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Permanent wave contact dermatitis: Contact allergy to glyceryl monothioglycolate
Journal of the American Academy of Dermatology
Kennedy and kyell
mending his working clothes a few days before the onset of the lesion Exammatmn revealed a well chdd with a dusky, purphsh nodule, approximately 2 5 cm m diameter, at the base of the scrotum (Fig 4) There was no regmnal lymphadenopathy Viral partmles consistent wlth the morphology of off were seen by electron mmroscopy m scrapmgs from the lesmn DISCUSSION O f f IS c a u s e d by a m e m b e r of the parapox family o f viruses It lS w i d e s p r e a d in sheep, mainly affecting lambs, where ~t p r o d u c e s nodules and e r o d e d lesmns, particularly around the mouth and nose H u m a n lesions usually o c c u r by &rect contact and are thus c o m m o n a m o n g shephmds, farmers, and veterinary surgeons Infection may occur m & r e c t l y , h o w e v e r , for e x a m p l e , from a c o n t a m i n a t e d pasture
In the first case described in this report, the permnal lesmns presumably arose by automoculatmn from the d~gltal lesmn, whmh had gone unnotmed until a full e x a m m a t m n was carried out by the dermatologist Because o f the lntertngmous site, the macerated permnal lestons were not &agnostm of orf in appearance and bore a resemblance to secondary syphdls In the second case, it was presumed the mother had acted as an asymptomatlc carrier for the off wrus since she both changed the b a b y ' s drapers and had m e n d e d her farmwinking husband's clothes These cases Lllust~ate the potentml ~mportance o f knowing the parental occupatmns and enwronments o f pedmtrlc patmnts
Permanent wave contact dermatitis: Contact allergy to glyceryl monothioglycolate Frances J Storrs, M D , Portland, OR Eight hairdressers and four chents were found to be allergic to glyceryl monthloglycolate (GMTG) contained m " a m d " permanent waves used m American beauty salons only since 1973 Previous studms m Germany showed that compounds closely related to GMTG were strong sensmzers In contrast, ammonmm thloglycolate (ATG) has been used since 1943 m cold "alkahne" permanent waves both m homes and m salons with no clearly documented cases of contact allergy Our allergm patmnts reacted to GMTG m concentrations as low as 0 25%, although thmr exposure m practice could reach concentrations of 20% to 80% GMTG-allergm patients reacted to GMTG when tt was tested thlough a variety of glove fabrics Household-weight neoprene gloves were protectlve (J AM ACAD DERMATOL 11 74-85, 1984 )
From the Department of Dermatology The Oregon Health Scmnces Umvers~ty Accepted for pubhcat{on Nov 9 1983 Reprint reqtmsts to Dr Frances J Storrs Department of Dermatology The Oregon Health Setences UmVmSlty, 3181 S W Sam Jackson Park Rd , Portland, OR 97201/503-225 8597
74
Mllllons o f permanent waves are g~ven each year to American men and women both in their homes and m beauty salons In 1976, it was estimated that 57 m d h o n dollars was spent on home permanent Mts and another 30 mllhon dollars on permanent waves ( " o e r m s " ) given in
Volume 11 Number 1 July, 1984
Table I. GMTG-containing permanent waves 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24.
Rilling Perfect Touch (Rilling) One Better (Helene Curtis) Uniperm Acid Wave (Helene Curtis) Quantum (Helene Curtis) Apple Pectin Acid pH Perm (LaMaur) Full Dimension (LaMaur) Zotos Warm and Gentle (Zotos) Pliance (Tressa) Belgian Formula Special (Fermodyl) Day Into Night (Redken) Creative Curl (Redken) Thermo Curl (Naturelle) Patent 289 (Wella) Great Feeling (Revlon) Sensor Perm (Revlon) Lush & Lovely (Revlon-Realistic) Sensor Curl (Revlon-Realistic) Great Feeling for Blondes (Revlon-Realistic) Genus-30 Celsius Perm (Revlon-Realistic) No Rods Just Rollers (Revlon-Realistic) Living Curl (Revlon-Realistic) Sensor Supreme (Revlon-Realistic) Special Feeling (Revlon-Realistic) Texture Silk (Revlon-Realistic)
beauty shops.' These figures are much higher today. It is fortunate that the problems associated with properly performed permanent waving are few. In fact, from 1977 to 1980, problems with permanent wave ingredients accounted for only three of the 487 patients described in a study of cosmeticsrelated skin reactions. 2 Heat and water have been used to curl hair for thousands of years. The first real permanent waving was accomplished in 1906, when Nessler applied heat to hair that had been wound on the head and treated with alkali. :~'4 Few changes were made in this basic method until 1943, when cold waving using ammonium thioglycolate (ATG) came into general use and the first home kits were introduced. :~ Their use was great from the start, and by 1949, the chief of the division of pharmacology at the Food and Drug Administration was able to state that "the judicious use of ammonium thioglycolate as a hair-waving preparation should prove a relatively innocuous procedure. '''~ Although reports of allergy to ATG do exist, they are rare and astute observers have doubted their veracityfi '7 Today, salts of thioglycolic acid (TGA)
Permanent wave contacl dermatitis
75
i
[s-cH2_C~oNH," Ammonium Thioglycolale
HS- CH2-C .. O_ CH2..CH-CHz-OH OH Glyceryl Monothioglycola e Fig. 1. Both ATG and GMTG contain a sulfhydryl (SH) group. The GMTG side chain appears to enhance allergenicity. still represent the greatest proportion of home and salon permanent waving preparations (Fig. 1). Although these permanent waves are efficient and relatively safe, they do, nonetheless, damage the hair with frequent use and not uncommonly irritate the scalp. Titus manufacturers have sought milder products. If the carboxylic acidity of TGA is blocked by esterification or acidification, the resulting compounds are active at lower pHs and are said to be less damaging, s In the late 1950s and early 1960s, such compounds were widely used in Germany. "~ Unfortunately, both the hydrazide and the glycolic ester of TGA caused over 100 reported cases of allergic contact dermatitis and sale o'f these preparations was stopped) In the published review of the German outbreak, and in screening studies of other mercaptans (sulfhydryl-containing compounds) for skin sensitization as a prelude to selecting yet other compounds for permanent waving, the glycerylic ester of TGA [glyceryl monothioglycolate (GMTG)] was not included 'a''~ (Fig. 1). This compound (GMTG) was, however, being manufactured in Germany in the early 1970s and in 1973 was imported to the United States and repackaged for distribution here. By September, 1973, it was being manufactured in the United States, and in 1979, six "acid p e r m s " containing G M T G were available for use only in salons. Today over
76
Journal of the American Academy of Dermatology
Storrs
T a b l e I I . G M T G - p o s i t i v e hairdressers GMTG Atopic history Patients
Age (yr) [
Personal , [
1
27
Hay fever
2
34
--
3
36
Eczema (child)
4
21
Hay fever
5
30
Hay fever
6
29
Keratosis pilaris
7
28
Hay fever
8
41
Hand eczema
Family
GMTG exposure history
ACD before diagnosis
Distribution
Lowest % concentration
Lowest % concentration through gloves
4 mo
31/z yr
Fingertips
0.25
0.25
5 mo
2 yr
Fingertips
0.50
0.50
Eczema, asthma, hay fever Hay fever, asthma --
7 mo
8 mo
Fingertips, palms
0.50
2.5
21 mo
4 mo
0.50
0.50
11 mo
4 mo
0,25
0.25
Hay fever
1 mo and penn 2 yr previously 10 mo
2 mo
0.50
0.50
1.0
NT
10 mo
3 yr
Sides of fingets, arms Fingertips, under ring Dorsal aspects of fingers; arms Dorsal aspects of fingers Fingertips, sides of fingers
0.25
NT
Eczema
Eczema, asthma
1% yr
ACD: Allergic contact dermatitis; e: no standard tray applied; NT: not tested; -: negative.
twenty " a c i d p e r m s " for salon use exist (Table I). W e k n o w o f only two G M T G - c o n t a i n i n g permanent w a v e s sold in G e r m a n y (Goldwell and Wella). G M T G is not c o n t a i n e d in any h o m e perm a n e n t w a v i n g product. G M T G - c o n t a i n i n g p e r m s were not used widely in O r e g o n until 1977 or 1978. We saw our first G M T G allergic contact dermatitis in a hairdresser in July, 1980. This r e p o r t will describe eight hairdressers and four clients with G M T G allergic contact dermatitis w h o m we studied between July, 1980, and March, 1983. CASE REPORTS
A representative hairdresser and client are described. Details of the other patients are outlined in Tables II and III. Hairdresser
A
A 27-year-old white male hairdresser developed a hand dermatitis 4 months after acid perms had been introduced into his beauty salon. The dermatitis began
on his fingertips and only occasionally involved the skin over the dorsa of his fingers. He had hay fever and a sister with hand eczema, but he had never before had a hand dermatitis despite 6 years of work as a hairdresser with considerable exposure to cold (alkaline) permanent waves. He suspected the acid perms were causing his difficulty, particularly since he had developed forehead and scalp dermatitis when he was given an acid perm. Before his referral to us in August 1980, he had been troubled by incapacitating hand dermatitis for 31h years, for which he had received intramuscular injections of long-acting corticosteroids every 6 weeks. He developed striae, bruisability, and fatigability and also gained 30 pounds. He consulted an endocrinologist, who referred him to us. We patch-tested him (see "Patch Testing Methods") to our hair dye tray, the North American Contact Dermatitis Group's (NACDG) standard tray, and to our vehicle and preservative tray. He performed open patch tests to the waving solution of one of his acid perms, He developed positive reactions to paraphenylenediamine (PPD) and to two PPD analogs, His open test was also positive.
