Pittsburgh's contribution to radium recovery - Journal of Chemical

Pittsburgh's contribution to radium recovery. Alexander Silverman. J. Chem. Educ. , 1950, 27 (6), p 303. DOI: 10.1021/ed027p303. Publication Date: Jun...
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PITTSBURGH'S CONTRIBUTION TO RADIUM RECOVERY' ALEXANDER SILVERMAN University of Pittsburgh, Pittsburgh, Pennsylvania

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there is a rich background of historical material which precedes the discovery of radium and radioactivity, it will suffice for our present purpose to refer to the vacuum tubes of William Crookes in England in 1878, in which strange phenomena were observed, including the fluorescence of the tube wall. In 1895 Wilhelm Konrad Von Roentgen observed that the rays which escaped from Crookes tubes would penetrate black paper in which photographic plates were wrapped and even plateholders in which they were held, affecting the normally protected plates and producing shadow images of various shades depending on the nature of the material which was interposed. It is told that when Roentgen's findings were reported a t the Academy of Sciences in Paris in 1896, Henri Poincare suggested to Henri Becquerel that the fluorescent patches on the walls of the X-ray tubes might be the source of the highly penetrative X-rays. The suggestion prompted the study of fluorescent materials and it was among these, in uranium compounds, that Henri Becquerel observed radiations that were similar to X-rays in their penetrating power. In December of 1898 Maria Sklodowska Curie announced the discovery of polonium (and later radium) which had been isolated from the mineral pitchblende or uraninite, a complex oxide of uranium with small amounts of lead,'the rarer elements polonium, thorium,,yttrium, helium, and argon, and some nitrogen. Thls ore was found in Joachimsthal, in old Bohemia in Austria. It is the black mineral in which helium had been discovered in 1895 by William Ramsay. The writer visited the mines in Joachimsthal, then rechristened Jachymov, in Czechoslavakia in 1928, and learned a bit of interesting history of the uraninite deposits. It seems that the mines a t Joachimsthal had already been operated early in the 16th century for the recovery of silver from a vein which occurred in the uraninite deposits. The old cupola in which the silver was refined still stands and one goes up an attractive hand-wrought iron stairway to a mezzanine entrance of the cupola which was still used in 1928 for radium, vanadium, and uranium recovery. It seems that in the earlv centuries the silver was smelted and

the rest of the gangue used as road-building material or dumped into the streams of the region with no knowledge of the value of the other components of the ore. When the silver content got too low, the ore was processed for the recovery of uranium which was used as a pigment in ceramics for the production of a greenishyellow color. It was prized because of the fluorescence of the uranium colored ware. Before 1898 it was not known that this ore might contain something which would some day be valued a t three million dollars an ounce. It is to the credit of the Austrian government that a ton of the concentrate was shipped to Paris for the researches of the Curies. This yielded the highly radioactive components polonium and radium. According t o Joseph A. Kelly,* formerly president of the Radium Chemical Company, Inc., Radium Sales Division of Standard Chemical Company, the late Joseph M. Flannery of Pittsburgh was gravely concerned about a sister who was afflicted with cancer. Trying to locate a cure, Mr. Flannery went to Europe hoping that radium might help. Finding it impossible to purchase radium, Mr. Flannery felt that it should be made available for experimentation. In 1911 prospecting disclosed that in southwestern Colorado and in southeastern Utah carnotite Kp(U02)2(V04),.8H20oecurred in deposits in a tract covering about 800 square miles. The deposit was about 65 miles from the nearest railroad and in mountainous country about 7000 feet above sea level. Mr. Flannery organized the Standard Chemical Company, locating a plant a t Canonsburg, Pennsylvania, and a laboratory in Pittsburgh, in a building then known as the Vanadium Building and now occupied by the Oakland Branch of The Peoples First National Bank and Trust Company of Pittsburgh. The European ore, pitchblende or uraninite, contained about one gram of radium in every five or six tons of ore. The Colorado ores contained only one gram in five or six hundred tons. Men had to be trained to work the Colorado mines. Burros and wagon teams carried the ore from mine to mill, about 60 miles, and brought back water and supplies. Ore bodies in the various Dockets ranwd from a few ~ o u n d s , A paper first presented April 16 at the 25th Anniversary of mineral to deposits of 1800 tons in rare cases. From Meeting of the Pennsylvania Academy of Science, Lanoaster, the mill the ore went in 80-ponnd sacks by wagon or Pennsylvsninirt; later revised and presented before the Division motor truck to Placersville, Colorado. Then a narrowof History of Chemistry of the American Chemical Society at the gauge railroad carried it to Salida, Colorado. Thence 116th meeting in Atlantic City, New Jersey, Sept. 14 to 23,1949; Contribution No. 724, Department of Chemistry, University of Pittsburgh.

