Testing Penetration of Epoxy Resin and Diamine Hardeners through Protective Glove and Clothing Materials.

Efficient, comfortable, yet affordable personal protective equipment (PPE) is needed to decrease the high incidence of allergic contact dermatitis arising from epoxy resin systems (ERSs) in industrial countries. The aim of this study was to find affordable, user-friendly glove and clothing materials that provide adequate skin protection against splashes and during the short contact with ERS that often occurs before full cure. We studied the penetration of epoxy resin and diamine hardeners through 12 glove or clothing materials using a newly developed test method. The tests were carried out with two ERS test mixtures that had a high content of epoxy resin and frequently used diamine hardeners of different molar masses. A drop (50 µl) of test mixture was placed on the outer surface of the glove/clothing material, which had a piece of Fixomull tape or Harmony protection sheet attached to the inner surface as the collection medium. The test times were 10 and 30 min. The collecting material was removed after the test was finished and immersed into acetone. The amounts of diglycidyl ether of bisphenol A (DGEBA), isophorone diamine (IPDA), and m-xylylenediamine (XDA) in the acetone solution were determined by gas chromatography with mass spectrometric detection. The limit for acceptable penetration of XDA, IPDA, and DGEBA through glove materials was set at 2 µg cm(-2). Penetration through the glove materials was 1.4 µg cm(-2) or less. The three tested chemical protective gloves showed no detectable penetration (<0.5 µg cm(-2)). Several affordable glove and clothing materials were found to provide adequate protection during short contact with ERS, in the form of, for example, disposable gloves or clothing materials suitable for aprons and as additional protective layers on the most exposed parts of clothing, such as the front of the legs and thighs and under the forearms. Every ERS combination in use should be tested separately to find the best skin protection material, and this can be done by using this simple test method.

Role of dermal exposure in systemic intake of methylenediphenyl diisocyanate (MDI) among construction and boat building workers.

The causal relationship between inhalation exposure to methylenediphenyl diisocyanate (MDI) and the risk of occupational asthma is well known, but the role of dermal exposure and dermal uptake of MDI in this process is still unclear. The aims of this study were to measure dermal exposure to and the dermal uptake of MDI among workers (n=24) who regularly handle MDI-urethanes. Dermal exposure was measured by the tape-strip technique from four sites on the dominant hand and arm. The workers with the highest exposure (n=5) were biomonitored immediately after their work shift, in the evening and the next morning, using urinary 4,4´methylenedianiline (MDA) as a marker. Dermal uptake was evaluated by comparing workers' MDA excretions both when they were equipped with respiratory protective devices (RPDs) and when they did not use them. The measured amounts of MDI on their hands varied from below 0.1 to 17 µg/10 cm(2) during the test. MDI concentrations were in the range of 0.08 to 27 µg m(-3) in the breathing zone outside the RPDs. MDA concentrations varied from 0.1 to 0.2 µmol mol(-1) creatinine during the test period. The decreasing effect of RPDs on inhalation exposure was absent in the next morning urine samples; this excretion pattern might be an indication of dermal uptake of MDI.

Permeation tests of glove and clothing materials against sensitizing chemicals using diphenylmethane diisocyanate as an example.

Diphenylmethane diisocyanate (MDI) is a sensitizing chemical that can cause allergic contact dermatitis and asthma. Protective gloves and clothing are necessary to prevent skin exposure. Breakthrough times are used for the selection of chemical protective gloves and clothing. In the EN 374-3:2003 European standard, breakthrough time is defined as the time in which the permeation reaches the rate of 1.0 µg min(-1) cm(-2) through the material. Such breakthrough times do not necessarily represent safe limits for sensitizing chemicals. We studied the permeation of 4,4'-MDI through eight glove materials and one clothing material. The test method was derived from the EN 374-3 and ASTM F 739 standards. All measured permeation rates were below 0.1 µg min(-1) cm(-2), and thus, the breakthrough times for all the tested materials were over 480min, when the definitions of EN 374-3 and ASTM F 739 for the breakthrough time were used. Based on the sensitizing capacity of MDI, we concluded that a cumulative permeation of 1.0 µg cm(-2) should be used as the end point of the breakthrough time determination for materials used for protection against direct contact with MDI. Using this criterion for the breakthrough time, seven tested materials were permeated in <480min (range: 23-406min). Affordable chemical protective glove materials that had a breakthrough time of over 75min were natural rubber, thick polyvinylchloride, neoprene-natural rubber, and thin and thick nitrile rubber. We suggest that the current definitions of breakthrough times in the standard requirements for protective materials should be critically evaluated as regards MDI and other sensitizing chemicals, or chemicals highly toxic via the skin.

Respiratory symptoms and conditions related to occupational exposures in machine shops.