Volume 1l Number I July, 1984
Other positive reactions
Permanent wave contact dermatitis
Owns shop
Follow-up
ATG, PPD
Yes
Clear; avoids acid perms Clear; avoids acid petals Better; quit; atopic hands
Neomycin
Yes
Bronopol
No
0§
No
Flares; works
Potassium dichromate 0
Yes No
Flares; works; atopic hands Clear; quit
ppD +
Yes
Flares; works
Quaternum- 15, formaldehyde, imidazolidinyl urea
Yes
Fl~tres; works; atopic hands
After consulting the very cooperative manufacturer of one of his acid perms, we obtained some GMTG. This was prepared 2.5% in petrolatum as was the ATG. Both of these tests were 2+ positive at 2-day and 1-week readings. Fourteen months after first seeing this man, we tested him again. This time we tested him to dilutions of GMTG that we applied over various glove fabrics (Table IV). He developed positive reactions through most of the gloves down to a concentration of 0.25% GMTG in petrolatum. ATG, 2.5% in petrolatum, was also tested but did not penetrate a lightweight vinyl glove, which cast some doubt on its original validity as an allergic reaction. This man owned his own beauty salon and continued to work. He was free of dermatitis as long as he completely avoided acid perms. Client A A 67-year-old white housewife had experienced lifelong hay fever and had had one outbreak of flexural eczema in her late forties. Occasionally, she developed patchy dermatitis on her arms, bands, and the posterior portion of her neck, which she could control with corticosteroid creams. She had received salon cold perms and home perms wit~aout incident throughout her adult
77
life. In a 2-year period, she received three acid perms. After the second one, she noted some itching and irritation on her forehead. In July, 1982, after her third perrn, she noted itching of her scalp in the evening, Her skin was clear on the day of her July perm, but she developed an acute oozing dermatitis of her neck, ears, and scalp by the next morning. Her eyelids were edematous. The acute dermatitis subsided but left a chronic eczema in its wake, for which she refused treatment because of her concern with steroid side effects. After tolerating this dermatitis for 6 months, she was referred by her general physician to the dermatology department of the Oregon Health Sciences University. Patch testing to the NACDG standard tray and the hairdresser tray (see "Patch Testing Methods") provided positive reactions only to 1% GMTG in petrolatum and questionably to formaldehyde. She was further tested to four dilutions of G M T G through a variety of glove fabrics (Table IV). She reacted positively through most of the gloves to concentrations of GMTG as low as 0.5% in petrolatum. Her dermatitis quickly cleared with cortieosteroid ointments. She had had no more permanent waves and remained free of dermatitis as of April, 1983. Other hairdressers Details of seven other hairdressers are included in Table II. The hairdressers' average age was 31 and all but Patient 1 were women (five Caucasian, one Cuban, one Iranian). Seven hairdressers had personal histories of atopy (asthma, hay fever, or eczema), but only one of the seven had had hand eczema prior to GMTG exposure. Five hairdressers had family histories of atopy. Both the hairdressers and clients were seen in The Oregon Health Sciences University's general dermatology clinics and on referral to our private clinics and contact dermatitis evaluation clinic. There was no significant difference between the average period of time required to sensitize hairdressers who worked 1 to 4 years in salons before G M T G perms were introduced (Patients 1, 2, 5, 7, and 8) and those who had been exposed to acid perms from the onset of their work experience (Patients 3, 4, and 6); 8 versus 10 months. The patient who appeared to sensitize most rapidly (Patient 6) had received an acid perm 2 years previously. In every instance, there was a delay in diagnosing the cause of the hairdressers' dermatitis. As word of our interest spread into the community, this time was shortened from years (Patients 1 and 2) to months (Patients 4, 5, and 6). A predilection for the fingertips was the distinguishing feature of the hairdresser's hand dermatitis (Fig, 2 and 3). In several instances, dorsal surfaces of the distal
Journal of the American Academy of Dermatology
Stot~
78
Table III. GMTG-posmve
chents
Atople history Patient
(yr)
Personal
Famdy
1
67
H a y fever
2
59
H a y fever, eczema --
3
43
--
4
60
--
exposure history
--
Oceupatmn
Housewife
3 yr
Neck, scalp, ears, hands, arms Neck, scalp, ears
Housewife
24 hr
Neck, ears
Cook
Neck, scalp, forehead, ears
Secretary
6 mo
4 perms/ 4 yr 2 perms/ 1% yr
--
Distribution
diagnosis
3 perms/ 2 yr 6 perms/ 3 yr
Eczema
ACD Allergic contact dermatms -
ACD before
GMTG
Age
1
mo
negatwe
*Only Chent 3 was tested to compIete concentratton panel without gloves fOnly concentratmn tested
Table IV. GMTG reacnons through gloves G M T G concentration (%) giving positive reactmn through gloves
Butadlene
Latex surgeon)s
polymer
Patients, I (HD)
05
2 3 4 5 6
1 0 NT NT 0 25 NT NT NT I 0 --
(HD) (HD) (HD) (HD) (HD)
1 (C)
2 (C*) 3 (C) 4 (C) -
2D
7I)
2D
}
7D
Neoprene household
Vinyl exam
2D
]
7D
2D
]
7D
Vinyl household 2D
7D NT
--
l 0
--
025
25
--
--
NT
-NT NT 2 5 NT NT NT ---
1 0 -0 5 NT --
---NT --
0 2 0 0 0
-2 5 -0 25 0 5
--
--
NT
--
--
25
25
05
25
1 0
1 0
05
05
-025 2 5
10 25 --
-05 2 5
10 10 2 5
5 5 5 25 5
NT
--
--
--
--
NT
NT
--
--
NT
NT
--
--
10
10
--
--
10
10
--
--
0 25
0 25
--
--
NT
NT
Negative C chent, HD hmrdresser NT not tested 2D 2 days, 7D 7 days
*Only 1% concentration tested
aspects o f the fingers were involved primarily (Fig 4) An especmlly interesting pattern of dermatms revolved the radml and ulnar sides of the second and third fingers and appeared to correspond to skm exposed to test curl hatr before the neutrahzatton process (Figs 2 and 5) Arm mvolvement corresponded to "spatters" o f curlmg solution There was no web space mvolvement Five o f the eight hatrdressers own thear salons and have continued to work Patient 2 allows no acid perms m her shop and is clear Pataent 1 has acid perms in his shop but does none himself He also ts clear The other three owners (Patients 5, 7, and 8) g w e acid perms occasionally but always have a flare o f their dermatms ff they do not wear gloves of a wmght that wall protect
them Pattent 8, who had hand eczema before sen slhzatlon, stall has it and ~t flares addmonally wlth acJd perms Patient 5 developed a mild coexisting, probably atoplc, hand eczema that served as a background to flares of her dermatitis with acid perm exposure If she wears neoprene household-weight gloves whde giving acid perms, she has almost no trouble Of the three non-shopowners, two have qmt working One of these (Patient 3) continues to be troubled by an atoplc hand eczema, which flared for the first time m 20 years (coincident with her G M T G sensmzanon) The other (Patient 6) is tully clear Patient 4 did not qmt working and her dermatms flares when she g~ves acid perms JUSt like the shopowner's does
Volmne 11 Number 1 July, 1984
Permanent wave contact dermatitis
79
GMTG*
Lowest % concentration
Lowest % concentration through gloves
Other positive reactions
0.5
0.5
Formaldehyde
1.0q"
1.0t
0.25
0.25
Nickel, fragrance mix, plants, Thiuram Nickel, epoxy
1.0
2.5
Nickel Fig. 2. Dermatitis corresponds to the place where the test curl hair touches the fingers (Hairdresser 5).
Other clients Details of three other clients (all Caucasian women) are tabulated in Table [II. Their average age was 57. Only Patient 1 had had a personal history of atopy, whereas Patients 1 and 3 had family histories. All the clients had received at least one acid perm before becoming sensitized. This is a difficult interval to ascertain in that, as with Patient I, most patients noted some slight hairline dermatitis before their explosive episode. Patient 2 tolerated postperm dermatitis for several years before a diagnosis was made. The dermatitis in the other three patients was diagnosed within hours or months after their acute experience. The neck and ears were the skin sites most commonly involved with acute dermatitis. The scalp was also extensively involved in three patients. Two patients worked outside of their homes. Clients 3 and 4 have had several cold (alkaline) perms without incident since their GMTG allergy was diagnosed.
!iiii! il84
PATCH TESTING METHODS Allergens were applied to aluminum discs (Finn chambers) and then secured to the upper portion of the back of each patient with a porous tape (Scanpor). They were left in place for 48 hours and then removed and read 30 minutes later. A second reading was done at 7 days. Only reactions present at both the 48-hour and the 7-day reading were recorded as positive. All patients except Hairdressers 4 and 7 were tested to the NACDG's standard tray of allergens.* A hairdresser tray was applied to all the patients. During the 30 months of the study, this tray's constituents varied but consisted of the following allergens (prepared in pet*See Patch Testing in Allergic Contact Dermatitis. Evanston, IL, 1982, American Academy of Dermatology, Inc.
