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THK AMERICAN JOURNAL OF CLINICAL PATHOLOGY Vol. 44, No. 5 Copyright © 1965 by The Williams & Wilkins Co. Printed in U.S.A. BARIUM SULFATE AND ZINC SULFIDE DEPOSITS RESULTING FROM GOLF-BALL INJURY TO THE CONJUNCTIVA AND EYELID FRANK B. JOHNSON, M.D., AND LORENZ E. ZIMMERMAN, M.D. Armed Forces Institute of Pathology and the Veterans Administration Central Laboratory for Anatomic Pathology and Research, AFIP, Washington, D.C. 80805 Iii May 1961, sections of a conjunctival lesion, originally interpreted as a pigmented nevus, were received in consultation. The contributing pathologist was puzzled by the fact that, although microscopically the lesion seemed to be deeply pigmented (Fig. 1), grossly it had appeared nonpigmented. Our review of the sections led to the conclusion that the lesion was not a nevus, but rather an accumulation of crystalline foreign bodies that were so dense and opaque when viewed microscopically that they appeared to be pigmented. By means of x-ray diffraction and histochemical study, the conjunctival foreign bodies were found to consist of barium sulfate. But how could barium sulfate get into the conjunctiva? Obviously the material was exogenous, and a good history should provide the answer. The patient was an 11-year-old boy. The child's mother stated she had first noted the lesion on the upper nasal portion of the bulbar conjunctiva of the right eye 8 days before the ophthalmologist first examined the patient. According to the mother, the lesion had never appeared inflamed. Upon excision it had a white, caseous appearance and the consistency of a sebaceous cyst. After having been informed of the foreign nature of the contents of this peculiar lesion, the ophthalmologist queried the patient and his mother, both of whom denied any knowledge of injury. One interesting piece of information was obtained, however, that in retrospect proves to be most significant. The mother stated that on the day when she had first noted the lesion, her son had been cutting a golf Received, May 5, 1905. This studj' was supported in part by a Public Health Service Training Grant, 3T1 NB 5379-03S1, from the National Institute of Neurological Diseases and Blindness, United States Public Health Service. ball apart. He insisted, however, that he had not got anything in his eyes and had not hurt himself in any way. In spite of this negative history of trauma, and because the golf ball provided the only clue, an attempt was made to determine whether golf balls contain barium sulfate. The one golf ball examined gave- negative results, and the case was dropped from active study, but it was not forgotten! Three and one-half years later, Major Robert Penner, MC, USA, who had just been assigned to Walter Reed General Hospital from a tour of duty at Tripler General Hospital in Hawaii, informed us of 2 similar cases he had seen at Tripler.8 In his cases, however, the 2 children involved were brought in for examination because they were struck in the face by contents of the liquid center of golf balls that they were dissecting. In 1 case, radiopaque material was demonstrable in the lower lid and orbit. After excision of a portion of the lid containing the foreign body, the specimen was shown to be opaque to x-rays. We have been able to obtain some of this specimen (Fig. 2) for comparative studies, and as a result we. have been able to establish the identity of the substance microscopically and chemically in our case and in Penner's Case 1. In Penner's second case, the injuries were trivial and nonpenetrating, and the eye was not involved. In that case, however, the golf ball was brought along for examination. X-ray revealed it to contain radiopaque material, and chemical analysis established the presence of barium salt in the remnants of the ball. According to Penner, a variety of materials are used in the liquid center of golf balls produced by different manufacturers. At least 1 American manufacturer is known to incorporate lithopone (a mixture of barium sulfate and zinc sulfide) in golf balls. The fact that many other golf balls do not 533 534 J O H N S O N AND contain barium sulfate explains the negative results we obtained in our much-toocursory investigation in 1961. The material contained in the liquid center of these golf balls is under extremely high pressure. Apparently in our case, a fine stream of liquid containing lithopone was ejected under such great pressure that it was able to strike the eye and penetrate the conjunctiva without, producing pain—much in the fashion that the new hypodermic devices can inoculate the skin as a painless procedure. HISTOPATHOLOGIC AND H1STOCHEMICAL STUDIES Iii the 2 cases that we have studied, the lesions were remarkably similar, notwithstanding the fact that in our case the foreign material was believed to have been present for only 11 days, whereas in Peniier's case it had been present for more than a year. The barium sulfate deposits were located in the substantia propria of the conjunctiva