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"Radium, some interesting facts," Tha Midwest Purchiw

Agent, May, 1934.

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to produce bromides. This "medium" bromide liquor, as it was called, was subjected to thirty primary crystallizations when it contained 500,000milligrams of radium element per ton. The radium and harium bromides were next dissolved in a minimum of water and filtered into a fused quartz dish. Sixteen primary crystallizations were now conducted increasing the radium content to 516,000,000 milligrams per ton as radium bromide. Pure radium bromide (58.5 per cent radium) would contain 585,000,000 milligrams of radium element per ton. This fractionating principle is illustrated in figure 195, page 433 of P a r t i n g t ~ n . ~ The laboratory in Pittsburgh was first under the direction of a Dr. Otto Brill of Austria. I t is said that he was an arrogant person who insisted on his own methods for the recovery of radium and would not listen to suggestions from others. Among his associDr. Charles H. Viol and Dr. Otto Brill in the Radium Mensurementa ates the first was Glenn Donald Kammer, Bachelor of Labolatory Science in Chemical Engineering, University of Pittsit traveled by rail to Canonshurg, Pennsylvania, where burgh, 1912. Years later (1925) he obtained the Doctor of Philosophy degree with a major in chemistry in the Louis F. Vogt was superintendent. According to Arthur Louis Miller of Pittsburgh, University of Pittsburgh. Kammer had ideas of his Purdue chemical engineer, who was employed by the own concerning the recovery of radium from the low Standard Chemical Company in 1914 to recover the radium-containing carnotite ore, hut Brill simply would radium, 125 tons of ore containing 10 to 12 milligrams not listen. Dr. Charles H. Viol, a young University per ton, were boiled or fused with sodium carbonate to of Chicago graduate, succeeded Brill as director of the convert radium and barium to carbonates. Dilute laboratory. Viol had studied under the eminent hydrochloric acid converted the precipitate to chlorides physicists Albert A. Michelson and Robert A. Millikan in a liquor now containing 1900 to 2000 milligrams of a t Chicago, and with chemist Herbert N. McCoy who radium per ton, and radium and harium were precipi- also became an authority on radioactivity. Then tated with sulfuric acid. The sulphates, after filtering Henry Titus Koenig, Bachelor of Science in Chemistry, and washing, were fused or boiled again with sodium University of Pittsburgh, 1912, joined the others. carbonate, filtered and washed sulfate-free. Their Kammer, Viol, and Koenig, with no prior knowledge of solution in hydrochloric acid produced liquor 11. I t the subject, tackled the recovery of radium from carnowas neutralized with sodium carbonate and crystallized tite and succeeded. In December, 1912 Standard Chemical Company in a bathtub. After nine primary crystallizations, 1000 liters of solution contained about 125 kilograms of produced the first commercial radium in the world. mixed salts having ahout 200 milligrams of radium ele- As intimated previously, radium sought by Joseph M. ment or about 8 to 10 g. per ton. Flannery for treating his sister was not available anyThere were 45 secondary crystallizations of another where in Europe. liquor which usually contained about 80 milligrams of In 1938 an informative article on the Standard Chemradium element. The concentration of the new liquor ical Company of Pittsburgh appeared in The Crucible, was about 200 milligrams, hut the liquor remaining official organ of the Pittsburgh Section of the American after crystallization always held ahout 80 milligrams. The 15 primary liquors and the more concentrated In January of 1913 the Union Miniere de Haut Katsecondary liquors (about 100 liters) were then shipped anga of Brussels, Belgium, one of the world's largest from Canonsburg to the Pittsburgh laboratory where copper producers, discovered uranium ores in the copper fractional crystallization continued until the chlorides deposits in the Belgian Congo, but development was contained 40,000 milligrams per ton of radium element. postponed until 1921. The ore was refined in Belgium The next 10 to 12 fractionations brought the radium and was first marketed in December of 1922, ten years after Pittsburgh had placed radium salts on themarket. concentration up to 200,000 milligrams per ton. In 1912 Madame Curie established an international Now the radium and barium chlorides were made alkaline with sodium hydroxide and heated with hydrogen radium standard, which was located in, Paris; she presulfide to 'remove lead. The solution was filtered to pared a second standard for the Pittsburgh laboratory remove sulfur. The filtrate was made strongly alkaline of the Standard Chemical Company. This weighed with ammonium hydroxide and precipitated by satua PARTINGTON, J. R., "Gene~.aland Inorganic Chemistry for rated ammonium carbonate. The carbonates of radium University Students," Macmillan and Company, London, 1949. and harium were washed with hot water and dried in a * "Famous Pittsburgh industries," The Standard Chemical silica dish. Water and ammonium carbonate were Company, of Pittsburgh, Pennsylvania, The Crucible, XXII, 86-9 driven off by heating and hydrobromic acid was added (April); 109-13 (May); 134-7 (June, 1938).