OBJECTIVES: Since there are few data on the effects of metalworking in populations representing a variety of metal companies or on dose-response relationships concerning metalworking, this study investigated the relationship between occupational exposures in machine shops and the occurrence of upper and lower respiratory symptoms, asthma, and chronic bronchitis. METHODS: A cross-sectional study of 726 male machine workers and 84 male office workers from 64 companies was conducted in southern Finland. All of the participants filled out a questionnaire, and aerosol measurements were performed in 57 companies. RESULTS: Exposure to metalworking fluids (MWF) showed a greater risk [odds ratio (OR)>or=2) for upper-airway symptoms, cough, breathlessness, and current asthma than exposures in office work did. Exposure to aerosol levels above the median (>or=0.17 mg/m3 in the general workshop air) was related to an increased risk (OR>or=2) of nasal and throat symptoms, cough, wheezing, breathlessness, chronic bronchitis, and current asthma. Machine workers with a job history of >or=15 years experienced increased throat symptoms, cough, and chronic bronchitis. CONCLUSIONS: This large study representing machine shops in southern Finland showed that machine workers experience increased nasal and throat symptoms, cough, wheezing, breathlessness, and asthma even in environments with exposure levels below the current occupational exposure limit for oil mists. The study suggests that improving machine shop environments could benefit the health of this workforce. It also suggests that it is time to consider reducing the current Finnish occupational exposure limit for oil mist or introducing the use of other health-relevant indicators of exposure.

Occupational contact allergy to glyoxal.

Glyoxal is a dialdehyde that is used as a disinfectant in health care and dentistry work. Allergic contact dermatitis from glyoxal has been described in these occupations. We analysed our patient data from 1998 to 2004 for allergic reactions to glyoxal. 20 patients had allergic reactions to glyoxal on patch testing. 5 of these patients worked in dentistry and 4 of them had present exposure to glyoxal. 9 patients were machinists without obvious exposure to glyoxal. A grinder with work-related facial dermatitis is described in detail. The chemical analysis of air samples from his workplace revealed 9.4-21 microg/m3 glyoxal. Glyoxal was also present in the used metal-working fluid, and apparently it had been formed during grinding. The remaining 6 patients worked in miscellaneous occupations and had no present exposure to glyoxal. Glyoxal is irritant on patch testing. Especially, solitary reactions to glyoxal 10% in aq. may be false-positive irritant reactions. 9 (45%) of our patients reacted to formaldehyde or glutaraldehyde. Glyoxal is an important allergen in dentistry and medical care, and we recommend it to be added to the antimicrobial patch test series. It also seems to be a 'hidden' allergen in the metal industry.

The permeability of surgical gloves to seven chemicals commonly used in hospitals.

Disinfectants may cause adverse effects directly on the skin or systemically by permeating through the skin. In this study breakthrough times were measured for surgical gloves with chemicals which are commonly used in healthcare. Classical methods of analytical chemistry were tailored for the permeation tests, which were carried out according to the European standard EN 374 and the American standard ASTM F739. An exception to the EN 374 standard was made by using a 4 h testing time instead of 8 h. The gloves did not exhibit permeation of potassium hydroxide (45%), sodium hypochlorite (13%) or hydrogen peroxide (30%). Furthermore, neither glutaraldehyde (2%) nor chlorhexidine digluconate (4%) in the commercial disinfectant solutions studied exhibited permeation. Slight permeation of peracetic acid (0.35%) and acetic acid (4%) from a disinfectant agent was observed through single layered natural rubber materials. Clear evidence of formaldehyde permeation was detected through single layered natural rubber gloves, where the ASTM breakthrough times were 17-67 min, but the permeation rates were not high enough for breakthrough to have occurred according to the EN standard. The gloves in this study which offered most protection from chemical permeation were the chloroprene gloves and the thick double layered natural rubber gloves.

Permeation of 70% isopropyl alcohol through surgical gloves: comparison of the standard methods ASTM F739 and EN 374.

Standard test methods ASTM F739 and EN 374 were compared by assessing the permeation of 70% isopropyl alcohol (2-propanol) through seven brands of surgical gloves. The two standards differ in the flow rates of the collection medium and in the chemical permeation rate at which the breakthrough time (BTT) is detected, the EN detection level being 10 times higher than the permeation rate used by ASTM. In a departure from the EN standard method, a 4 h testing time was used instead of 8 h. All of the tested gloves were from the same manufacturer and were made from either natural rubber (NR) (six brands) or chloroprene rubber (CR) (one brand). Two of the NR glove brands were double layered. For the thin NR gloves (0.22, 0.28 and 0.27 mm) the permeation rates were higher throughout the tests with a flow rate of 474 ml/min (EN) of the collection medium (nitrogen) compared with the permeation rates obtained with a flow rate of 52 ml/min (ASTM). These resulted in BTTs of 4.6, 6.5 and 7.6 min (EN) and 4.8, 6.5 and 9.1 min (ASTM), respectively. No statistical difference could be observed between the BTT values obtained with the two standard methods for any of the thin gloves. Thus, although the ASTM standard has a lower criterion for the detection of permeation, it does not necessarily produce shorter BTTs. For the better barriers the methods yielded more equivalent permeation rate curves and thus the EN BTTs were longer than the ASTM BTTs: the EN results were 21, 80, 122 and >240 min compared with the ASTM results of 12, 32, 38 and 103 min for glove thicknesses of 0.37 (NR), 0.22 + 0.22 (double layered NR), 0.31 + 0.29 (double layered NR) and 0.19 mm (CR), respectively.