Fig. 3. Fingertip dermatitis was the most common distribution pattern (Hairdresser 2). rolatum unless otherwise specified) during the majority of the time: quaternium-15, 2% in water; p-aminophenol, 10%; m-phenylenediamine, 2%; resorcinol, 2%; 2,5-toluenediamine, 1%; p-phenylenediamine (PPD), 1%; hydroquinone, 1%; 4-aminodiphenylamine, 0.25%; fragrance mix; 2-nitro-p-phenylenediamine, 2%; pyrocatechol, 2%, in 95% ethanol; 4ethoxy-m-phenylenediamine, 1%; ATG, 2.5%; formaldehyde, 2% in water; ammonium persulfate, 2% in water; GMTG, l%; pyrogallol, 1%; glycerin, 100%. GMTG was used at a concentration of 2.5% early in the study, but this was subsequently lowered to 1%. All
80
Journal of the American Academy of Dermatology
Storrs
Fig. 4. Occasionally the skin of the dorsal surface of the fingers was involved. The webs were spared (Hairdresser 7).
Fig. 6. Pieces of glove separated the allergen from the patient's back. Fig. 5. Hairdresser performing a test curl. Note position of thumb and ~nde• finger and compare to Fig. 2. patients except Client 2 were tested to dilutions of GMTG down to 0.25%. Additionally, all patients except Hairdressers 7 and 8 were tested to four dilutions (2.5%, 1.0%, 0.5%, and 0.25%) of GMTG applied over a variety of gloving fabrics (Fig. 6 and Table IV). These glove fabrics included a styrene butadiene block polymer surgeon's glove (Elastyren), a synthetic rubber surgeon's glove (Perry), a light- and medium-weight polyvinyl glove [Tru Touch (Edmont Wilson) and Allerderm], and a household-weight neoprene glove [Super Ebonette (Pioneer)]. Client 2 was tested only at 1%. These more cumbersome patches were also left in place for 48 hours and read at 48 hours and 1 week. Finn chambers and Scanpor tape were again used. GMTG was evaluated for irritancy by including it wi~h allergens on the standard tray we use to investigate patients with saspect alIergic contact dermatitis. Forty-five patients (twenty-four women and twenty-one
men) were tested at 2.5%, and sixty patients (twentynine women and thirty-one men) were tested at 1%. G M T G was also tested at 2.5% and at 10% through vinyl gloves on a smaller and different group of patients with suspect allergic contact dermatitis from cause~ other than GMTG. PATCH T E S T RESULTS At 2.5%, G M T G gave no irritant reactions in twenty-one control men but did produce one irritant reaction among twenty-four control women. At 1%, thirty-one men and twenty-nine women showed no irritant reactions to G M T G . Our 2.5% G M T G in petrolatum was shared with colleagues in Vancouver, BC, who noted two irritant reactions in twenty eczema patients. 11 W e now test G M T G at 1.0% because G M T G 2.5% in petrolatum is occasionally irritating and because 1% identified all our positive patients. One GMTG-ailergic hairdresser and one client
Volume 1l Number I July, t984
gave no positive GMTG reaction below 1.0%. Client 2 was not included in this analysis because she was tested only at 1%. Three hairdressers and one client reacted down to a GMTG concentration of 0.25% and four hairdressers and one client gave reactions no lower than 0.5%. All our patients were tested with ATG, 2.5% in petrolatum. Only Hairdresser A had a positive reaction. This reaction could not penetrate a lightweight vinyl glove, but it was positive on two separate testings without a glove. Glycerine, 100%, was added to the hairdresser's tray halfway through the study. Nine patients had negative reactions to it. Hairdressers 4 and 7 were not tested to the standard tray. Among the other patients a few coincident positive :reactions were common. Two hairdressers were concomitantly positive to PPD. One hairdresser reacted to neomycin and two to formaldehyde or formaldehyde-releasing preservatives (Patients 3 and 8). Three of the four clients were nickel-sensitive. In all the patients, we were able to establish clinical relevance for their additional positives except for Hairdresser 5's chromate sensitivity and Client 3's epoxy reactivity. Eleven control women and seven control men showed no irritancy to 2.5% GMTG applied over vinyl examination-weight gloves. None of the seven control women tested to 10% GMTG over vinyl gloves had an irritant reaction, but one of the five control men had a definite irritant reaction at 10%. He was negative to 1% GMTG applied without the glove barrier and negative to the glove applied alone. All GMTG-allergic patients tested to GMTG through various gloves (Figs. 6 and 7 and Table IV) reacted through at least one kind of gloving fabric. Only Hairdresser 3 and Client 4 did not have positive reactions through gloves at the same low concentration to GMTG that they achieved without the glove barrier (Tables II and III). The household-weight neoprene glove (Super Ebonettes) was the only gloving fabric that universally blocked penetration of the allergen (Table IV). None of the other gloves provided regular protection, although in many instances reactions positive at 48 hours were negative at 7 days or remained positive only at the higher concentrations.
Permanent wave contact dermatitis
81
Fig. 7. Positive patch tests occurred even when the allergen had to pass through some glove fabrics (Hairdresser 5). DISCUSSION Permanent waving is a chemically active process, the efficacy of which depends on marked rearrangement in hair proteins (keratin). Keratin fibers are composed of polypeptide chains that are attached laterally to adjacent chains by chemical bonds. Hydrogen bonding can be disrupted by heat and water and then re-formed by drying. The changed configuration of the hair, however, is not long-lasting. The prevailing influence on the cohesion of hair keratin can be attributed to covalent disulfide cross-linkages between polypeptide strands.:~'4"7"~ When these "keratocystine" cross-linkages are disrupted in a wet, alkaline environment, such as that provided by the alkaline salts of TGA, the hair becomes softened and then plastic. Once the desired realignment is achieved, the broken (reduced) disulfide bonds can be reformed in the presence of a neutralizer (oxidizing
82
Journal of the American Academy of Dermatology
Storrs
PERMANENT WAVE CHEMISTRY K-CH2--S-S--CH2-K
+
-S-CH2-CO2THIOGLYCOLATE
+
--02C-CH2--S-S--CH2--CO 2-
"'KERATOCYSTINE"
K-CH2-S"KERATOCYSTEINE"
DITHIOGLYCOLATE
Fig. 8. When the disulfide bond in hair keratocystine is reduced to a cysteine sulfhydryl group, the hair becomes plastic and its configuration can be changed. Oxidizing the cysteine back to disulfide linkages renders the change permanent. agent). This " h a r d e n i n g " produces new bonds that hold the hair in a curled position until it grows out or is re-treated (Fig. 8). 1"~'~ Voss 10 postulated that chemicals related to TGA (mercaptans) are capable of inducing contact sensitization by this same splitting o f disulfide bonds o f skin proteins and forming derived proteins that serve as the actual allergens. Since 1943, most cold permanent waving used in salons and in homes has contained ATG. This compound must be used at a pH between 9.3 and 9.5. Esterification of the carboxylic acidity of TGA produces compounds that, although less potent reducing agents, can be used at more neutral or even slightly acid p H s - - h e n c e , the popularity of so-called " a c i d " permanent waving since 1976 or 1977, which utilizes GMTG and is said to "protect" hair, particularly that weakened by previous permanent waving. The term acid, however, is often a misnomer because the pH varies from manufacturer to manufacturer and is often alkaline. Knowledge of the actual procedure used in performing an acid perm can be of value in questioning patients and in informing them how best to protect themselves. This is especially true in that permanent waving products used by professionals are generally packaged without ingredient labels. Most acid perms consist of three parts (Fig. 9): the curling lotion, which contains ammonium hydroxide, water, various surfactants, fragrances, and sequestering agents; a small tube-shaped bot-
tle, which contains GMTG in concentrations up to 80% plus up to 5% residual TGA and as much as 20% glycerin plus various diluents; a neutralizer, which contains oxidizing agents such as bromates, perborates, hydrogen peroxide, or ammonium persulfate, as well as various preservatives, citric acid, surfactants, and fragrances.l'a'~ The small GMTG-containing tube is mixed with the water-based ammonium hydroxide solution and applied directly to the wound hair on the client's head (Fig. 10) (note position of hairdresser's fingers). Very rarely the mixed curling solution is applied to the hair before the hair is wound. The concentration of GMTG in this mixed solution is somewhere between 18% and 20%. The curlers are covered by a plastic cap, the excess lotion is blotted away, and the client is then seated under a hot hair dryer for 15 to 20 minutes. This heating quickens the chemical process and probably also maximizes irritation. Until very recently, all acid perms required the addition of heat and could be identified by noting the words "heat activated acid p e r m " printed on their labels. Now, however, some GMTG-containing acid perms [e.g., Quantum (Helene Curtis)] are done "cold" and maintain their efficacy by increasing their pHs. Additionally, all perms now labeled "acid" do not necessarily contain GMTG. Perms in which the waving solution requires premixing and are boxed as those in Fig. 9 are most likely to contain GMTG. Before the drying operation is complete, the hairdresser does a "test curl" (Fig. 5). The
Volume 11 Number 1 July, 1984
Fig. 9. Permanent waves containing GMTG usually
Pe~vnanent wave c o n t a c t d e r m a t i t i s
83
have three parts. The GMTG is in the small tube.
