A Pilgrimage Into the Archives of Nickel Toxicology

ANNALS OF CLINICAL AND LABORATORY SCIENCE, Vol. 19, No. 1 Copyright © 1989, Institute for Clinical Science, Inc. A Pilgrimage into the Archives of Nickel Toxicology F. WILLIAM SUNDERMAN, M.D., Ph .D. Institute for Clinical Science, Pennsylvania Hospital,. Philadelphia, PA 19107 Introduction the contributors to this and the three previous symposia, with special com It is my great pleasure to address this mendation to my beloved son, Bill Jr. assembly of learned scientists on the My memory with respect to nickel tox occasion of the Fourth International icology goes back to 1943 when I Conference on Nickel Metabolism and attended my first nickel meeting at Los Toxicology. Alamos, New Mexico. This initial meet When I seriously sat down to prepare ing was arranged out of necessity. It was remarks for this evening’s program, I held for the purpose of devising methods became aghast as I pondered upon the to protect workers in nuclear energy title that I had submitted. How could I from the hazards of acute and chronic presume to cover such a colossal subject exposure to nickel tetracarbonyl in the course of a brief address? It is true Ni(CO)4. It was recognized then that that the hazards of exposure to nickel nickel carbonyl was one of the most toxic and nickel compounds have been recog of all gases. At our first meeting, those in nized only within recent decades; how attendance set three goals: (1 ) to obtain ever, the number of research contribu accurate toxicity data on nickel carbonyl; tions and publications on nickel (2 ) to establish programs for the protec toxicology that have appeared during the tion and treatment of workers who might past three decades has been substantial. in ad v ertan tly be exposed; and (3) to In my ponderings, I harbored the wish undertake studies for the acquisition of that I could call for help from my knowledge on the metabolism of nickel. esteemed friends and scientific col It is heartening to note that these initial leagues of World War II who instigated goals have, in large measure, been real many of our early interests in the toxicol ized. And now, 45 years later, the extent ogy of nickel. These eminent scientists to which studies on nickel metabolism are now deceased. At this time may I pay have expanded, as evidenced by this tribute to them and to the early pioneer conference, is noteworthy and evokes a ing contributions of the International modicum of satisfaction. Nickel Company especially through Although metals have been known and their Medical Director, J. Gwynne Mor used by man since antiquity, it is note gan; to the U.S. Atomic Energy Com worthy that it has been only within the mission and the Rohm and Haas Com past two centuries that nickel was pany, — the two organizations which acknowledged to be a primary element. supported our research studies; and to Furthermore, nickel has been refined for large scale commercial distribution only Plenary Address given at the Fourth International within the last 1 0 0 years. Conference on Nickel Metabolism and Toxicology, Hanasaari Cultural Centre, Espoo, Finland, Sep Nickel is ubiquitous and is estimated tem ber 5, 1988. to be present in 0.008 percent of the 1 0091-7370/89/0100-0001 $02.00 © Institute for Cìinicaì Science, Inc. 2 SUNDERMAN earth’s crust. The core of the earth is The hazards from exposure to nickel believed to be similar in composition to appear to have been first recognized meteorites, which consist of iron-nickel during the period of the Renaissance. alloys averaging about 8.5 percent Agricola (1490-1555) referred to the nickel. The presence of nickel may be toxic effects of “Kupfer-nickel” ores on detected spectrographically in the sun the lungs of workers in the Schneeberg and celestial bodies in which the ele area in Germany.22 Nickel does not occur ments are present as incandescent gases. in nature by itself but is associated with Nickel in the sun is estimated to be cobalt or as an alloy with copper, zinc, present in 0 .0 0 0 2 percent by volume. iron, and arsenic. In the 17th century, In an interesting review on the medic the German Erzgeburg miners found a inal use of nickel, Koplinski in 1911 red-colored ore which they mistakenly stated, “Nickel and nickel salts, except thought was copper and which they ing for the very poisonous nickel car named “Kuper-nickel” (copper-nickel). bonyl, have no place or record in toxicol While possessing the appearance of cop ogy ” . 