Ingrid E.
Liljelind
*a,
Annika
Hagenbjörk-Gustafsson
a and
Leif O.
Nilsson
b
aOccupational Medicine, Dept of Public Health and Clinical Medicine, Umeå University, SE-90187, Umeå, Sweden. E-mail: ingrid.liljelind@envmed.umu.se; Fax: +46 90 785 24 56; Tel: +46 90 785 24 52
bDept of Mathematical Statistics, Umeå University, S-901 87, Umeå, Sweden
First published on 19th November 2008
Methyl methacrylate (MMA) is a commonly used chemical in dental work that can cause dermatitis. Nineteen dental technicians participated in a field study in which potential dermal exposure to MMA and exposure determinants, including glove use and MMA vapour in the breathing zone, were repeatedly monitored during three consecutive days. Using patches placed on various parts of their hands we observed that the fingers and palms of the dental technicians were exposed to MMA, and their forefingers were significantly more exposed than their ring fingers; this is based on pooled data for both left and right hands (p = 0.04). The exposure variability was greater between workers than within worker (i.e. day-to-day variability), but the between worker variability was to some extent explained by a model which included the tested determinants. Neither the amount of MMA vapours in the breathing zone nor glove use was consistently correlated with the dermal exposure. Thus, the effects of glove use and the distribution of exposure to MMA on the hands in working environments needs to be further investigated.
The importance of taking valid, appropriate, dermal exposure measurements and assessing the effects of key determinants (factors, e.g. work tasks and practices, which increase or decrease the exposure) has been emphasized in recent papers.13,14 Failure to do so will inevitably reduce the value of the information obtained, and the scope for thoroughly evaluating the dermal exposure hazards. In addition, knowledge of determinants could lead to improvements in working environments by identifying risk factors related to “actual” exposure and provide objective reasons for introducing appropriate preventive measures in workplaces. Examples of working environments in which dermal determinants have been evaluated are those of farmers using pesticides and insecticides,15–17 asphalt roofing workers18 and workers in the rubber and wood pellets industries.19,20 However, we are not aware of any previous study in which dental technicians' potential dermal exposure to MMA and its determinants were simultaneously evaluated. Knowledge of exposure and simultaneous determinants would improve understanding of dermal risks and how to improve preventive measures.
The ideal strategy for measuring dermal exposure to chemicals in a given environment and the interpretation of the acquired data strongly depend on the variability of the exposure between workers and within workers (i.e. day-to-day variability), and between body locations (i.e. between different parts of an exposed individual). According to a recent review by Vermeulen et al.,13 temporal and personal variability, i.e. the proportions of the total variation in dermal exposure accounted for by within and between worker variability components, are quite similar to the corresponding proportions for respiratory exposure. However, the between-body location variance component is dermal-specific, since spillage and contact with contaminanted surfaces can be significant for exposure of a defined body part. In the study earlier referred to by Liljelind et al.,12 they selected measurement spots on the hands and lower arm, since they assumed that these skin areas would be the most contaminanted during the dental work tasks. The results showed that the hands were the main exposed skin area.
The aims of this study were to obtain measurements of potential dermal exposure to MMA on different parts of the hands of dental technicians working at several dental laboratories, to acquire estimates (from repeated measurements) of the between- and within-worker variance components of exposure and to assess the effects of possible exposure determinants.
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Fig. 1 The positions of the patches on the hand (here attached to a cotton glove with small safety pins) referred in the text as sampling sites. |
In order to assess the technicians' exposure determinants they were also asked to complete a questionnaire including questions about their use of protective gloves (always, occasionally or never), the brand of protective glove they wore (if used), MMA-work tasks and time expended on each task.
Field spikes were prepared daily by evenly spreading 2.8 mg or 5.6 mg MMA monomer (Aldrich, Germany, 99%) onto each of six patches. One field blank for each person and day was also prepared. After sampling, each patch was placed in a separate 20 ml glass bottle to which 10 ml of acetone (Burdick & Jackson, Fluka, Germany) had been added. The bottle was sealed with a screw lid equipped with a Teflon lining (CIAB, Sweden). In the analytic laboratory an internal standard (3 µl of 99.8% n-nonane, Fluka, Switzerland) was added with a calibrated pipette (Finnpipette, Thermo Labsystems, Finland) and the samples were automatically shaken for 30 min and stored at −18 °C with the patch left in the sample solution until analysis (within 10 days of the sampling). This procedure was followed at all but one of the dental laboratories, where the patches were stored in empty 20 ml glass bottle at + 8 °C for 1–4 days, and then at −18 °C at the analytical laboratory. The samples were extracted with 10 ml of acetone within ten days after sampling and treated as described above.
In a stability study12 the between-day variability obtained by repeatedly analysing three field samples was estimated to be 11–14% after 10 days and 3.5–8% after 20 days at −18 °C.