Fig. 10. Curling lotion containing ammonium hydroxide and GMTG is applied directly to the wound hair. Note fingertip exposure. (See Fig. 3.)
finger dermatitis of many of our hairdresser patients corresponds exactly to where this curl lies on their fingers. When the curl is satisfactory, the scalp is rinsed with water. The neutralizer is next applied to the rods (mandrels) wound with hair and is left in place 5 minutes. The neutralizer is then thoroughly rinsed off with water and the rods are removed. Finally, the hair is styled as desired. Hand dermatitis is uncommon among hairdressers but irritant hand dermatitis is by far the most common skin problem afflicting them. 6'7"r' Allergic dermatitis occurs in about 23% of hairdressers with hand dermatitis. 7 Surveys of responsible allergens have always found hair dyes (PPD) to be the most frequent culprits. Depending on the referral pattern of the patients tested, the prevalence of this sensitivity may be 8% 7 or 32% ~ or 45%. ~a Nickel gives positive results 19% to 27% of the time, and rubber additives and formaldehyde account for most of the other relevant positivesY '7'~:~ Ammonium persulfate can produce urticaria-like reactions as well as a dermatitis, but patch test responses to this chemical are difficult to interpret.~;'~4 ATG is found in cold permanent waves at a concentration of 1% to 9%. Allergic contact dermatitis to ATG is very rare in hairdressers or clients. Croniff~ believes that it may never occur, and James and Calnan 7 doubted that the ten reactions to 1% ATG which they saw were truly allergic reactions. They believe that ATG allergy has been exaggerated. We found it of special interest,
however, that the pattern of dermatitis which James and Calnan observed in their ATG-"posit i r e " patients corresponded exactly to the fingertip pattern we saw in our GMTG patientsF Lynde and Mitchell ~:~ did not test ATG because of its irritant properties. Downing ~'~was able to sensitize only one of 213 patients to 0.55 N ATG in repetitive testing conducted over 2 weeks. Voss ~~ was unable to sensitize any guinea pigs or humans to 1.25% (0.14 molar) TGA. Other mercaptans in his testing series produced sensitization in 90% to 100% of cases. We had only one patient react to ATG. Unlike his GMTG reaction, this ATG reaction was blocked by a vinyl glove and our patient is able to give cold (alkaline) perms without problems. In 1961, Schulz '~ described 121 patients who reacted to the hydrazide and the glycolic ester of TGA, which were being used in Germany for permanent waving; 35% of the hydrazide patients and 29% of the glycolic ester patients also had reactions to ATG in concentrations as low as 0.5%. Schulz '~ could not, however, sensitize guinea pigs to ATG. Schulz's studies implied that patients sensitized to mercaptans via the esters of TGA are more likely to become "group"sensitized to ATG than are patients whose primary exposure is to ATG itself. This has not occurred in our patients and we are not aware of any instances of GMTG-ATG co-sensitivity, thus far, in the United States. One might have inferred from the studies of
84
Storrs
Schulz 9 and Voss 1~ that GMTG is a sensitizer. Neither o f these papers mentions GMTG, however, nor does a third analysis of mercaptans presented in 1959.* The seventh edition of Harry's cosmeticology ~ mentions the "revival" of GMTG acid perms but does not comment on toxicity or sensitizing potential. A recent comprehensive consumers' guide to cosmetics does not mention GMTG. 1 Despite the fact that GMTG has been synthesized and sold in this country since 1973 and used widely in salon perms since at least 1977 or 1978, I found only one published description of its toxicity tl and no descriptions of predictive patch testing. Some o f our hairdressers complained that the gloves they wore while giving acid perms provided no protection. Many of the manufacturers recommend that hairdressers wear rubber or vinyl gloves while giving perms. Our patch testing through various gloving fabrics confirmed our patients' suspicions. In several instances, patients appeared to get a small amount of protection from gloves (Hairdresser 3 and Client 4), which suggests that even thin gloves worn during the application o f the curling lotion or during the test curl step might be helpful. Perhaps sensitization itself could be minimized by such a precaution, although the GMTG concentration to which the hairdressers and clients are exposed is much greater than the concentrations that we tested. The heavier household-weight neoprene glove, which protected all our patients, would be ideal but is sufficiently cumbersome as to render it less practical. At least one of our control patients developed an irritant reaction to G M T G 10% applied over a vinyl glove, which suggests that such gloves can allow access o f GMTG to the skin (see "Patch Test Results"). The penetration of protective gloves by allergens is well known. ~ci-Z:~ Acrylic monomers, hair dyes, neomycin, parabens, nickel, and nitrogen mustard have all been shown to penetrate gloving fabrics of various types, la-"~ Now GMTG can be added to this list.
*Haefele JW, Broge RW: The synthesis and properties of mercaptans having different degrees of acidity of the sulfhydryl group. Proceedings of Seientific Section, The Toilet Goods Association, 1959, no. 32, pp. 52-59.
Journal of the American Academy of Dermatology
The Oregon State Board of Barbers and Hairdressers has 16,000 active licensees registered. It is the practice of modern hairdressing and barbering schools to teach permanent waving. If we estimate that two thirds of Oregon's licensees give acid perms, our eight GMTG-allergic hairdressers would place a prevalence of GMTG sensitivity among Oregon hairdressers at a level of 0.08%. During the past 11/2 years, we have shared supplies of 2.5% and 1.0% GMTG with our co!leagues in the NACDG and with several other interested dermatologists in the United States and Canada. These people are experienced and critical evaluators of allergic contact dermatitis. Thus far, we have learned of twenty-nine additional hairdressers and seventeen additional clients with documented and relevant GMTG allergy. The fifty-eight patients reported were from Canada and from the East, Midwest, and West areas of the United States (including Oregon). Only four of these fifty-eight patients were men; all were hair, dressers. Three were white and one, black. We are now evaluating the persistence of the dermatitis we have observed in some of our client patients. Some of our hairdresser patients have commented that recently " p e r m e d " hair (1 to 2 weeks old) makes their hands itch. In very preliminary testing, diglyceryl dithioglycolate (see Fig. 8), 1% in petrolatum, has produced positive patch test reactions in three of our four clients and in two of six hairdressers we have tested. It is entirely unknown whether or not this reaction product remains in " p e r m e d " hair for any length of time. Such a possibility will require careful evaluation if we are to give the best advice to our patients. Several manufacturers of permanent waves have estimated that approximately 20 million units of GMTG-containing perms are used each year only in beauty salons in the United States and constitute about 25% of all perms given in salons. If one person receives three to four acid perms a year, this would put the risk group at between 5 and 7 million people. Obviously, the prevalence of GMTG allergy among this group of potential clients is small. When one considers, however, that cold (alkaline) permanent waves utilizing ATG have been used by the hundreds of millions since 1943 both in homes and in salons with vir-
Volume 11 Number 1 July, 1984
tually no allergic reactions, the identification in clients of twenty-one allergic reactions to G M T G perms in 1 or 2 years is rather impressive. Manufacturers claim that acid perms offer a real advantage in minimizing the damage to hair that can occur from a permanent wave, and it is unlikely that they will soon be replaced. There is no doubt, however, that the manufacturers will continue in their search for less allergenic chemicals. In the interim, the few hairdressers and clients who do develop allergy to G M T G can minimize their exposure by adequate gloving and by avoidance, or by using cold (alkaline) permanent waves containing A T G rather than the G M T G containing " a c i d " perms.
REFERENCES 1. Conry T, Fry D, Fry N, Okagaki A: Permanent waving, in Consumers guide to cosmetics. New York, 1980, Anchor Press/Doubleday & Co., pp. 94-108. 2. Eiermann HF, Larsen W, Maibach HI, Taylor JS: Prospective study of cosmetic reactions: 1977-1980. J AM ACAD D~R~ATOL6:909-917, 1982. 3. Wells FV, Lubowe II: Permanent waving, in Cosmetics and the skin. New York, 1964, Reinhold Publishing Co., pp. 458-474. 4. Gershon SD, Goldberg MA, Rieger MM: Permanent waving, in Balsam MS, Sagarin E, editors: Cosmetic science and technology, ed. 2. New York, 1972, John Wiley & Sons, Inc., vol. II, pp. 167-250. 5. Lehman AJ: Health aspects of common chemicals used in hair-waving preparations. JAMA 141:842-845, 1949. 6. Cronin E: Contact dermatitis. New York, 1980, Churchill Livingstone, Inc., pp. 126-139.
Permanent wave contact dermatitis
85
7. James J, Calnan CD: Dermatitis of the hands in ladles' hairdressers. Trans St. Johns Hosp Dermatol Soe 42:19-42, 1959. 8. Wilkinson JB, Moore RJ, editors: Permanent waving and hair strengtheners, in Harry's eosmeticology, ed. 7. New York, 1982, Chemical Publishing Co., Inc., pp. 555580. 9. Schulz KH: Durch Thioglykolsaurederivate ausgeloste Kontaktekzeme im Friseurberuf. Berufsdermatosen 9: 244-257, 1961. 10. Voss JG: Skin sensitization by mercaptans of low molecular weight. J Invest Dermatol 31:273-279, 1958. 11. Warshawshki L, Mitchell JC, Storrs FJ: Allergic contact dermatitis from glyceryl monothioglycolate in hairdressers. Contact Dermatitis 7:351-352, 1981. 12. Cronin E, Kullavanijaya P: Hand dermatitis in hairdressers. Acta Derm Venereol (Stockh) 59(suppl 85):47-50, 1980. 13. Lynde CW, Mitchell JC: Patch test results in 66 hairdressers. Contact Dermatitis 8:302-307, 1982. 14. Ca.lnan CD, Shuster S: Reactions to ammonium persulfate. Arch Dermatol 88:812-815, 1963. 15. Downing JG: Dangers involved in dyes, cosmetics and permanent wave lotions applied to hair and scalp. Arch Dermatol Syph 63:561-564, 1951. 16. Pegum JS, Medhurst FA: Contact dermatitis from penetration of rubber gloves by acrylic monomer. Br Med J 2: 141-143, 1971. 17. Moursiden HT, Faber O: Penetration of protective gloves by allergens and irritants. Trans St. Johns Hosp Dermatol Soc 59:230-234, 1973. 18. Pegum JS: Penetration of protective gloves by epoxy resin. Contact'.Dermatitis 5:281-283, 1979. 19. Thomsen K, Mikelsen HI: Protective capacity of gloves for handling nitrogen mustard. Contact Dernmtitis 1: 268-269, 1975.