in our case (Fig. 1) and in the dermal, subcutaneous, and muscular tissues of the lid in Peniier's case (Fig. 2). The overlying epithelial tissues were not significantly altered (Figs. 3 and 4). Under low magnification, the deposits were so dense that they appeared pigmented and resembled a mass of carbon particles, but examination of deparaffinized unstained sections with the naked eye revealed the deposits to be white. With high magnification, and wi'th~*th'e~ aid of polarized light, examination of stained sections showed the deposits to consist of birefringent white crystalline particles (Figs. 5B and 6B). This foreign substance had provoked a rather bland macrophagic response. With ordinary illumination it was difficult to ZIMMERMAN Vol. U visualize the relation of the crystalline particles to the cells, but with polarized light it was very clear that virtually all of the foreign particles were contained in the cytoplasm of macrophages. Very few foreign body giant cells were present, and these usually contained other unidentified, more highly birefringent crystalline particles. A light infiltrate of lymphocytes, plasma cells, and polymorphonuclear leukocytes was observed in the conjunctival lesion, which had been present for only 11 days. In the lesions of the lid, which had been present for more than a year, the inflammatory reaction was minimal. Vascular proliferation, scarring, and degenerative changes in the skin appendages and orbicularis muscles were also minimal. Stains for iron and calcium were negative. Bleaching with potassium permanganate and microincineration did not change the deposits. Treatment of the ash obtained by microincineration with acid failed to produce any gas bubbles, indicating the absence of carbonates and oxalates.6 Crystalline material was collected from the sections and subjected to x-ray diffraction studies. In both instances a pattern identical with barium sulfate was obtained (Fig. 7). Histochemical confirmation of the presence of sulfates was obtained with Johnson's sections were method. 6 Deparaffinized covered with black spray paint and then burned in the reducing flame of a Bunsen burner. This procedure converts sulfates to sulfides. Sulfide is then recognized by the release of bubbles of nitrogen from the crystalline deposits when the sections are treated with iodine-azide reagent. 3 When deparaffinized sections were tested with the iodine-azide reagent prior to the use of the reduction procedure, small quan- FIG. 1 (upper left). Section of excised conjunctival lesion reveals an accumulation of dense, opaque foreign material (barium sulfate and zinc sulfide) in the substantia propria. Hematoxylin and eosin. X 40. Ordinary illumination. (AFIP Ace. 1004233, Neg. 65-1397.) FIG. 2 (upper right). Section of excised eyelid (from Penner's Case 1) containing several large deposits of barium sulfate and zinc sulfide in the dermal, subcutaneous, and muscular tissues. Hematoxylin and eosin. X 15. Ordinary illumination. (AFIP Ace. 1159449, Neg. 65-1400.) FIG. 3 (lower left). The conjunctival epithelium is not significantly altered over the mass of barium sulfate and zinc sulfide, and the tissue reaction to the foreign material appears minimal. Hematoxylin and eosin. X 115. Ordinary illumination. (AFIP Ace. 1004233; Neg. 65-1396.) FIG. 4 (lower right). The epidermis of the eyelid over the barium sulfate and zinc sulfide deposits is not significantly altered, and the tissue reaction to the foreign material appears minimal. Hematoxylin and eosin. X 70. Ordinary illumination. (AFIP Ace. 1159449, Neg. 65-1401.) V ^>U 1 n \ X 0 * 3 ^Sj, » ^% «b "5 >-V ^ l * 5 L « * . « r F I G S . 1, 2, 3 and 535 4 /f'/ * 536 J O H N S O N AND tities of bubbles were released over the crystals. This indicated the presence of preformed sulfides such as the zinc sulfide component of lithopone. Following the reduction step, however, the release was copious, indicating further formation of sulfide from the barium sulfate. Lithopone, according to Craig,1 is a mixture of about 30 per cent zinc sulfide and 70 per cent barium sulfate. This mixture presents a curious matrix problem of the sort mentioned by Klug and Alexander7 when studied by the powder method of x-ray diffraction. Some crystalline substances, which can be identified by their characteristic powder patterns when studied in pure form, yield such poor patterns that they may not be detected in mixtures even when they are present to the extent of 50 per cent. This phenomenon accounts for the fact that our x-ray diffraction patterns revealed no evidence of zinc sulfide, even though this compound is said to be an important constituent of lithopone. Through the kind cooperation of Dr. A. J. Tousimis, sections were studied by means of electron probe x-ray microanalysis with the technic he has described elsewhere.10 His studies revealed the definite presence of zinc as well as barium and sulfur in both instances. COMMENT The potential danger to which children expose themselves when they engage in unravelling or cutting