edned by

JOHN H. WOTlZ Soulham Illlnals Unlvenlty Carbondale, 62901

Recognition of the Biological Action of Radium Radiation

J o h n Harley Warner 520 Plantation Road Tallahassee, Florida 32303

Between the discovery of radium in 1898 by Pierre and Marie Curie and the 1930's, many people were injured and some killed as the result of radium exposure (1). The effect of radium on living tissue was recognized a t the turn of the century, yet in the absence of a well-developed knowledge of the hazards of radium radiation, significant protective mea- sures were not taken until the 1920's. The dearth of radi- oprotection during this period is clearly illustrated by the fact that out of about eieht thousand pages in the notebooks used by the Curies, four I k d r e d were iatkr found to he radioactive (2) .

A widespread mis(.onceprion exists that Henri Becquerel WRZ thc firs1 toobsewe the biological actions of radium 1S5). In fact, the earliest report of phjsiological effects of radium radiation was made hv a Munich scientist, Walkhoff, in 1900 (6). Walkhoff's ohsekations did not, as might he expected, appear in a journal of chemistry or physics, hut rather were published in a German photography journal, Photographkche Rundschau, and were initially presented t o the Amateur Photographers Club of Munich.

Walkhoff was interested in the similarities between the properties of Rontgen-rays and those of radium radiation. Although the physiological effects of Rontgen-rays had been recognized since 1896, there had been no report of similar ef- fects of radium radiation. Walkhoff turned to his friend "Fritz" Giesel for a samnle of radium. and reported that "Dr. Giesel has had the kindness to put a tmy disposal 0.2 g of ra- dium. now much soueht-after hv physicists, for phvsiolo~ical investigation2' (7). '"~alkhoff-ekiosed this &ple in a celluloid capsule and exposed his arm to the radiation for two 20-min intervals. Within two weeks, a skin inflammation de- veloped which he observed to be analogous to that produced by excessive exposure to Rontgen-rays. In December 1900, Giesel reported that he had repeated Walkhoffs experiment with nea;ly identical results (8).

These German ohservations soon came to the attention of the Curies, and in the following year, Pierre Curie repeated Giesel's experiment using himself as the subject (9). Curie exposed hi; arm 10 radium radiation for I 10-hr period and, as hi3 d~ught(~ohaerved, "to his joy, a lesion appeared" (10) . Pierre Curit:. Walkhoff. and Giesel had all intrntioonllv ex- - -.--- - ~ ~ - - ~ . ~~ . posed themselves to radium radiation as a part of their own exnerimental d e s i e n ~ . ~ hut several incidents of accidental ~~ ~~~ - , exposure to radium leading to physiological harm were also renorted durine this period. The first. those of Marie Curie v

and Becquerel, were described in the same paper as Pierre Curie's earliest observations (9).

In April 1901, Becquerel carried in his vest pocket for about six hours "several decigrams of very active radioactive barium

chloride" contained in a sealed glass tuhe wrapped in paper and enclosed in a cardboard box. A red spot appeared on the skin under the pocket in about ten days. Subsequently, the skin fell off, leaving an open wound which healed into a scar about 49 days after the ray's action. During this period, "the same quantity of radioactive material, enclosed in a lead tuhe whose sides were about five millimeters thick. was kept for forty hours in another vest pocket and did not produce any action" (11). Marie Curie. relatine Becauerel's reaction to this incident, noted that "hecame to tell i s of this evil effect of radium, exclaiming in a manner a t once delighted and an- noyed: 'I love it, but I owe i t a grudge' " (12).

Marie Curie sustained burns similar to. thoueh less severe than, those of Becquerel. In addition, pieke Curie noted that both he and his wife had experienced pain and inflammation of the hands as a result of handling radioactive products. From the evidence gathered from these intentional and accidental exposures to radium, Pierre Curie and Becquerel were able to conclude that "the duration of the development of changes varies with the intensity of the active raysand with the du- ration of the irritating action" (11).