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0.96 milligram. In 1914, our National Bureau of Standards, then known as the United States Bureau of Standards, acquired a third. N. F. Dorsey of the Bureau, visited Pittsburgh before organizing the Radium Standards Division. World War I began July 28, 1914. Europe wanted radium. On August 1, Glenn Kammer sailed for England, remaining there five months, and not returning until late December. Incidentally, he returned bn the "Lusitania," later sunk so catastrophically by a German submarine. Kammer carried four grams of radium as radium-barium bromide, value almost a half million dollars, product of the Pittsburgh laboratory. British newspaper headlines read "Carries Fortune in Radium," and told of Kammer's trip. On September 25 Kammer wrote: "We have just delivered Manchester's (the University of Manchester's) first shipment and got the money. Rutherford is in Australia, which disappointed me somewhat, but it turned out beautifully for his assistant (E. Marsdeu, noted for researches on actinium and thorium) was most courteous, inviting me to watch the measurements, which I was glad to do . . . . I got some very useful information.. . . Marsden found in the six tubes 106.54mg. Ra and our (Pittsburgh) figures were 106.59 mg. Marsden thought our measurements were quite marvelous." Let us remember that Kammer had not received any formal training in radioactivity, and that he was only 26 years old. The radium was consigned to the Royal Infirmary in Manchester. All purchasers were afraid that the American radium had been contaminated with the less valuable mesothorium. Sheffield insisted on an assay by the National Physical Laboratory in Teddington. On October 4 Kammer wrote: "You know the trouble we had with Sheffield about mesc-thorium. Well, now we have Northampton. I expect they will not pay unless N. P. Lab. makes a mes&horium determination, for N. P. Lab. will not certify to radium without this.. . . They do not have to take the radium a t all unless we have Teddington certify.. . . Northampton has not decided yet to accept the bromide as they have been advised to use sulfate.. . . Greenwich let the mesothorium go on recommendation of Teddington." Bear in mind that the United States of America mas not yet a t war with Germany. The Pittsburgh company furnished radium to various nations. A cable to Joseph A. Kelly, who had accompanied Kammer to England, mentioned Maine and Strassburg. Kelly Kammer had Scotland Yard on their necks "like a ton of brick. . . . We &ally cleared ourselves." On October 24 Kammer wrote to Viol: "I have been having a circus. My signature is no good a t all and I had to cable for a power of attorney for England. I have to go through all sorts of maneuvers to get the money to Pittsburgh. If I ask for cash, they think I am going to steal it. They kick a t everything. Swansea thought they were getting 100 milligrams of the element for $7000 and now when thev came to settle and saw 54 milligrams, they had to go and hold more

