in Gemengen betreffend.” Breslau u. Leipzig, 1873.

Eulenberg, Dr. Hermann.—“Handbuch der Gewerbe-Hygiene.” Berlin, 1876.

Falck, C. Ph.—“Die Klinischwichtigen Intoxicationen.” (Handbuch der spec. Pathologie u. Therapie red. von R. Virchow, Bd. 2.) Erlangen, 1854.

Falck, Ferd. Aug.—“Lehrbuch der praktischen Toxicologie.” Stuttgart, 1880.

Flandin, C.—“Traité des Poisons, ou Toxicologie appliquée à la Médecine Légale, à la Physiologie, et à la Thérapeutique.” Paris, 1847, 1853.

Fröhner, Eug.—“Lehrbuch der Toxicologie für Thierärzte.” Stuttgart, 1890.

Galtier, C. P.—“Traité de Toxicologie Médico-Légale et de la Falsification des Aliments,” &c. Paris, 1845.

—— “Traité de Toxicologie Médicale, Chimique et Légale,” &c. Paris, 1855. A later edition of the same work.

Greene, Will. H.—“A Practical Handbook of Medical Chemistry, applied to Clinical Research and the Detection of Poisons.” Philadelphia, 1880.

Guérin, G.—“Traité Pratique d’Analyse Chimique et de Recherches Toxicologiques.” Paris, 1893.

Guy, W. A., and Ferrier, David.—“Principles of Forensic Medicine.” London, 1874.

Harnack, Erich.—“Lehrbuch der Arzneimittellehre,” &c. Hamburg, 1883.

Hasselt, van, A. W. M.—“Handbuch der Giftlehre für Chemiker, Aerzte, Apotheker, u. Richtspersonen.” (A German translation of the original Dutch edition, edited by J. B. Henkel. Braunschweig, 1862. Supplemental vol. by N. Husemann, Berlin, 1867.)

Helwig, A.—“Das Mikroskop in der Toxicologie.” 64 photographs, roy. 8vo, Mainz, 1865.

Hemming, W. D.—“Aids to Forensic Medicine and Toxicology.” London, 1877.

Hermann, L.—“Lehrbuch der experimentellen Toxicologie.” 8vo. Berlin, 1874.

Hoffmann, E. R.—“Lehrbuch der gerichtlichen Medicin.” 5th ed. Wien, 1890–91.

Husemann and A. Hilger.—“Die Pflanzenstoffe in chemischer, pharmakologischer, u. toxicologischer Hinsicht.” 2nd ed. Berlin, 1882.

Husemann, Th., and Husemann, A.—“Handbuch der Toxicologie.” Berlin, 1862. (Suppl. Berlin, 1867.)

Kobert, Rud.—“Lehrbuch der Intoxicationen.” Stuttgart, 1893.

Koehler, R.—“Handbuch der speciellen Therapie, einschliesslich der Behandlung der Vergiftungen.” 3rd ed. 2 vols. roy. 8vo. Tübingen, 1869.

Lesser, Adolf.—“Atlas der gerichtlichen Medicin.” Berlin, 1883.

Loew, Oscar.—“Ein natürliches System der Gift-Wirkungen.” München, 1893.

Ludwig, E.—“Medicinische Chemie in Anwendung auf gerichtliche Untersuchungen.”

Mahon, A.—“Médecine Légale et Police Médicale.” Paris, 1807.

Marx, K. F. H.—“Die Lehre von den Giften.” Göttingen, 1827–29.

Maschka, J.—“Handbuch der gerichtlichen Medicin.” Tübingen, 1881–82. This work is under the editorship of Dr. Maschka, and contains separate articles on medico-legal and toxicological questions by various eminent toxicologists, somewhat after the manner of Ziemssen’s Cyclopædia.

Mende, Lud. Jul. Casp.—“Ausführliches Handbuch der gerichtlichen Medicin.” 1819–32.

Mohr, Fried.—“Chemische Toxicologie.” Braunschweig, 1874.