Kennedy and kyell
mending his working clothes a few days before the onset of the lesion Exammatmn revealed a well chdd with a dusky, purphsh nodule, approximately 2 5 cm m diameter, at the base of the scrotum (Fig 4) There was no regmnal lymphadenopathy Viral partmles consistent wlth the morphology of off were seen by electron mmroscopy m scrapmgs from the lesmn DISCUSSION O f f IS c a u s e d by a m e m b e r of the parapox family o f viruses It lS w i d e s p r e a d in sheep, mainly affecting lambs, where ~t p r o d u c e s nodules and e r o d e d lesmns, particularly around the mouth and nose H u m a n lesions usually o c c u r by &rect contact and are thus c o m m o n a m o n g shephmds, farmers, and veterinary surgeons Infection may occur m & r e c t l y , h o w e v e r , for e x a m p l e , from a c o n t a m i n a t e d pasture
In the first case described in this report, the permnal lesmns presumably arose by automoculatmn from the d~gltal lesmn, whmh had gone unnotmed until a full e x a m m a t m n was carried out by the dermatologist Because o f the lntertngmous site, the macerated permnal lestons were not &agnostm of orf in appearance and bore a resemblance to secondary syphdls In the second case, it was presumed the mother had acted as an asymptomatlc carrier for the off wrus since she both changed the b a b y ' s drapers and had m e n d e d her farmwinking husband's clothes These cases Lllust~ate the potentml ~mportance o f knowing the parental occupatmns and enwronments o f pedmtrlc patmnts
Permanent wave contact dermatitis: Contact allergy to glyceryl monothioglycolate Frances J Storrs, M D , Portland, OR Eight hairdressers and four chents were found to be allergic to glyceryl monthloglycolate (GMTG) contained m " a m d " permanent waves used m American beauty salons only since 1973 Previous studms m Germany showed that compounds closely related to GMTG were strong sensmzers In contrast, ammonmm thloglycolate (ATG) has been used since 1943 m cold "alkahne" permanent waves both m homes and m salons with no clearly documented cases of contact allergy Our allergm patmnts reacted to GMTG m concentrations as low as 0 25%, although thmr exposure m practice could reach concentrations of 20% to 80% GMTG-allergm patients reacted to GMTG when tt was tested thlough a variety of glove fabrics Household-weight neoprene gloves were protectlve (J AM ACAD DERMATOL 11 74-85, 1984 )
From the Department of Dermatology The Oregon Health Scmnces Umvers~ty Accepted for pubhcat{on Nov 9 1983 Reprint reqtmsts to Dr Frances J Storrs Department of Dermatology The Oregon Health Setences UmVmSlty, 3181 S W Sam Jackson Park Rd , Portland, OR 97201/503-225 8597
74
Mllllons o f permanent waves are g~ven each year to American men and women both in their homes and m beauty salons In 1976, it was estimated that 57 m d h o n dollars was spent on home permanent Mts and another 30 mllhon dollars on permanent waves ( " o e r m s " ) given in
Volume 11 Number 1 July, 1984
Table I. GMTG-containing permanent waves 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24.
Rilling Perfect Touch (Rilling) One Better (Helene Curtis) Uniperm Acid Wave (Helene Curtis) Quantum (Helene Curtis) Apple Pectin Acid pH Perm (LaMaur) Full Dimension (LaMaur) Zotos Warm and Gentle (Zotos) Pliance (Tressa) Belgian Formula Special (Fermodyl) Day Into Night (Redken) Creative Curl (Redken) Thermo Curl (Naturelle) Patent 289 (Wella) Great Feeling (Revlon) Sensor Perm (Revlon) Lush & Lovely (Revlon-Realistic) Sensor Curl (Revlon-Realistic) Great Feeling for Blondes (Revlon-Realistic) Genus-30 Celsius Perm (Revlon-Realistic) No Rods Just Rollers (Revlon-Realistic) Living Curl (Revlon-Realistic) Sensor Supreme (Revlon-Realistic) Special Feeling (Revlon-Realistic) Texture Silk (Revlon-Realistic)
beauty shops.' These figures are much higher today. It is fortunate that the problems associated with properly performed permanent waving are few. In fact, from 1977 to 1980, problems with permanent wave ingredients accounted for only three of the 487 patients described in a study of cosmeticsrelated skin reactions. 2 Heat and water have been used to curl hair for thousands of years. The first real permanent waving was accomplished in 1906, when Nessler applied heat to hair that had been wound on the head and treated with alkali. :~'4 Few changes were made in this basic method until 1943, when cold waving using ammonium thioglycolate (ATG) came into general use and the first home kits were introduced. :~ Their use was great from the start, and by 1949, the chief of the division of pharmacology at the Food and Drug Administration was able to state that "the judicious use of ammonium thioglycolate as a hair-waving preparation should prove a relatively innocuous procedure. '''~ Although reports of allergy to ATG do exist, they are rare and astute observers have doubted their veracityfi '7 Today, salts of thioglycolic acid (TGA)
Permanent wave contacl dermatitis
75
i
[s-cH2_C~oNH," Ammonium Thioglycolale
HS- CH2-C .. O_ CH2..CH-CHz-OH OH Glyceryl Monothioglycola e Fig. 1. Both ATG and GMTG contain a sulfhydryl (SH) group. The GMTG side chain appears to enhance allergenicity. still represent the greatest proportion of home and salon permanent waving preparations (Fig. 1). Although these permanent waves are efficient and relatively safe, they do, nonetheless, damage the hair with frequent use and not uncommonly irritate the scalp. Titus manufacturers have sought milder products. If the carboxylic acidity of TGA is blocked by esterification or acidification, the resulting compounds are active at lower pHs and are said to be less damaging, s In the late 1950s and early 1960s, such compounds were widely used in Germany. "~ Unfortunately, both the hydrazide and the glycolic ester of TGA caused over 100 reported cases of allergic contact dermatitis and sale o'f these preparations was stopped) In the published review of the German outbreak, and in screening studies of other mercaptans (sulfhydryl-containing compounds) for skin sensitization as a prelude to selecting yet other compounds for permanent waving, the glycerylic ester of TGA [glyceryl monothioglycolate (GMTG)] was not included 'a''~ (Fig. 1). This compound (GMTG) was, however, being manufactured in Germany in the early 1970s and in 1973 was imported to the United States and repackaged for distribution here. By September, 1973, it was being manufactured in the United States, and in 1979, six "acid p e r m s " containing G M T G were available for use only in salons. Today over
76
Journal of the American Academy of Dermatology
Storrs
T a b l e I I . G M T G - p o s i t i v e hairdressers GMTG Atopic history Patients
Age (yr) [
Personal , [
1
27
Hay fever
2
34
--
3
36
Eczema (child)
4
21
Hay fever
5
30
Hay fever
6
29
Keratosis pilaris
7
28
Hay fever
8
41
Hand eczema
Family
GMTG exposure history
ACD before diagnosis
Distribution
Lowest % concentration
Lowest % concentration through gloves
4 mo
31/z yr
Fingertips
0.25
0.25
5 mo
2 yr
Fingertips
0.50
0.50
Eczema, asthma, hay fever Hay fever, asthma --
7 mo
8 mo
Fingertips, palms
0.50
2.5
21 mo
4 mo
0.50
0.50
11 mo
4 mo
0,25
0.25
Hay fever
1 mo and penn 2 yr previously 10 mo
2 mo
0.50
0.50
1.0
NT
10 mo
3 yr
Sides of fingets, arms Fingertips, under ring Dorsal aspects of fingers; arms Dorsal aspects of fingers Fingertips, sides of fingers
0.25
NT
Eczema
Eczema, asthma
1% yr
ACD: Allergic contact dermatitis; e: no standard tray applied; NT: not tested; -: negative.
twenty " a c i d p e r m s " for salon use exist (Table I). W e k n o w o f only two G M T G - c o n t a i n i n g permanent w a v e s sold in G e r m a n y (Goldwell and Wella). G M T G is not c o n t a i n e d in any h o m e perm a n e n t w a v i n g product. G M T G - c o n t a i n i n g p e r m s were not used widely in O r e g o n until 1977 or 1978. We saw our first G M T G allergic contact dermatitis in a hairdresser in July, 1980. This r e p o r t will describe eight hairdressers and four clients with G M T G allergic contact dermatitis w h o m we studied between July, 1980, and March, 1983. CASE REPORTS
A representative hairdresser and client are described. Details of the other patients are outlined in Tables II and III. Hairdresser
A
A 27-year-old white male hairdresser developed a hand dermatitis 4 months after acid perms had been introduced into his beauty salon. The dermatitis began
on his fingertips and only occasionally involved the skin over the dorsa of his fingers. He had hay fever and a sister with hand eczema, but he had never before had a hand dermatitis despite 6 years of work as a hairdresser with considerable exposure to cold (alkaline) permanent waves. He suspected the acid perms were causing his difficulty, particularly since he had developed forehead and scalp dermatitis when he was given an acid perm. Before his referral to us in August 1980, he had been troubled by incapacitating hand dermatitis for 31h years, for which he had received intramuscular injections of long-acting corticosteroids every 6 weeks. He developed striae, bruisability, and fatigability and also gained 30 pounds. He consulted an endocrinologist, who referred him to us. We patch-tested him (see "Patch Testing Methods") to our hair dye tray, the North American Contact Dermatitis Group's (NACDG) standard tray, and to our vehicle and preservative tray. He performed open patch tests to the waving solution of one of his acid perms, He developed positive reactions to paraphenylenediamine (PPD) and to two PPD analogs, His open test was also positive.