committee meetings.. . . I think the whole truth of the matter is that these people do not want the radium." Northampton had also demurred until Kam; mer threatened to take the radium back to America. Things went better a t Hull. On November 15 Kammer wrote that Northampton had agreed to pay for the radium without a meso-thorium test (actually the mesc-thorium content of the carnotite product was negligible). N. P. Lab. tinally convinced Greenwich, Swansea, and Northampton that the meso-thorium test was unnecessary. Warning Dr. Viol, Kammer continued: "Let Miller (Viol's assistant) weigh some of the tubes as you will expose yourself too much.5 They held up their hands in horror here when I told them what I have done with radium. Marsden (Rutherford's associate) said 'You have done a life's work.' A Radium Institute man warned 'watch out in four or five years from now' and Doctor Robeson, an X-ray man from Northampton, commented, 'I hope you get paid well for the chances you take."' Kammer closed this letter by again happily commenting on the close checks between the N. P. Lab. tests and the Pittsburgh measurements. In a letter sent to Kammer on December 14, Manden wrote: "I had no idea you were still in England. You could have come up (to Manchester) and had the run of the laboratory." In England, Kammer addressed numerous groups of physicians a t various hospitals. Newspaper articles and letters commended him for his services. During World War I Kammer got the idea that radioactive substances could play an important par6 in chemical ~ a r f a r e . He ~ was interested in radioluminescence? He and Miller in 1921 produced a t least a Quarter of a million luminous beads for use bv the MemurementS were made with electrometers (quantified electroscopes) read through small telescopes. The modern counters and remote control recording devices were not yet available. "The application of radium VIOL,C. H., AND G. D. KAMMER, in warfare," Trans. Am.,Eleetroehem. Soc., 32, 381 (1917). 'VIOL.C. H.. G. D. KAMMER. AND A. L. MILLBR."Deeav and regeneration of rsdiolumineseence,"Science, 61, 489 (1925); Nature, 115, 801 (1925).