Montgarny, H. de.—“Essai de Toxicologie, et spécialement avec la Jurisprudence Médicale.” Paris, 1878.

Montmahon, E. S. de.—“Manuel Médico-Légale des Poisons,” &c. Paris, 1824.

Mutel, D. Ph.—“Des Poisons, considérés sous le rapport de la Médecine Pratique,” &c. Montpellier et Paris, 1835.

Nacquet, A.—“Legal Chemistry: A guide to the detection of Poisons, Examination of Stains, &c., as applied to Chemical Jurisprudence.” New York, 1876.

A translation from the French; see “Foods, their Composition and Analysis,” page 43.

Nicolai, Joh. Ant. Heinr.—“Handbuch der gerichtlichen Medicin.” Berlin, 1841.

The chemical portion is by F. R. Simon.

Ogston, F.—“Lectures on Medical Jurisprudence.” London, 1878.

Orfila, Matthieu Jos. Bonaventura.—“Traité des Poisons, ou Toxicologie Générale.” Paris, 1st ed., 1814; 5th ed., 1852.

Orfila et Lesueur.—“Traité de Médecine légale.” Paris, 1821; 4th ed., Paris, 1848.

Otto, F. G.—“Anleitung zur Ausmittelung der Gifte.” Braunschweig, 1856; 5th ed., 1875. 6th ed. by Robert Otto, Braunschweig, 1884.

Praag van, Leonides, u. Opwyrda, R. J.—“Leerboek voor practische giftleer.” In Zwei Theilen. Utrecht, 1871.

Rabuteau, A.—“Élémens de Toxicologie et de Médecine Légale, appliquées à l’Empoisonnement.” Paris, 1873. 2nd ed. by Ed. Bourgoing. Paris, 1888.

Reese, John J.—“Manual of Toxicology, including the consideration of the Nature, Properties, Effects, and Means of Detection of Poisons, more especially in their Medico-legal relations.” Philadelphia, 1874.

Remer, W. H. G.—“Lehrbuch der polizeilich-gerichtlichen Chemie.” Bd. 1 u. 2. 3. Auflage, Helmstadt, 1824.

Schneider, F. C.—“Die gerichtliche Chemie für Gerichtsärzte u. Juristen.” Wien, 1852.

Schneider, P. J.—“Ueber die Gifte in medicinisch-gerichtlicher u. gerichtlich-polizeilicher Rücksicht.” 2nd ed., 1821.

Selmi, F.—“Studi di Tossicologia Chimica.” Bologna, 1871.

Sobernheim, Jos. Fr. u. Simon, J. F.—“Handbuch der praktischen Toxicologie,” &c. Berlin, 1838.

Sonnenschein, L.—“Handbuch der gerichtlichen Medicin.” Berlin, 1860. A new edition by Dr. A. Classen. Berlin, 1881.

Tardieu, A.—“Étude Médico-Légale et Clinique sur l’Empoisonnement, avec la Collaboration de M. T. Roussin pour la partie de l’expertise relative à la Recherche Chimique des Poisons.” Paris, 1867.

Taylor, Alfred Swaine.—“On Poisons in relation to Medical Jurisprudence and Medicine.” 3rd ed. 1875. Manual, 1879.

—— “Principles and Practice of Medical Jurisprudence.” 3 vols. London, 1873.

Werber, Ant.—“Lehrbuch der praktischen Toxicologie.” Erlangen, 1869.

Wood, Horatio C.—“Therapeutics, Materia Medica, and Toxicology.” Philadelphia, 1874.

Woodmann, W. Bathurst, and Tidy, Ch.—“A Handy-Book of Forensic Medicine and Toxicology.” London, 1877.

Wormley, Theodore G.—“Micro-Chemistry of Poisons, including their Physiological, Pathological, and Legal Relations.” New York, 1857.

Wurtz, A.—“Traité Elémentaire de Chimie Médicale, comprenant quelques notions de Toxicologie,” &c. 2nd ed. Paris, 1875.

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