apart a golf ball has long been recognized, not only by such eminent and authoritative sources as DukeElder2 and Grant, 4 but also by the children themselves. In his delightful book "Where Did You Go?" "Out." "What Did You Do?" Vol. U ZIMMERMAN "Nothing," Robert Paul Smith 9 relates the following: "After a certain amount of time, the golf ball—which we wouldn't have had at all unless the cover was cut almost to ribbons—would have enough cuts in it so you could pull off the white covering. Then for another three days, what you did was unwind the rubber band. I am not sure what you did with the rubber string you unwound, except to wrap it around various parts of your body until the circulation stopped. Mostly, once again, it was just what kids did. Unwound the rubber. In the center was a little white ball the size of an immie. Inside it, we knew, was something which was so dangerous it was inconceivable. There were two schools of thought. One, that it was an explosive so powerful that, that, that—well jeez, it was an explosive] The other school of thought held that it was a poison that killed not only on contact anybody who was foolhardy enough to open it, but it would strike dead, on the whole block, every person, cat, collie dog. It could also wither trees and probably melt the pavement." Duke-Elder2 and the manufacturers of golf balls assure us that today the liquidcenter golf ball is no longer the ghastly thing that it was when Mr. Smith was a kid. Apparently the "poisonous" element has been removed, but the explosive force with which the contents are ejected when the liquid center is opened remains a hazard. SUMMARY Deposition of barium sulfate and zinc sulfide in the conjunctival and palpebral tissues of 2 children occurred as a consequence of taking golf balls apart. These compounds are known to be ingredients of FIG. 5 (upper). A. The barium sulfate and zinc sulfide crystals are tightly packed within the cytoplasm of macrophages. The foreign material obscures the nuclei of these macrophages. Conjunctival lesions. Hematoxylin and eosin. X 305. Ordinary illumination. (AFIP Ace. 1004233, Neg. 65-1392.) B. Same field shown in A but photographed with polarized light to reveal the birefringence of the intracellular deposits. The nonbirefringent nuclei of the macrophages can now be identified (arrows). (AFIP Neg. 65-1393.) FIG. 6 (lower). A. Barium sulfate and zinc sulfide deposits contained within the cytoplasm of macrophages deep in the muscle layer of the lid. Hematoxylin and eosin. X 395. Ordinary illumination. (AFIP Ace. 1159449, Neg. 65-1398.) B. Same field shown in A but photographed with polarized light to reveal the birefringence of the intracellular deposits. The muscle fibers (M) and nuclei (arrows) are not birefringent. (AFIP Neg. 65-1399.) Nov. 1965 BaSC-4 AND ZnS IN CONJUNCTIVA AND EYELID 537 538 JOHNSON AND ZIMMERMAN Vol. U F I G . 7. X - r a y diffraction p a t t e r n s . A. Barium sulfate standard. B. Crystals obtained from sections of eyelid lesions (AFIP Ace. 1159449). C. Crystals obtained from sections of conjunctival lesion (AFIP Ace. 1004233.) the liquid center of at least 1 American golf ball. In the first of the 2 cases, the child was unaware of being struck in the eye, and the source of the conjunctival foreign body remained a mystery for Zl/i years. Information about the second case provided the clues needed to solve the mystery of the first case. Barium sulfate and zinc sulfide seem to be remarkably inert, provoking chiefly a macrophagic reaction, and even after 1 year there was negligible evidence of tissue damage. The presence of barium sulfate in the tissues was proved by x-ray diffraction studies as well as by use of the electron probe, but the presence of zinc sulfide could be demonstrated only by the latter. REFERENCES 1. Craig, A.: Rubber Technology, Edinburgh and London: Oliver & Boyd, Ltd., 1903, p . 114. Duke-Elder, S.: Text-Book of Ophthalmology, Vol. VI, Injuries. London: Henry K i m p 1,o», 1954, p . 6582. Feigl, F . : Qualitative Analysis by Spot, T e s t s . Ed. 3. New York: Elsevier Press, Inc., 1947, p. 228. Grant, W. M.: Toxicology of the E y e . Springfield, 111.: Charles C Thomas, Publisher, 1902, p. 257. Johnson, F . B . : A method for demonstrating calcium oxalate in tissue sections. J . Histochem., 4: 404-405, 1950. Johnson, F . B . : Demonstration of sulfates of alkaline-earth metals in tissue sections. J. Histochem., 8: 332, 1900. Klug, H., and Alexander, L.: X - r a y Diffraction Procedures. New York: John Wiley & Sons, Inc., 1954, p . 414. Penner, R.: The liquid center golf ball—a potential ocular hazard. Arch. Ophthal. (Chicago), in press. Smith, R. P . : "Where did you g o ? " " O u t . " "What did you d o ? " " N o t h i n g . " New York: W. W. Norton & Company, Inc., r 1957. 10 Tousimis, A. J . : Electron probe x-ray microanalysis of medical and biological specimens. In Symposium on X-ray and Electron Probe Analysis, Special technical publication no. 349, American Society for Testing and Materials, 1903, p p . 193-200.