To verify the FID identification of MMA, and calibrate the FID signals, the compound was also identified in 12 field samples with high levels of MMA (above LOQ) and 8 field samples with low levels of MMA (close or below to LOQ) using a mass spectrometric system consisting of an autoinjector (Agilent 7683B Series injector) and a GC (Agilent 6890N) equipped with the same column as above coupled to a mass spectrometer (Agilent Technologies 5975 inert XL MSD) operating in full-scan mode. MMA was identified by comparing the spectra obtained to library spectra (NIST '05). One of the most abundant fragment ions of MMA, m/z 100, was used to verify and calibrate the FID signals.
ln(Xij) = Yij = µy + αi + βj + χRij + εij | (1) |
The amounts in the spiked samples seems to be reasonably relevant since 38 collected samples (14%) had MMA amounts greater than 5.6 mg and 23 (8%) had amounts between 2.8 and 5.6 mg MMA.
The concentration of MMA was below the LOQ in 36 of the blank samples and very close to or slightly above the LOQ in the other ten. Hence, adjustments were made to the amounts found in the samples to account for the blank levels. A mean blank level for each measurement day was calculated and subtracted from the samples for each day, respectively, before the statistical analysis.
Therefore, the results below are based on data obtained from 12 workers with complete measurement records from three days, four with records from two days and two from only one day, giving a total of 46 measurement days. The time estimates for different MMA work tasks were incomplete and therefore not included in subsequent statistical analysis.
The MMA contents of 276 dermal patch samples were analysed in total. Of these 18 (7%) showed MMA amounts below the LOQ but above LOD, and 20 (7%) was assigned LOD/2. These low amount samples are derived from individuals who had low exposure days and thus distributed evenly among the sample sites on the hands. Table 1 presents: the highest amount detected on any patch, the mean exposure and variance components for each sampling site (1–6); corresponding exposure levels for the left hand (summed values for sampling sites 1, 2 and 3), the right hand (summed values for sites 4, 5 and 6) and both hands; the arithmetic mean exposure at each of the dermal sites (which varied from 0.21 to 0.77 mg/cm2) and the geometric means (which were ca. 10-fold smaller than the arithmetic means); and the variance components for each sample site (1–6). The between- worker variability was two to six times higher than the within-worker variability. The variance components indicate that 66% to 85% of the total variability (σ2B + σ2W) was due to variations between workers (σ2B) rather than between days for the same worker, and this distribution was consistent across all the sampling sites (data not shown). These findings are consistent with the results of studies by Kromhout and co-workers13,24 in which a database of dermal exposure measurements (DERMDAT) was constructed from 20 surveys of workers from agricultural settings, the rubber industry, as well as coke-oven and paving workers. Further, in these cited studies13,24 the variability components and factors influencing the exposure (determinants) were estimated and the results indicated that the tested determinants influenced the between-worker variance but not the within-worker variance. Statistical analysis of our data shows that the between-worker variability could be explained (but not significantly) by the amount of MMA found on the background patches and by glove usage, which reduced the between-worker variance component of approximately 50% and 30% for left and right hand, respectively (σB2 in tables 1 and 2), while the within-worker variability was relatively unaffected by the determinants (σW2 in tables 1 and 2). The small increase of the within-worker variability in our study is possibly because of the small samples available for our statistical analysis. Furthermore, the cited authors13,24 attributed this to dermal exposure being “event-based” to a certain extent, occurring when workers touch contaminated surfaces and/or when occasional spills or splashes contaminate the workers' skin.
Site | Max exposure mg/cm2 (raw data) | Mean, arithmetic mg/cm2 (raw data) | Mean, geometric mg/cm2 (anti-logged data) | Between-worker variance component (logged data, σB2) | Within-worker variance component (logged data, σW2) |
---|---|---|---|---|---|
1 | 4.36 | 0.426 | 0.0515 | 6.79 | 2.84 |
2 | 2.03 | 0.220 | 0.0257 | 7.29 | 2.96 |
3 | 2.27 | 0.212 | 0.0328 | 4.95 | 1.96 |
4 | 6.53 | 0.661 | 0.0266 | 7.99 | 2.96 |
5 | 6.46 | 0.768 | 0.0379 | 7.43 | 3.86 |
6 | 6.68 | 0.552 | 0.0251 | 6.87 | 1.17 |
Left hand | 6.22 | 0.857 | 0.150 | 5.15 | 2.04 |
Right hand | 19.0 | 1.98 | 0.121 | 6.80 | 2.16 |
Both hands | 25.2 | 2.84 | 0.308 | 6.07 | 1.94 |
Sample site | Between-worker variance component (logged data, σ2B) | Within-worker variance component (logged data, σ2W) | Glove use estimate for 0; 1 (logged data) | Background patch estimate (logged data) |
---|---|---|---|---|
Significance of the fixed effects (gloves and background patch): * p < 0.05; ** p < 0.01. | ||||
1 | 4.13 | 3.11 | 3.36; 3.32* | 0.131 |
2 | 4.76 | 3.30 | 2.55; 2.51 | 0.414 |
3 | 2.91 | 1.84 | 1.83; 2.34 | 0.609** |
4 | 6.02 | 3.12 | 3.89; 2.98 | 0.00368 |
5 | 5.75 | 4.12 | 3.36; 2.79 | 0.00860 |
6 | 5.18 | 1.20 | 2.73; 2.39 | 0.298 |
Left hand | 2.62 | 2.26 | 2.33; 2.78* | 0.413 |
Right hand | 4.66 | 2.36 | 3.11; 2.88 | 0.196 |
Both hands | 3.69 | 2.14 | 2.64; 2.87 | 0.303 |
The background patches provide indications of the amount of MMA in the air of the work environment, but the exposure to MMA is not related to direct spills on the hand. On eleven low dermal exposure measurement-days, the amount of MMA extracted from the background patches corresponded to more than 21% of the total amount of MMA extracted from the six patches on the respective workers' pairs of gloves, while the corresponding proportions for the other measurement-days were all less than 14% (mean 2.1%, median 0.5%; data not shown). The background patch data did not improve the models for the sample sites (table 2), except for one site; left palm of the hand. At this specific site, the amount MMA found seems correlated to the background levels, which might be explained by the fact that all but one of the dental technicians were right-handed. They used their right hand to carry contaminated bottles or utensils in their hands, while the left palm of the hand was less exposed by direct contact with contaminated objects. However, the work task “kneading dough” is an exception. Overall, the amount MMA found on the background patches is not correlated to the dermal exposure. Despite the fact that MMA is a volatile substance that is likely to be absorbed by patches sampling the air surrounding a dental technician who is handling it, we could not find that association. Thus, MMA levels in the surrounding air seem not to be a predictor of dermal exposure.
