PORTRAIT: NATIONAL LIBRARY OF MEDICINE . The passedthe of ’s wives andkilledhisbrother with er namedLocusta,whomurdered several emperor Nero employed apersonalpoison- secret weapons inancientRome. The of Athens. theyouth drink hemlockforcorrupting execution, aswhenSocrates wasforced to terestedly butusedthemasameansof Gr ian scroll datingto1500B.C. Later, the concerning toxic substancesisanEgypt- ancient. The oldestwrittendocument one wasmadesickby poisoned arrows. “intoxicated,” whichinitiallymeant that a .Asanaside,italsoledtotheterm thus theword tips ofarrows tomakethemmore lethal; were occasionallyplacedonthe for shootingarrows. In theancientworld, Gr player inmoderninvestigative policework. cology thatmadethechemistanessential toxic effectinthebody. It isforensic toxi- the studyofsubstancesthatcanhave a branch offorensic scienceistoxicology— father’s murder. prints usedtoframeablindmanofhis Qu of thefirstmillennium,Roman orator documents. Sometime nearthebeginning the firsttimetoestablishidentityof China,fingerprintswere usedfor century witnesses intheRoman In courts. 8th- or Justinian recognized physiciansasexpert A.D.,theEmper- ple, inthe6thcentury of forensic scienceare ancient.For exam- cases.Butage offamouscourt theorigins novels, cover- televisionprograms, ornews © Richard A.Pizzi Mathieu OrfilaandtheMarshtestin19thcentury. Modern forensictoxicologywas establishedby P W 2004 A eeks didnotsimplystudypoisonsdisin- eek term To ofpoisonisitself The formalhistory The word “” derives from the F intilian describedacaseofbloodypalm ointing toPoison or chemists,themostimportant xins were alsoextremely popularas MERICAN it isusuallythrough popular exposed toforensic science, hen thegeneralpublicis toxon toxicos C HEMICAL , whichmeantabow came torefer tosuch S OCIETY became renowned fortheiruseofpoisons ill. Indeed, theillustriousMedici family of various poisonsonthepoorand become queenofFrance, tested theeffects ine deMedici ofFlorence, whowouldlater we poisoners duringandaftertheRenaissance ofdeceitfulfemininenature.view assault anditfittheprevailing prejudiced ers, asitdidnotrequire adirect frontal the weapon ofchoiceforfemalemurder- tional, andsinister. Poison wasconsidered ascrafty,poisoner wasviewed unemo- by its heightduringtheRenaissance. Murder according tomanyhistorians,itreached the demiseofRoman Empire, and in popularitythecenturiesfollowing P A Poisoner’s Renaissance known asthe“kingofpoisons.” choice forRoman assassinsandbecame ly from leadortinore, wasthepoisonof from poisoners.,derived primari- lies hired foodtesterstoprotect themselves poison. Roman emperors and noble fami- an attempttostemthetideofmurder by first lawagainstpoisoningin82B.C. Mathieu Joseph Bonaventure Orfila oisoning as a criminal art formincreasedoisoning asacriminalart

re poison wasastealthyendeavor, andthe S ome ofthemostnotoriouscriminal

women. In the16thcentury, Cather- r ing withpoison. people how tobecomeadeptatmurder- also schoolsinRome and Venice toteach contracts are stillpreserved. There were people forafee. The records oftheir ry much sothatthere existedin15th-centu- also remarkably efficientaspoisoners,so ing corpse.Other Renaissance Italians were prepared intheabdomenofahog’s decay- andcopper,tion ofarsenic,, odd mixture acombina- waspurportedly family poisoncalledLaCantarella. This killed several oftheirfoeswithasecret and Lucrezia Borgiaare supposedtohave with poison. for itsskillindispatchingadversaries Italy,16th-century wasalsowidelyknown R to dealwithenemies.Anotherfamous H method forthedetectionofpoisons was change. the dawnof19th,things began to to from themiddleof18thcentury cally identifyapoisoninthebody. But as there wasnoscientificbasistochemi- r poison inamurder. Most convictions difficulttoproveas itwasvery theuseof escapedprosecution, throughout history executed forhercrimes,manypoisoners two popes. was allegedlyinvolved inthemurder of deaths, eitherdirectly orindirectly, and To ested buyers andtrainedtheminitsuse. To arsenic called invented apoisonousliquidcontaining M elied oncircumstantial evidenceorintent, eputed tohave beenanItalian woman. enaissance clan,theBorgiasof15th-and