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technicians in the laboratories in the Vanadium Building. As is so often the case, facts were misrepresented. Unscrupulous individuals advertised radium water, making great curative claims. The water was exposed to a small tube of radium salt but was not radioactive and had no curative value. This was the forerunner of our experience today with "fake cures" for cancer. About 1918 radium salt losses in hospitals were prevented. It was observed that the shorter-lived radon could be used as a gas in implants or spicules, which could be inserted into cancerous areas through a hypodermic needle andleft there. Even today, radon plants are being designed and constructed in various American cities by Arthur L. Miller, aforementioned. The author recalls that before radon was sold in these tiny implants for cancer treatment Kammer would send three 100-milliliter sealed bulbs of the radium emanation (so-called before it was rechristened radon) on V d h . Used by GIann Donald K a m m e ~ for Transporting Feu. Grams. orrasions tn.iw n year whrn three lertures rac-hday were the First Shipm-nt of American Radium to E u ~ o p oto , England d u r i n s eiwn 111 the Uniwrsitv's smnll lcctnre room. A milliWorld War I i u i e of the most diluie radon, hardly more than 0.05 cubic milliliter, for medical use, now sells a t about $2.50. United States Navy. Perplexing problems were en- On this basis, with the greater dilution of the large countered. On sealing the radioactive zinc sulfide into samples, the lecture demonstration gifts of Kammer in capillary tubes, luminescence was lost. This difficulty those earlier days would have been worth about $750 was finally overcome by placing a tiny bit of asbestos each.8 When the radium-emanation bulbs were opened fluff in the opening before sealing. The beads were in tall glass cylinders, coated with slightly impure zinc tubular with a lens on one end, diameter l/ls-inch, plus sulfide, the luminous effect was superb. Strangely or minus '/lm-inch, and of a maximum length of I/,enough, although we were unaware of the dangers of inch, with a minimum length of '/binch, and hermeti- the radioactive material, no harm befell us. cally sealed. Kammer had worked with zinc sulfide Among other contributions to the field of radium and and other compounds, studying the relative influence of radioactivity, were the devices of various kinds which various impurities on their radium-induced lumines- have been designed safely to handle and measure the cence. He objected seriously to the use of costly long- dangerous substance and to h e l p - m m ~ l o s t m d i w r n ~ ~ life radioactive substances for watch and clock dials Time and again, dressings in hospitals were lost. Ocand other luminous devices, when radium was so casionally the patient would slough off a dressing in a badly needed for the treatment of cancer. Further- toilet room, or a nurse would inadvertently throw it more, the life of these devices was usually limited to out with material that was to be discarded and burned. five or ten years. As a consequence, radioactive sub- It was necessary not only to trace radium in sewers, but stances of shorter life replaced rad'ium in luminous ma- to recover it from incinerator residues in the ash heaps. terials. Small spinthariscopes, retailing a t one dollar Henry Titus Koenig, another Pittsburgher, also was each, were made so that teachers, students, and even a factor. During 1913 and 1914, he was associated laymen could view the alpha scintillations in the dark. with fellow classmate Kammer and Dr. Viol in the labThe possible value of radium to the medical profes- oratory of Standard Chemical Company. In 1914-15 sion had to be developed. Clinics were held in various he studied under Professor George H. Hulett a t Princeparts of the United States and Canada, and in Europe. ton; while there, with Dr. Willey A. Schlesinger, heesThe approval of the American Medical Association was tablished an experimental laboratory of radioactivity. needed in this country. Finally, clinics were estah- The two incorporated the Schlesinger Radium Comlished by the Mayos in Rochester, Minnesota, a t the pany, which began operating in 1915. In this laboraHaward Cancer Clinic, and the Memorial Hospital of tory, in Denver, Koenig developed luminous materials New York, in the Columbia University Cancer Clinic, which were employed by the United States Governthe University of Pennsylvania, the Johns Hopkins ment during World War I. In 1919 Koenig, while on Hospital, and-in many others. he London ~ i d i u m leave of absence, spent six months with Professor HerInstitute and similar institutions in Germany, Austria, man Schlundt in the University of Missouri. He conand Italy, followed. Today, most recognized hospi- tinued as chief chemist for the Schlesinger Radium tals are equipped for radium therapy. Before radiotherapy was even suggested to the medical profession, 8 Erroneously reported value of $5,000,000 on basis of pure considerable chemical research on test animals had been radon in ~~-"Radioactivitv and the Universitv of Pittsburah." J. , (i945). conducted in Pittsburgh by a group of physicians and CHEM.E ~ u c .22,483 ~