Volume 1l Number I July, 1984
Other positive reactions
Permanent wave contact dermatitis
Owns shop
Follow-up
ATG, PPD
Yes
Clear; avoids acid perms Clear; avoids acid petals Better; quit; atopic hands
Neomycin
Yes
Bronopol
No
0§
No
Flares; works
Potassium dichromate 0
Yes No
Flares; works; atopic hands Clear; quit
ppD +
Yes
Flares; works
Quaternum- 15, formaldehyde, imidazolidinyl urea
Yes
Fl~tres; works; atopic hands
After consulting the very cooperative manufacturer of one of his acid perms, we obtained some GMTG. This was prepared 2.5% in petrolatum as was the ATG. Both of these tests were 2+ positive at 2-day and 1-week readings. Fourteen months after first seeing this man, we tested him again. This time we tested him to dilutions of GMTG that we applied over various glove fabrics (Table IV). He developed positive reactions through most of the gloves down to a concentration of 0.25% GMTG in petrolatum. ATG, 2.5% in petrolatum, was also tested but did not penetrate a lightweight vinyl glove, which cast some doubt on its original validity as an allergic reaction. This man owned his own beauty salon and continued to work. He was free of dermatitis as long as he completely avoided acid perms. Client A A 67-year-old white housewife had experienced lifelong hay fever and had had one outbreak of flexural eczema in her late forties. Occasionally, she developed patchy dermatitis on her arms, bands, and the posterior portion of her neck, which she could control with corticosteroid creams. She had received salon cold perms and home perms wit~aout incident throughout her adult
77
life. In a 2-year period, she received three acid perms. After the second one, she noted some itching and irritation on her forehead. In July, 1982, after her third perrn, she noted itching of her scalp in the evening, Her skin was clear on the day of her July perm, but she developed an acute oozing dermatitis of her neck, ears, and scalp by the next morning. Her eyelids were edematous. The acute dermatitis subsided but left a chronic eczema in its wake, for which she refused treatment because of her concern with steroid side effects. After tolerating this dermatitis for 6 months, she was referred by her general physician to the dermatology department of the Oregon Health Sciences University. Patch testing to the NACDG standard tray and the hairdresser tray (see "Patch Testing Methods") provided positive reactions only to 1% GMTG in petrolatum and questionably to formaldehyde. She was further tested to four dilutions of G M T G through a variety of glove fabrics (Table IV). She reacted positively through most of the gloves to concentrations of GMTG as low as 0.5% in petrolatum. Her dermatitis quickly cleared with cortieosteroid ointments. She had had no more permanent waves and remained free of dermatitis as of April, 1983. Other hairdressers Details of seven other hairdressers are included in Table II. The hairdressers' average age was 31 and all but Patient 1 were women (five Caucasian, one Cuban, one Iranian). Seven hairdressers had personal histories of atopy (asthma, hay fever, or eczema), but only one of the seven had had hand eczema prior to GMTG exposure. Five hairdressers had family histories of atopy. Both the hairdressers and clients were seen in The Oregon Health Sciences University's general dermatology clinics and on referral to our private clinics and contact dermatitis evaluation clinic. There was no significant difference between the average period of time required to sensitize hairdressers who worked 1 to 4 years in salons before G M T G perms were introduced (Patients 1, 2, 5, 7, and 8) and those who had been exposed to acid perms from the onset of their work experience (Patients 3, 4, and 6); 8 versus 10 months. The patient who appeared to sensitize most rapidly (Patient 6) had received an acid perm 2 years previously. In every instance, there was a delay in diagnosing the cause of the hairdressers' dermatitis. As word of our interest spread into the community, this time was shortened from years (Patients 1 and 2) to months (Patients 4, 5, and 6). A predilection for the fingertips was the distinguishing feature of the hairdresser's hand dermatitis (Fig, 2 and 3). In several instances, dorsal surfaces of the distal
Journal of the American Academy of Dermatology
Stot~
78
Table III. GMTG-posmve
chents
Atople history Patient
(yr)
Personal
Famdy
1
67
H a y fever
2
59
H a y fever, eczema --
3
43
--
4
60
--
exposure history
--
Oceupatmn
Housewife
3 yr
Neck, scalp, ears, hands, arms Neck, scalp, ears
Housewife
24 hr
Neck, ears
Cook
Neck, scalp, forehead, ears
Secretary
6 mo
4 perms/ 4 yr 2 perms/ 1% yr
--
Distribution
diagnosis
3 perms/ 2 yr 6 perms/ 3 yr
Eczema
ACD Allergic contact dermatms -
ACD before
GMTG
Age
1
mo
negatwe
*Only Chent 3 was tested to compIete concentratton panel without gloves fOnly concentratmn tested
Table IV. GMTG reacnons through gloves G M T G concentration (%) giving positive reactmn through gloves
Butadlene
Latex surgeon)s
polymer
Patients, I (HD)
05
2 3 4 5 6
1 0 NT NT 0 25 NT NT NT I 0 --
(HD) (HD) (HD) (HD) (HD)
1 (C)
2 (C*) 3 (C) 4 (C) -
2D
7I)
2D
}
7D
Neoprene household
Vinyl exam
2D
]
7D
2D
]
7D
Vinyl household 2D
7D NT
--
l 0
--
025
25
--
--
NT
-NT NT 2 5 NT NT NT ---
1 0 -0 5 NT --
---NT --
0 2 0 0 0
-2 5 -0 25 0 5
--
--
NT
--
--
25
25
05
25
1 0
1 0
05
05
-025 2 5
10 25 --
-05 2 5
10 10 2 5
5 5 5 25 5
NT
--
--
--
--
NT
NT
--
--
NT
NT
--
--
10
10
--
--
10
10
--
--
0 25
0 25
--
--
NT
NT
Negative C chent, HD hmrdresser NT not tested 2D 2 days, 7D 7 days
*Only 1% concentration tested
aspects o f the fingers were involved primarily (Fig 4) An especmlly interesting pattern of dermatms revolved the radml and ulnar sides of the second and third fingers and appeared to correspond to skm exposed to test curl hatr before the neutrahzatton process (Figs 2 and 5) Arm mvolvement corresponded to "spatters" o f curlmg solution There was no web space mvolvement Five o f the eight hatrdressers own thear salons and have continued to work Patient 2 allows no acid perms m her shop and is clear Pataent 1 has acid perms in his shop but does none himself He also ts clear The other three owners (Patients 5, 7, and 8) g w e acid perms occasionally but always have a flare o f their dermatms ff they do not wear gloves of a wmght that wall protect
them Pattent 8, who had hand eczema before sen slhzatlon, stall has it and ~t flares addmonally wlth acJd perms Patient 5 developed a mild coexisting, probably atoplc, hand eczema that served as a background to flares of her dermatitis with acid perm exposure If she wears neoprene household-weight gloves whde giving acid perms, she has almost no trouble Of the three non-shopowners, two have qmt working One of these (Patient 3) continues to be troubled by an atoplc hand eczema, which flared for the first time m 20 years (coincident with her G M T G sensmzanon) The other (Patient 6) is tully clear Patient 4 did not qmt working and her dermatms flares when she g~ves acid perms JUSt like the shopowner's does
Volmne 11 Number 1 July, 1984
Permanent wave contact dermatitis
79
GMTG*
Lowest % concentration
Lowest % concentration through gloves
Other positive reactions
0.5
0.5
Formaldehyde
1.0q"
1.0t
0.25
0.25
Nickel, fragrance mix, plants, Thiuram Nickel, epoxy
1.0
2.5
Nickel Fig. 2. Dermatitis corresponds to the place where the test curl hair touches the fingers (Hairdresser 5).
Other clients Details of three other clients (all Caucasian women) are tabulated in Table [II. Their average age was 57. Only Patient 1 had had a personal history of atopy, whereas Patients 1 and 3 had family histories. All the clients had received at least one acid perm before becoming sensitized. This is a difficult interval to ascertain in that, as with Patient I, most patients noted some slight hairline dermatitis before their explosive episode. Patient 2 tolerated postperm dermatitis for several years before a diagnosis was made. The dermatitis in the other three patients was diagnosed within hours or months after their acute experience. The neck and ears were the skin sites most commonly involved with acute dermatitis. The scalp was also extensively involved in three patients. Two patients worked outside of their homes. Clients 3 and 4 have had several cold (alkaline) perms without incident since their GMTG allergy was diagnosed.
!iiii! il84
PATCH TESTING METHODS Allergens were applied to aluminum discs (Finn chambers) and then secured to the upper portion of the back of each patient with a porous tape (Scanpor). They were left in place for 48 hours and then removed and read 30 minutes later. A second reading was done at 7 days. Only reactions present at both the 48-hour and the 7-day reading were recorded as positive. All patients except Hairdressers 4 and 7 were tested to the NACDG's standard tray of allergens.* A hairdresser tray was applied to all the patients. During the 30 months of the study, this tray's constituents varied but consisted of the following allergens (prepared in pet*See Patch Testing in Allergic Contact Dermatitis. Evanston, IL, 1982, American Academy of Dermatology, Inc.