Research efforts inquiring into the biologically active properties of radium radiation and attempts to employ radium as a therapeutic agent soon followed the recognition of its physiological action (13). In addition to the initial use of ra- dium by the scientific community, the quack was also quick to capitalize on this ill-understood curiosity, and the public was rapidly confronted with a wide selection of radium nos- trums (14). Interest in the biological actions of radium, therefore, provided an opportunity for extensive exposure to radioactivity. Without the benefits of adequate protective measures, which appeared only in the late 1920's, both the public and members of the scientific community were exposed to dangerous levels of radium radiation.

1 Frederieh Giesel was employed as a chemist at a quinine factory in Braunschwieg, and by 1900 had developed a greatly improved methd for producing radium salts (15). One writer noted that "While Marie Curie was still struggling to accumulate enough pure radium chloride for an atomic weight determination,.Giesel was purifying radium bromide routinely in about eight crystallizations. By 1902 he was producing radium as a sort of hobby and offering it for sale, at a nominal price, toanyone who wantedit" (16). Walkhoff stated in 19W that Giesel had produced 2.0 g of radium (7). Indeed, Giesel was the only person (including the Curies) from whom Walkhoff could have obtained 0.2 g of radium at that time. Giesel stated that in his ex- ~eriment he used radium-barium-bromide (17), and it is most likely that Walkhoffs "0.2 g of radium" was actually a mixture of radium and barium salts.

2 It is interesting to place these early experiments of Walkhoff, Giesel, and Pierre Curie in what Altman has called "one of the strongest and yet least appreciated traditions in medical research," that of autoexperimentation. Possible motives for experimenting on themselves include convenience, curiosity, a spirit of adventure, re- liability, self-interest, and availability. See reference (18).

Volume 53, Number 9, SeDtember 1976 / 579

( I ) Evma, R. D..J 1ndu.f. Hyp and Toriol.. 25.253(1943). (2) Pnvste mmmunicetion with Monique Bardry. Char@. d.8 Archiueade I'1nstitut d"

Radium. Fondation Curie, Paris, 1975. (3) Case. James T.. Amer J. RmntgewI.. S2.574!1959). (4) Finzi,N. S.,CIin. Rodiol., 12.143!1961). (5) Alexander, Peter, ',Atomic Radiation and Life: Penguin Books, London, 1967, p.

89. ikhoff.PhofogrophiJehp Rundsehou. 14,189iI9W).

Rat (6). p. 190. Giesel. F. Bor, 33,3569119W). Becquerel, Henri, end Curie, Pierre, Comptrs Rend., I32.128911901). rll,ip EVP. "Madame Curio." ITmmloior Sheoan. Vincent). Doubldav Doran and ~. ~ ~ ~

Company, Inc. New ~ o r k . 1939,~. 198. Ref. 191. p. 1290. Curie. Marie, "Pierre Curie," (Tramlotors: Kellogg, Charlotte, and Vernon)

Mscmillian Compsny, NewVork. 1923, p. 118. Looney. WilliamE.,Amrr. J. Roentgmoi.. 72.8381195B.pp.83b9. RcL (3). pp. 576-8: Ret (13). pp. 838-9. Ciilispie. C. C.. (Editor), "Didlonary of Scientific Biogrephy." Charles Scribner's

Now York. 1972.~5 "" Kirhu. H. W.. lsis 62. . . Ref. (B), p. 3570. ~ 1 h m . L . K..N Engl J. Mod., 286.348(19721

The First Actinium Claim

. The

som.

William H. Waggoner University of Georgia Athens, Georgia 30602

When nresent-dav chemists refer to actinium, the reference almost certainly is to the radioactive elementisolated from nitchblende residues (1) hv Andre Dehierne (1874-1949) in . . . 1899. Nearly two decades earlier, however, a claim of the discovery of a quite different element for which the same name was suggested had been advanced as a result of an investiga- tion of far more prosaic materials.