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Compnny until 1921. Them, he developed methods the cost of nulium could have been appreriably lower for inrrrasing the rndium rrrovery from .50 per rent of had it not hrrn for American husiness nrumen. I t the rontent of the ore to f!8 per cent, thus ohtnining e m s thnt the Rdgians had even thrrntenrd to market ahout one grnm of rndium from MO tons of handpirkrd their p r d u r t at n lower c-ost, until what rrwmhlrd the orr. Then the rirh om from Kntangn in the Relginn mnlem rnrtel was estnhlishrd hy the Standard ChemiCongo wns n n n o u n r d Knrnig \van rallrd I)? the ml Compnny of Pittsburgh in confrrrnrr with the Union XIinierr of Oolrn in Rn~ssrls,Relgium, to apply E ~ m p r n nprdurers. At any mte, the prire rrmained his rrrovery methnls to the richer ow. At the .-me SI20 prr milligram. Consiclering thnt rndium hns a time, he instnllerl nppnrntus for the rrrovery of rnclium long lifr-a hnlf life of 1500 years-and thnt. only ahout emanation, or rndon. The Belgian drrelopmrnt out, 1 prr rent is lmt in 25 yrnrs, the snle to thr mediral the pricv of rndium in hnlf and the Amerirnn industry profewion and others w o ~ ~ knerrssnrily l fnll off with c r a . d . After the Bdginn work he sprnt ntmot thrre time, for it is not n materid whirh has to IIC rrplnrecl months with .\fnclamr ('uric in Pnris, nnd frrqumtly ronstantly like other rommotlities. Under those rirvisited Professor Anrtz in Hollnnd. In 1923 he IF- rumstnnrrs prrhnps the mnintrnanrr of high price turnrd to Amcrira, whrn his interest shifterl from rn- levels w s justifinl~lr. dium to vnnnclium. For his Ph.D. diswriation Glenn Knmmer rompleteil The value of rndium in 1014 \va. $120 per milligrnm, an important trr11ti.w on ioniom, whir11 was puldishd $120,000 per grnm, or n h u t %3,000,m per nunre. under the joint nuthomhip of Knmmrr and the writrr.* Sow the prire hns dropped to -50 or lrss per milligrnm. This wn- in line with his effort to clisrover sul~stnnresof for the mow p w From 1898, the date of disrovery of rndium, until shorter life whirh ronld hrsuhPtit~~trd 1924 the \vorlcl prwlurcd ahout 150 gmms or five rious rndium in luminous mntrrinls uwtl in commerrial onnres of rndium yi~lts. In 1020 the United Stntes artirles of romparnl~lyshort lirrs. As a conwquence, alone p d u r e c l 30 grnms, or ahout one ounre. During the rndium with its longer life, could iw consrrvrcl for that year Frnnre and Germany had p d u r c d only two mrdirnl nse. grnms, hustrin one nnd a half grnms, and Rndnncl oneKnmmer," Knrnig," and Yiol all died from the harmhalf gram. From 1913 to 1920 Knmmer, Viol, Knrnig, ful eflrrts of the po\verful gamma rnys of rndium. On and .\filler rrystallizrcl over hnlf the rndium mlts pro- the other hand, thousands of persons have benefited d u d in the entirr \vorld. Their work is an aclmirnhle from their proper npplirntion i n the trmtmrnt of rnnexample of American rnterprisc. Eurnpe first utilizrd e r . ,I he pionrrrs s ~ ~ f f e mthe l ronmqumres of inexthe rirher rndium ow, hut Amerirn took an o n whirh prrimre in the handling of this sulatnnre, whirh is so lvtm only onehundredth as rirh as that of the Boheminn ileadlv and yet so t~nefirial. Considering the thirk deposits and surressfull~woverwl the rndium. This lend shields nnd the hrnvy ronrrrtr \vnlls, the latter trndency hns r e p e a t ~ litwlf time and time appin in usonlly many frrt in thirkness, whirh nre employ4 commerrializing pnwraurs for the rerovew of n n t ~ ~ t x l ! a . I. Ilwovrry of ionium irnm rarnotilr; 11. suhstnnrm ocrurring in very low coneentrntions. A Adnorption of innium-thorium by hnrium nulf~te;Ill. 10niun1sprrimen of the original rndium-barium hromide pro- thorium rstin in rrtrnotite." J. A m . Chrm. Snr.. 47. 4512-22 clnred hy Knmmer nnd his assnrintes is still in I I . ~in the (l!K2.5). lo Slr.vmrrN. A,, "Glenn Donald Jiammer," N m Edition, I'nivemity of Pittxhurgh. One milligrnm whirh wns I d . Eng. Chrm., 5. So. 23.!1(1!127). p w n t e l hy linmmrr is exhibited rrpt~lnrlyto r l s ~ s c s Stwrnu~N.A,, "llmry Titua Koeni~,"Seimcr, 80. So. at the time when rnclium and rndioartivity a m stndirrl. 20(12, R (1!131). In 1921 the women of Amerirn s u h s r r i k l $100,0W, hy giving one dollnr enrh, toward n fund for thr purchaw of n grnm of radium for .\Indnmr Curie, for use in her rrwnrrhes i n Pnris. The prrsrntntion was mnde to .\ladame ('urie in .June. 1921. in T h r White House. hv Prrsidrnt Hardina. 0"the krnsion of this visit to Amerira she nlso spent some time at. the Stnndnrd Chemiral Company's plant in Cnnonshurg and in the Iahnrntorirs in I'ittsh~~rgh. It was on t h r nrrnsion of this visit that the Vnivrmitv of Pittshuah .. ronfrrrrcl the honornrv denrrr of 11wto; of I,n\vs. The C'hemistrv lkpnrtment of the Univcmity hns n rrplirn of thr t m t n l r s whirh rontnined one-tenth of n grnm each. This rrplira is shown rrgulnrly at lrcturrs on rndium nnd rnclionctivity. It wns prrpnrrd hy Dr. Iiammrr. Hr, Viol. and .\Iiller had lxrn instmmmtnl in crvstnllizina the gift. Its normal vnlue at that time 1vo111d hnve hrrn S120,000. The Company prnvidrcl the sprrimen for S100,Oo. uoth.. L~.UO. tor r . . ~ t i . ~ c-tr~~iution .~ -I ~ . d Ri ~ o~. . . v~ t. ~ . PI.^^ ~ ~ ~ In informal chats with Kammer it developed that,