Fig. 3. Fingertip dermatitis was the most common distribution pattern (Hairdresser 2). rolatum unless otherwise specified) during the majority of the time: quaternium-15, 2% in water; p-aminophenol, 10%; m-phenylenediamine, 2%; resorcinol, 2%; 2,5-toluenediamine, 1%; p-phenylenediamine (PPD), 1%; hydroquinone, 1%; 4-aminodiphenylamine, 0.25%; fragrance mix; 2-nitro-p-phenylenediamine, 2%; pyrocatechol, 2%, in 95% ethanol; 4ethoxy-m-phenylenediamine, 1%; ATG, 2.5%; formaldehyde, 2% in water; ammonium persulfate, 2% in water; GMTG, l%; pyrogallol, 1%; glycerin, 100%. GMTG was used at a concentration of 2.5% early in the study, but this was subsequently lowered to 1%. All
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Fig. 4. Occasionally the skin of the dorsal surface of the fingers was involved. The webs were spared (Hairdresser 7).
Fig. 6. Pieces of glove separated the allergen from the patient's back. Fig. 5. Hairdresser performing a test curl. Note position of thumb and ~nde• finger and compare to Fig. 2. patients except Client 2 were tested to dilutions of GMTG down to 0.25%. Additionally, all patients except Hairdressers 7 and 8 were tested to four dilutions (2.5%, 1.0%, 0.5%, and 0.25%) of GMTG applied over a variety of gloving fabrics (Fig. 6 and Table IV). These glove fabrics included a styrene butadiene block polymer surgeon's glove (Elastyren), a synthetic rubber surgeon's glove (Perry), a light- and medium-weight polyvinyl glove [Tru Touch (Edmont Wilson) and Allerderm], and a household-weight neoprene glove [Super Ebonette (Pioneer)]. Client 2 was tested only at 1%. These more cumbersome patches were also left in place for 48 hours and read at 48 hours and 1 week. Finn chambers and Scanpor tape were again used. GMTG was evaluated for irritancy by including it wi~h allergens on the standard tray we use to investigate patients with saspect alIergic contact dermatitis. Forty-five patients (twenty-four women and twenty-one
men) were tested at 2.5%, and sixty patients (twentynine women and thirty-one men) were tested at 1%. G M T G was also tested at 2.5% and at 10% through vinyl gloves on a smaller and different group of patients with suspect allergic contact dermatitis from cause~ other than GMTG. PATCH T E S T RESULTS At 2.5%, G M T G gave no irritant reactions in twenty-one control men but did produce one irritant reaction among twenty-four control women. At 1%, thirty-one men and twenty-nine women showed no irritant reactions to G M T G . Our 2.5% G M T G in petrolatum was shared with colleagues in Vancouver, BC, who noted two irritant reactions in twenty eczema patients. 11 W e now test G M T G at 1.0% because G M T G 2.5% in petrolatum is occasionally irritating and because 1% identified all our positive patients. One GMTG-ailergic hairdresser and one client
Volume 1l Number I July, t984
gave no positive GMTG reaction below 1.0%. Client 2 was not included in this analysis because she was tested only at 1%. Three hairdressers and one client reacted down to a GMTG concentration of 0.25% and four hairdressers and one client gave reactions no lower than 0.5%. All our patients were tested with ATG, 2.5% in petrolatum. Only Hairdresser A had a positive reaction. This reaction could not penetrate a lightweight vinyl glove, but it was positive on two separate testings without a glove. Glycerine, 100%, was added to the hairdresser's tray halfway through the study. Nine patients had negative reactions to it. Hairdressers 4 and 7 were not tested to the standard tray. Among the other patients a few coincident positive :reactions were common. Two hairdressers were concomitantly positive to PPD. One hairdresser reacted to neomycin and two to formaldehyde or formaldehyde-releasing preservatives (Patients 3 and 8). Three of the four clients were nickel-sensitive. In all the patients, we were able to establish clinical relevance for their additional positives except for Hairdresser 5's chromate sensitivity and Client 3's epoxy reactivity. Eleven control women and seven control men showed no irritancy to 2.5% GMTG applied over vinyl examination-weight gloves. None of the seven control women tested to 10% GMTG over vinyl gloves had an irritant reaction, but one of the five control men had a definite irritant reaction at 10%. He was negative to 1% GMTG applied without the glove barrier and negative to the glove applied alone. All GMTG-allergic patients tested to GMTG through various gloves (Figs. 6 and 7 and Table IV) reacted through at least one kind of gloving fabric. Only Hairdresser 3 and Client 4 did not have positive reactions through gloves at the same low concentration to GMTG that they achieved without the glove barrier (Tables II and III). The household-weight neoprene glove (Super Ebonettes) was the only gloving fabric that universally blocked penetration of the allergen (Table IV). None of the other gloves provided regular protection, although in many instances reactions positive at 48 hours were negative at 7 days or remained positive only at the higher concentrations.
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Fig. 7. Positive patch tests occurred even when the allergen had to pass through some glove fabrics (Hairdresser 5). DISCUSSION Permanent waving is a chemically active process, the efficacy of which depends on marked rearrangement in hair proteins (keratin). Keratin fibers are composed of polypeptide chains that are attached laterally to adjacent chains by chemical bonds. Hydrogen bonding can be disrupted by heat and water and then re-formed by drying. The changed configuration of the hair, however, is not long-lasting. The prevailing influence on the cohesion of hair keratin can be attributed to covalent disulfide cross-linkages between polypeptide strands.:~'4"7"~ When these "keratocystine" cross-linkages are disrupted in a wet, alkaline environment, such as that provided by the alkaline salts of TGA, the hair becomes softened and then plastic. Once the desired realignment is achieved, the broken (reduced) disulfide bonds can be reformed in the presence of a neutralizer (oxidizing
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PERMANENT WAVE CHEMISTRY K-CH2--S-S--CH2-K
+
-S-CH2-CO2THIOGLYCOLATE
+
--02C-CH2--S-S--CH2--CO 2-
"'KERATOCYSTINE"
K-CH2-S"KERATOCYSTEINE"
DITHIOGLYCOLATE
Fig. 8. When the disulfide bond in hair keratocystine is reduced to a cysteine sulfhydryl group, the hair becomes plastic and its configuration can be changed. Oxidizing the cysteine back to disulfide linkages renders the change permanent. agent). This " h a r d e n i n g " produces new bonds that hold the hair in a curled position until it grows out or is re-treated (Fig. 8). 1"~'~ Voss 10 postulated that chemicals related to TGA (mercaptans) are capable of inducing contact sensitization by this same splitting o f disulfide bonds o f skin proteins and forming derived proteins that serve as the actual allergens. Since 1943, most cold permanent waving used in salons and in homes has contained ATG. This compound must be used at a pH between 9.3 and 9.5. Esterification of the carboxylic acidity of TGA produces compounds that, although less potent reducing agents, can be used at more neutral or even slightly acid p H s - - h e n c e , the popularity of so-called " a c i d " permanent waving since 1976 or 1977, which utilizes GMTG and is said to "protect" hair, particularly that weakened by previous permanent waving. The term acid, however, is often a misnomer because the pH varies from manufacturer to manufacturer and is often alkaline. Knowledge of the actual procedure used in performing an acid perm can be of value in questioning patients and in informing them how best to protect themselves. This is especially true in that permanent waving products used by professionals are generally packaged without ingredient labels. Most acid perms consist of three parts (Fig. 9): the curling lotion, which contains ammonium hydroxide, water, various surfactants, fragrances, and sequestering agents; a small tube-shaped bot-
tle, which contains GMTG in concentrations up to 80% plus up to 5% residual TGA and as much as 20% glycerin plus various diluents; a neutralizer, which contains oxidizing agents such as bromates, perborates, hydrogen peroxide, or ammonium persulfate, as well as various preservatives, citric acid, surfactants, and fragrances.l'a'~ The small GMTG-containing tube is mixed with the water-based ammonium hydroxide solution and applied directly to the wound hair on the client's head (Fig. 10) (note position of hairdresser's fingers). Very rarely the mixed curling solution is applied to the hair before the hair is wound. The concentration of GMTG in this mixed solution is somewhere between 18% and 20%. The curlers are covered by a plastic cap, the excess lotion is blotted away, and the client is then seated under a hot hair dryer for 15 to 20 minutes. This heating quickens the chemical process and probably also maximizes irritation. Until very recently, all acid perms required the addition of heat and could be identified by noting the words "heat activated acid p e r m " printed on their labels. Now, however, some GMTG-containing acid perms [e.g., Quantum (Helene Curtis)] are done "cold" and maintain their efficacy by increasing their pHs. Additionally, all perms now labeled "acid" do not necessarily contain GMTG. Perms in which the waving solution requires premixing and are boxed as those in Fig. 9 are most likely to contain GMTG. Before the drying operation is complete, the hairdresser does a "test curl" (Fig. 5). The
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Fig. 9. Permanent waves containing GMTG usually
Pe~vnanent wave c o n t a c t d e r m a t i t i s
83
have three parts. The GMTG is in the small tube.