28 Koplinski elaborated on the per ore, it yielded no copper when exceptional medicinal value of nickel treated with the process then used to salts for the treatment of epilepsy, extract copper. Later, the red colored chorea, migraine, and neuralgia. He also ore was identified as nickel arsenide noted that “nickel acts as a sedative and (NiAs). A silver appearing metal emanat tonic of peculiar and elective power in ing from China during this period was controlling the damaging effects of sexual given the trade name “German Silver.” vice on the nervous system ”. And now, This is essentially a mixture of nickel, since World War II, the uses of nickel for copper, and zinc.59 medicinal purposes have been com The word “Kobalt” in German denotes pletely abandoned, and it has become a goblin and “Nickel ”, a scamp. These recognized that, in addition to nickel evil spirits (Kobalt and Nickel) were carbonyl, exposure to nickel and other believed to haunt the mines and do harm nickel compounds may be exceptionally to the miners. The church services dur deleterious to health. ing the 17th century in the mining dis On the other hand, nickel is probably tricts in Germany included prayers for an essential trace element required for the protection of miners from “Kobalt” mammalian life. In 1936, the studies of and “Kupfer-Nickel”. Howard-White20 Bertrand and Nakamura suggested that notes that the fume-emitting reddish ore nickel may play a normal physiological had a harmful effect on the health of the role in metabolism . 6 In 1974, Schwartz miners, so that they naturally thought indicated that nickel is probably an that the evil spirits or “Old Nick” himself essential element for the life and health had been at work. of anim als. 41 Within the past decade, Nickel was isolated as a metal early in nickel has been shown to be a compo the 19th century by Berthier. 5 Following nent of four plant enzymes of physiologic this isolation, a world-wide search for im portance.61 nickel-containing ores was made by a number of commercial companies. Dur ing the middle of the last century, ores Historical Items Pertaining to Nickel were found both in Europe and in the United States which contained from one A synopsis of historical items pertain to two percent nickel. These ores fur ing to nickel and its toxicology has been nished the only available nickel until the assembled (table I). A few of the perti much richer ore (called Garnierite, — a nent starred items will be discussed. silicate of nickel) was discovered in the A PILGRIMAGE INTO THE ARCHIVES OF NICKEL TOXICOLOGY 3 French penal colony, Noumea, — the this finding led to the economical com English name of which is New Cale mercial production of nickel.34* donia. The Noumean ores were found to The first deaths from nickel carbonyl contain from 1 0 to 2 0 percent nickel; were reported in 1903. Two workmen they were found to be abundant, near died from exposure to nickel carbonyl at the surface, easily mined, and close to the Mond Nickel Works at Clydach. The the seaboard so that they could be deliv report to the coroner’s jury by Dr. Tun- ered worldwide at a small cost for nicliffe stated, “Death was caused by freight. The Noumean mines were nickel carbonyl, a substance inhaled developed by a French company under from the dust given off during employ the House of Rothchild. In retrospect, m ent. ” 36 It might be noted that in the some of the difficulties and hardships previous decade, McKendrick and Snod that were encountered in their efforts to grass had reported a case of nickel car mine the ores are amusing. For example, bonyl poisoning in the same plant. 32 in trying to recruit laborers in New An important study on the toxicity of Caledonia, J. Garland wrote, “The native nickel carbonyl was reported in 1907 by Kanakas . hold strong views as to the Armit. 1 He studied the effects of expo folly of work and the stupidity of the sure to nickel carbonyl on rabbits, cats, white man who is addicted to it. ” 22 and dogs and found that nickel was the The first malleable nickel was pro toxic component in nickel carbonyl and duced in Philadelphia in 1865 by Joseph not carbon monoxide. Wharton (1826-1909) from ores mined A number of toxicologic investigations in Pennsylvania. The International on nickel toxicology were reported dur Nickel Company issued a medal in 1904 ing the beginning and middle of this commemorating this event (figure 1). It century (table I) and these have been might be noted that the U.S. Mint pur reviewed in some of our earlier pa chased $600,000 worth of nickel from p e rs .26'27,45,47 A noteworthy discovery Wharton in the course of 20 years to was made in our laboratory in 1957 when make three cent nickel coins (1865- sodium diethyldithiocarbamate (Dithio- 1889). It is also noteworthy that W harton carb) was found to be an effective anti donated $100,000 in 1881 to the Univer dote for nickel carbonyl poisoning.

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