The workers classified their glove use as never (three workers), occasionally (nine workers) or always (six workers) in their responses to the questionnaire. Glove use did not significantly explain the amount MMA collected on the sample sites, except for sample site 1(left forefinger) and left hand when added to the model (table 2). In the model including both of these determinants the effect of glove use is separated from the effect of background MMA, and it provides clear indications that in these two cases workers who occasionally used gloves were more heavily dermally exposed to MMA than the workers who always used gloves (p < 0.05, respectively). This shows that at one out of the six sample sites the gloves had a protective effect for the workers who always used gloves in comparison to those who used them “occasionally”. Remarkably, the estimated dermal exposure of individuals who never used gloves was only slightly higher than those of individuals who occasionally used gloves. For the left hand and both hands the estimates were even lower for the “never” group (table 2). One explanation could be the years of work tenure, i.e. work experience, which might have an impact on the exposure, but we have no information about years of experience for each worker. Further, it may also be at least partly because the former group only included three workers, a sample too small to facilitate reliable statistical analysis.
Overall, there is no convincing effect of glove use, which is not surprising since the gloves do not protect the workers from dermal MMA contamination. Several published papers have shown that MMA readily and rapidly penetrates the type of gloves the dental technicians use i.e.vinyl, nitrile and latex gloves.25–28 The breakthrough time for neat MMA is less than two minutes for all three glove types used by the technicians in our study.27 According to the responses to the questionnaire, the shortest work tasks involving handling MMA were estimated by the workers to last four minutes (data not shown). The workers also often kept the contaminated gloves on after they had finished their MMA work tasks, which extended the potential dermal exposure time.
MMA levels in one of the patches attached to the individuals' chests, representing background MMA exposure, and 36 (78%) attached to their chests within gloves, were below the LOQ. The means for these sets of patches were 0.018 mg/cm2 (max. 0.33 mg/cm2) and 0.0028 mg/cm2 (max. 0.037 mg/cm2), respectively, and we extracted quantifiable amounts of MMA from patches placed in gloves on the chest on 10 measurement-days (data not shown). Further, a poor association was found between the amounts in the background patches and the patches within gloves (r2 = 0.41). The patches in the glove may have been exposed through occasional splashes or diffusion of MMA through the glove from contaminated hands and utensils that touched the outside of the glove. Another possible explanation is that evaporated MMA may have diffused through the gloves, but this possibility has to be further investigated.
The mean exposure measurements obtained for each sample site (1–6) from the 16 dental technicians for whom measurements had been obtained on at least two days were compared using a paired t-test. No significant differences were found in the measurements between the right and left forefingers (sites 1 and 5), nor between the right and left ring fingers (sites 2 and 4). However, a significant difference was found between the summed exposure of both forefingers and the summed exposure of both ring fingers (p = 0.043). Further, there was a significant difference between the exposure measurements for the left forefinger and left ring finger (p = 0.019), but not between the corresponding right hand measurements. The ring finger can be regarded as a reference finger since it may not be used as frequently as the forefinger in the dental technicians' work tasks, although the validity of this hypothesis has to be further examined. In a previous Swedish study, dermatitis was found more frequently on the left hands than the right hands of dental personnel.29 However, we did not find a significant difference between the exposure on the technicians' left and right hands (p = 0.078) (according to measurements from all three sample sites on the two hands), and the mean exposure for all the workers was twice as high (arithmetic mean) on the right hand than the left hand (table 1). Thus, the distribution of exposure on technicians' hands, and its associations with clinical dermal symptoms warrants further investigation, especially in field studies.
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