ermann Boerhaave, althoughhistech- S adame Giulia Toffana (1635–1719) V ffana.” She soldherconcoctiontointer- ffana wasreputedly responsible for 600 The greatest poisoner in history isalso The greatest poisonerinhistory The brother–sister teamofCesare The firstpersontosuggestachemical Although Toffana wascaptured and EPTEMBER enice a“Councilof Ten” thatpoisoned CHRONICLES CHEMISTRY 2004 agua Toffana T ODAY ’ S C EITAT HEMIST , or“water of W ORK 43 CHEMISTRY CHRONICLES nique was rather unsophisticated. He The Marsh Test British medical examiners tested a placed suspicious substances on hot coals white powder found in Mary’s cooking and made distinctions between the odors. A new test for arsenic, designed by James pan. They noted that it gave off an odor An even more important event in the Marsh, a chemist at the British Royal Mili- of garlic if heated, and that if placed in history of modern toxicology was the tary Academy in the 1830s, greatly increased water it turned milky, with some sinking invention of the “arsenic mirror” in 1787. the contribution of the toxicologist to foren- to the bottom and part of it floating on Johann Daniel Metzger developed a sic science. Marsh treated a flask of suspect- top in a thin film. Its behavior was iden- method of detecting arsenic in solutions, ed arsenic solution with pure zinc and either tical to a white arsenic sample tested in although not in the human body. He sulfuric or hydrochloric acid. Gas was then the same way. learned that when arsenic oxide was heat- released through a narrow glass tube and In her trial, Mary claimed that the ed with charcoal, it formed a black, mirror- heated in a flame. If the solution contained chemical mixture she added to the food like deposit on a cold plate held over the arsenic, the heated gas would leave a deposit was meant to improve her father’s tem- coals. This dark substance was arsenic. of metallic arsenic on a white porcelain perament. This was not an utterly ludi- dish held in the flame, or white arsenic oxide crous assertion, as physicians of the time Murderous Mary if the dish was held above the flame. This often prescribed arsenic compounds as The first murder trial to feature toxico- test, hereafter known as the Marsh test, was tonics and antiseptics. But the evidence logical testimony from medical experts precise enough to test for minute amounts that seemed to be strongest against Mary took place in 1752 in England. Mary of arsenic. was the testimony of the servants that Blandy was accused of her she tried to destroy the arsenic residue father, a prominent attorney, with white in the pan by throwing it in a fire. She was arsenic (arsenous oxide). She had obtain- gruel, and this was more successful, convicted of murder and executed by ed the poison from Capt. William making her father and two servants ill. hanging. Cranstoun, a Scotsman who wished to Although the servants were suspicious of marry her. Blandy initially placed the Mary, her father continued to allow her Enter Orfila arsenic in her father’s tea, but this failed to prepare his food, and within a short These early tests for poisons like arsenic to work. Ultimately, she mixed it with time he died. were important but primitive. A strong theoretical apparatus was lacking. The critical historical moment in the devel- opment of toxicology as a science was the emergence of Mathieu Joseph Bonaven- ture Orfila. A Spaniard by birth, Orfila was profes- sor of legal medicine and chemistry at the University of Paris when he published a groundbreaking text on toxicology in 1814. His book, A Treatise of General Toxi- cology (loosely translated from the longer French title), was the first successful attempt to classify poisons as corrosives, astringents, acrids, stupefying or , narcotico-acrids, or putrefacients. An impressive achievement for a young man of 26, the book established Orfila’s inter- national reputation as the preeminent authority on toxicology; indeed, it essen- tially founded the discipline. Much of Orfila’s laboratory work dealt with arsenic. His experiments on animals demonstrated that arsenic was distributed throughout the body after ingestion, negating the previously dominant theory that poisons act on only one type of body tissue. Orfila was also the first scientist to extract arsenic from organs rather than just the contents of the stomach. But it was his testimony at an infamous murder trial that established Orfila’s reputation among the general public.

44 TODAY’S CHEMIST AT WORK SEPTEMBER 2004 www.tcawonline.org The Marsh test (see box, “The Marsh Stas discovered a method for the extrac- Test”) gained recognition for its creator Modified versions of tion of nicotine from the organs of a and for Mathieu Orfila in the 1840 trial murder victim. The Stas method became of Marie Lafarge. Madame Lafarge was the Stas method and the primary isolation technique for analy- accused of murdering her husband with the Marsh test are sis of nonvolatile organic substances. arsenic a year after they were married. Modified versions of the Stas method Initial tests of the deceased husband’s still used by forensic and the Marsh test are still used by foren- stomach contents did not locate arsenic. sic toxicologists today. There have been The prosecution had the body exhumed toxicologists today. significant advances in the field, howev- to test organ tissues but still found no er. GC and MS are used to confirm the arsenic. At the same time, however, the endorsing the use of toxicology in concert presence of the smallest chemical traces. food given to the victim before his death with all available evidence to give a more The development of modern instrumen- contained large amounts of arsenic. Orfi- complete picture of a crime. tation has made contemporary forensic la, engaged as an expert witness by the toxicology more complex, yet many of the prosecution, reexamined the evidence and A Poison Arms Race basic principles remain the same as in the determined that arsenic was present in The success of the Marsh Test reduced, early years. Thus, the achievements of every tissue sample. He concluded that the but by no means obliterated, the popu- Orfila, Marsh, and Stas live on as much previous testers had achieved false nega- larity of metallic poisons such as arsenic. more than mere historical footnotes. tive results because of their improper use Many killers turned instead to vegetable of the Marsh test. He also asserted that the alkaloids, for which there was no analyt- Suggested Reading presence of poison alone did not deter- ical procedure for isolation. Morphine, , 2nd ed.; Davies, G., Ed.; American Chemical Society: Washington, DC, 1986. mine guilt, but must be considered in light , and atropine were some of the More Chemistry and Crime: From Marsh Arsenic Test of all the additional evidence. Orfila’s testi- available in the mid-19th century. to DNA Profile; Gerber S. M.; Saferstein, R., Eds.; mony helped create a professional foren- But even these poisons became suscepti- American Chemical Society:Washington, DC, 1997. sic science by emphasizing the importance ble to discovery by toxicologists after 1850. Richard A. Pizzi is a freelance writer in Portland, ME, with of professional toxicological training and In that year, Belgian chemist Jean Servais an M.A. in history. ◆

www.tcawonline.org SEPTEMBER 2004 TODAY’S CHEMIST AT WORK 45