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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.)
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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.