Dr. Thomas Lamb Phipson (1833-1908) was an English analvtical chemist with a broad interest in things scientific. In d k , lohl , he puhlishvd a short account ( 2 ) of what he termrd '.a curious actinic phenumrnnn." The effect in ques- tion was a photwhernical one in which a painted Kate post was observed to rhnnre color, appearing hlack by day and white a t night. The process was &nplet& reversible and appar- ently was caused by a material in the white paint pigment reacting to sunlight. According to Phipson, this pigment was largely a mixture of co-precipitated BaS04 and ZnS, with smaller amounts of zinc and iron oxides and traces of lead, arsenic, and manganese. A darkening in the color from white through brown to a dark slate shade could he produced by exposing the pigment to direct sunlight for about 20 min. The orieinal hue was restored in darkness in several hours. No phosphorescence was observed and a plate of window glass nlaced over the white piament prevented the darkening. A . - chemical examination of the pigment failed to reveal any unknown material but Phioson hedged the question as to the real cause of the phenomenbn. Hew& also caieful to state that the unknown metal. should there Drove to be one, was "to he called 'Actinium'."

The manufacturer of the p iment replied to Phipson (3), pointing out that the phenom&on cited was not new,dthough it had not been explained. More importantly, he questioned

Phipson's analytical data, especially the high percentage of zinc oxide and the presence of iron, lead, and arsenic. Several weeks later. a second letter appeared ( 4 ) . this one from an American &ment manufact&. More caustic than his En- dish counterpart, Cawley also doubted Phipson's chemical ia ta and further stated that "I fmd that a she& of glass exerts no sensible protective action."

~ h i ~ s o n ' s second note (5) added little new information except to say that he now believed the darkening to he caused by a reversible oxidation-reduction process involving some material associated with the zinc components of the pigment. "It is by no means impossible that new metallic element, Actinium, may be present in the specimens of white zinc ex- aminrd hy me, andarruunt for the singular artinic phenom- enon." Two months later, he reported (61 that he had '.isolated the oxide and sulfide of the new metal in a state of tolerable purity." Actinium sulfide was obtained in about 4% yield and was found to he uhotosensiti\,e: the white oxide was not af- fected by sunlight. The metal &as not isolated.

Cawlev again responded (7). flatlv reiecting Phipson's . . . claimsand remarking rhar h~"seerns co ha\?a perulinr talent for making large inductions from scanty and inadequate dam" - - Concerning the "new element ~ c t l n i u m , . . . would not Phinsonium be a more suitable name if the new body should he iklated?"

Shortly thereafter, Phipson informed the readers in the Chemical News (8) that he had isolated actinium by precip- itating an ammoniacal solution with magnesium. The metal was said to form "a light grey deposit, which, by compression, becomes white like silver and extremely brilliant." I t was stahle under alcohol but oxidized slowlv in water and saline ~~- ~~~ ~~ ~

solutions. His final report on this iubjeciappeared in 1882 (9) but was more concerned with zinc and glass than withactin- ium, per se.

Twenty years elapsed before actinium was mentioned again in thk literature. In a footnote in his textbook, Mendeleeff (10) noted: "Amonest the metals accnm~auvine zinc which have . - - been named, gut not authentically separated, must be in- cluded the actinium of Phinson (1881) . . . As no further mention has been made of it since 1'882, its existence must be reearded as doubtful."

Phipson's alleged discovery thus passed from the chemical scene by default. Had it proved to be a photosensitive metal, the name he had suggested would have been appropriate and Debierne would have had to look elsewhere in the classical languages for a suitable root. It is to he regretted that no one, including the o r i ~ n a l claimant, ever confirmed the true nature of the material. '

Literature Cited

(41 Cswley,J.,Chem. NPUS, 44.51 (1831). (51 Phipson, T. L.,Chem. News, 44.73 118811. 161 Phip~n.T.L..Chem. Nems, 44,138 11881);Bn'L. Ass" Reps.,51,603 (1881). (71 Caw1ey.J.. Chom N e u , 44,167 (1881). (8) Phipron.T.L.. Chem.Neu8. 44,191 (18811. (9) Phipson,T.L., Chem. Neyis, 45.61 (1882).

(10) Mendeleeff, D.. "The P1incip1es of Chemistry: American Home Library company. New York. 1902. Pt. 3.p. 69.

580 / Journal of Chemical Education