Fig. 10. Curling lotion containing ammonium hydroxide and GMTG is applied directly to the wound hair. Note fingertip exposure. (See Fig. 3.)
finger dermatitis of many of our hairdresser patients corresponds exactly to where this curl lies on their fingers. When the curl is satisfactory, the scalp is rinsed with water. The neutralizer is next applied to the rods (mandrels) wound with hair and is left in place 5 minutes. The neutralizer is then thoroughly rinsed off with water and the rods are removed. Finally, the hair is styled as desired. Hand dermatitis is uncommon among hairdressers but irritant hand dermatitis is by far the most common skin problem afflicting them. 6'7"r' Allergic dermatitis occurs in about 23% of hairdressers with hand dermatitis. 7 Surveys of responsible allergens have always found hair dyes (PPD) to be the most frequent culprits. Depending on the referral pattern of the patients tested, the prevalence of this sensitivity may be 8% 7 or 32% ~ or 45%. ~a Nickel gives positive results 19% to 27% of the time, and rubber additives and formaldehyde account for most of the other relevant positivesY '7'~:~ Ammonium persulfate can produce urticaria-like reactions as well as a dermatitis, but patch test responses to this chemical are difficult to interpret.~;'~4 ATG is found in cold permanent waves at a concentration of 1% to 9%. Allergic contact dermatitis to ATG is very rare in hairdressers or clients. Croniff~ believes that it may never occur, and James and Calnan 7 doubted that the ten reactions to 1% ATG which they saw were truly allergic reactions. They believe that ATG allergy has been exaggerated. We found it of special interest,
however, that the pattern of dermatitis which James and Calnan observed in their ATG-"posit i r e " patients corresponded exactly to the fingertip pattern we saw in our GMTG patientsF Lynde and Mitchell ~:~ did not test ATG because of its irritant properties. Downing ~'~was able to sensitize only one of 213 patients to 0.55 N ATG in repetitive testing conducted over 2 weeks. Voss ~~ was unable to sensitize any guinea pigs or humans to 1.25% (0.14 molar) TGA. Other mercaptans in his testing series produced sensitization in 90% to 100% of cases. We had only one patient react to ATG. Unlike his GMTG reaction, this ATG reaction was blocked by a vinyl glove and our patient is able to give cold (alkaline) perms without problems. In 1961, Schulz '~ described 121 patients who reacted to the hydrazide and the glycolic ester of TGA, which were being used in Germany for permanent waving; 35% of the hydrazide patients and 29% of the glycolic ester patients also had reactions to ATG in concentrations as low as 0.5%. Schulz '~ could not, however, sensitize guinea pigs to ATG. Schulz's studies implied that patients sensitized to mercaptans via the esters of TGA are more likely to become "group"sensitized to ATG than are patients whose primary exposure is to ATG itself. This has not occurred in our patients and we are not aware of any instances of GMTG-ATG co-sensitivity, thus far, in the United States. One might have inferred from the studies of
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Schulz 9 and Voss 1~ that GMTG is a sensitizer. Neither o f these papers mentions GMTG, however, nor does a third analysis of mercaptans presented in 1959.* The seventh edition of Harry's cosmeticology ~ mentions the "revival" of GMTG acid perms but does not comment on toxicity or sensitizing potential. A recent comprehensive consumers' guide to cosmetics does not mention GMTG. 1 Despite the fact that GMTG has been synthesized and sold in this country since 1973 and used widely in salon perms since at least 1977 or 1978, I found only one published description of its toxicity tl and no descriptions of predictive patch testing. Some o f our hairdressers complained that the gloves they wore while giving acid perms provided no protection. Many of the manufacturers recommend that hairdressers wear rubber or vinyl gloves while giving perms. Our patch testing through various gloving fabrics confirmed our patients' suspicions. In several instances, patients appeared to get a small amount of protection from gloves (Hairdresser 3 and Client 4), which suggests that even thin gloves worn during the application o f the curling lotion or during the test curl step might be helpful. Perhaps sensitization itself could be minimized by such a precaution, although the GMTG concentration to which the hairdressers and clients are exposed is much greater than the concentrations that we tested. The heavier household-weight neoprene glove, which protected all our patients, would be ideal but is sufficiently cumbersome as to render it less practical. At least one of our control patients developed an irritant reaction to G M T G 10% applied over a vinyl glove, which suggests that such gloves can allow access o f GMTG to the skin (see "Patch Test Results"). The penetration of protective gloves by allergens is well known. ~ci-Z:~ Acrylic monomers, hair dyes, neomycin, parabens, nickel, and nitrogen mustard have all been shown to penetrate gloving fabrics of various types, la-"~ Now GMTG can be added to this list.
*Haefele JW, Broge RW: The synthesis and properties of mercaptans having different degrees of acidity of the sulfhydryl group. Proceedings of Seientific Section, The Toilet Goods Association, 1959, no. 32, pp. 52-59.
Journal of the American Academy of Dermatology
The Oregon State Board of Barbers and Hairdressers has 16,000 active licensees registered. It is the practice of modern hairdressing and barbering schools to teach permanent waving. If we estimate that two thirds of Oregon's licensees give acid perms, our eight GMTG-allergic hairdressers would place a prevalence of GMTG sensitivity among Oregon hairdressers at a level of 0.08%. During the past 11/2 years, we have shared supplies of 2.5% and 1.0% GMTG with our co!leagues in the NACDG and with several other interested dermatologists in the United States and Canada. These people are experienced and critical evaluators of allergic contact dermatitis. Thus far, we have learned of twenty-nine additional hairdressers and seventeen additional clients with documented and relevant GMTG allergy. The fifty-eight patients reported were from Canada and from the East, Midwest, and West areas of the United States (including Oregon). Only four of these fifty-eight patients were men; all were hair, dressers. Three were white and one, black. We are now evaluating the persistence of the dermatitis we have observed in some of our client patients. Some of our hairdresser patients have commented that recently " p e r m e d " hair (1 to 2 weeks old) makes their hands itch. In very preliminary testing, diglyceryl dithioglycolate (see Fig. 8), 1% in petrolatum, has produced positive patch test reactions in three of our four clients and in two of six hairdressers we have tested. It is entirely unknown whether or not this reaction product remains in " p e r m e d " hair for any length of time. Such a possibility will require careful evaluation if we are to give the best advice to our patients. Several manufacturers of permanent waves have estimated that approximately 20 million units of GMTG-containing perms are used each year only in beauty salons in the United States and constitute about 25% of all perms given in salons. If one person receives three to four acid perms a year, this would put the risk group at between 5 and 7 million people. Obviously, the prevalence of GMTG allergy among this group of potential clients is small. When one considers, however, that cold (alkaline) permanent waves utilizing ATG have been used by the hundreds of millions since 1943 both in homes and in salons with vir-
Volume 11 Number 1 July, 1984
tually no allergic reactions, the identification in clients of twenty-one allergic reactions to G M T G perms in 1 or 2 years is rather impressive. Manufacturers claim that acid perms offer a real advantage in minimizing the damage to hair that can occur from a permanent wave, and it is unlikely that they will soon be replaced. There is no doubt, however, that the manufacturers will continue in their search for less allergenic chemicals. In the interim, the few hairdressers and clients who do develop allergy to G M T G can minimize their exposure by adequate gloving and by avoidance, or by using cold (alkaline) permanent waves containing A T G rather than the G M T G containing " a c i d " perms.
REFERENCES 1. Conry T, Fry D, Fry N, Okagaki A: Permanent waving, in Consumers guide to cosmetics. New York, 1980, Anchor Press/Doubleday & Co., pp. 94-108. 2. Eiermann HF, Larsen W, Maibach HI, Taylor JS: Prospective study of cosmetic reactions: 1977-1980. J AM ACAD D~R~ATOL6:909-917, 1982. 3. Wells FV, Lubowe II: Permanent waving, in Cosmetics and the skin. New York, 1964, Reinhold Publishing Co., pp. 458-474. 4. Gershon SD, Goldberg MA, Rieger MM: Permanent waving, in Balsam MS, Sagarin E, editors: Cosmetic science and technology, ed. 2. New York, 1972, John Wiley & Sons, Inc., vol. II, pp. 167-250. 5. Lehman AJ: Health aspects of common chemicals used in hair-waving preparations. JAMA 141:842-845, 1949. 6. Cronin E: Contact dermatitis. New York, 1980, Churchill Livingstone, Inc., pp. 126-139.
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7. James J, Calnan CD: Dermatitis of the hands in ladles' hairdressers. Trans St. Johns Hosp Dermatol Soe 42:19-42, 1959. 8. Wilkinson JB, Moore RJ, editors: Permanent waving and hair strengtheners, in Harry's eosmeticology, ed. 7. New York, 1982, Chemical Publishing Co., Inc., pp. 555580. 9. Schulz KH: Durch Thioglykolsaurederivate ausgeloste Kontaktekzeme im Friseurberuf. Berufsdermatosen 9: 244-257, 1961. 10. Voss JG: Skin sensitization by mercaptans of low molecular weight. J Invest Dermatol 31:273-279, 1958. 11. Warshawshki L, Mitchell JC, Storrs FJ: Allergic contact dermatitis from glyceryl monothioglycolate in hairdressers. Contact Dermatitis 7:351-352, 1981. 12. Cronin E, Kullavanijaya P: Hand dermatitis in hairdressers. Acta Derm Venereol (Stockh) 59(suppl 85):47-50, 1980. 13. Lynde CW, Mitchell JC: Patch test results in 66 hairdressers. Contact Dermatitis 8:302-307, 1982. 14. Ca.lnan CD, Shuster S: Reactions to ammonium persulfate. Arch Dermatol 88:812-815, 1963. 15. Downing JG: Dangers involved in dyes, cosmetics and permanent wave lotions applied to hair and scalp. Arch Dermatol Syph 63:561-564, 1951. 16. Pegum JS, Medhurst FA: Contact dermatitis from penetration of rubber gloves by acrylic monomer. Br Med J 2: 141-143, 1971. 17. Moursiden HT, Faber O: Penetration of protective gloves by allergens and irritants. Trans St. Johns Hosp Dermatol Soc 59:230-234, 1973. 18. Pegum JS: Penetration of protective gloves by epoxy resin. Contact'.Dermatitis 5:281-283, 1979. 19. Thomsen K, Mikelsen HI: Protective capacity of gloves for handling nitrogen mustard. Contact Dernmtitis 1: 268-269, 1975.