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radioactivity in his lectures. These talks were included regularly in the introductory chemistry courses. He is eternally grateful to these martyrs to studies in radioactivity. A specimen of radium bromide, which was presented by Kammer, and the carnotite ore and willemite which he gave to the department, are still used to illustrn~clectures on radium 2nd radioactivity. J'h? old forwus and instruruenta with which the danerrous radium compounds are handled were given by Kammer. Also, there are the flasks which turned purple because they contained radioactive materials. These mere used in the Mayo Clinic in Rochester, Minnesota, in the early days. All of these were linked with the pioneer work which was begun in Pittsburgh. In conclusion, the ever-willing cooperation of Mrs. Glenn Donald Kammer, Arthur L. Miller, and Joseph A. Kelly is gratefully acknowledged. Without access to letters and other documents which Mrs. Kammer provided, much important information would have been lost.

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ADDITIONAL PUBLICATIONS OF CHARLES H. VIOL "Radium and its rays," Radium, 1, No. 1, 4-7 (1913). "The production and decay of radioactive matter," ibid., 1, No. 2. 4-7 - - f1914\. ~---"The radioactGe elements," ibid., 1, No. 3, 8-12 (1913). ''Firat pure radium salts prepared in America," ibid., 1, No. 6, S-9 (1913). "Production of radium in America," Mining and Sci. Press, 109, 4434 (1914). "Remarks on the production of radium by the Bureau of Mines," Ind. Eng. Chem., 8,284-6 (1916). "Extraction of radium, etc., by the U. S. Bureau of Mines," ibid., 8, 660-2 (1916). "Production of radium," Science, 43, 24-5 (1916). "Luminous Glaze for Clock and Watch Dials and for Other Uses, U. S. Patent 1,202,625, October 24, 1916. "Ra.dium and radioactivity," Chem. Met. Eng., 19, 752 (1918). "Radium production," Seimee, 49, 227-8 (1919). "Fused silica in radium production," Chem. Met. Eng., 28, 692

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in modern atomic energy plants, it is small wonder that the pioneer workers with gamma rays were the victims of their researches. The writer well recalls that Dr. Kammer, although he had repeated transfusions, sometimes several per day over a period of many weeks, never brought his red count back to normal because of the destruction of the bone marrow which functions in red cell formation. Kammer died of radium anemia .November 7,1927. Viol died in April, 1928, of radiuminduced cancer of the hand, arm, and lungs. Koenig died May 20, 1934, of a tumor of the hip joint. They shielded themselves as best they h e w how, hut not sufficiently toward off the deadly gamma rays. Miller, still active in the engineering field, has been physically handicapped, although he worked in the laboratory for only a comparatively short time. Through interest stimulated by his pupils, Kammer and Koenig, the writer was one of the first to include

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"Radon Tube or Implant of Intense Color and Ready Visibility," U. S. Patent, 1,574,456, February 23, 1926. "The Commercial production and uses of radium;' J. CHEM. EDUC.,3,757-72 (1926). N., "Chemical properties and relative With McCor, HERBERT activities of the radioactive ~roductsof thorium." Phil. Mao.. 25,33369 (1913). ~riginaicommunication,8th.1uternatioiai Congress of Applied Chemistry (Appendix) 26, 607-8. "The elimination of With SEIL,HARVEYA,, AND M. A. GORDON, soluble radium salts taken intravenously and per os," N. Y. State J . Med., 101, 896-7 (1915).