The aim of this work was to establish whether workers at sawmills where chlorophenol-containing anti-stain agents had been previously used were still exposed to chlorophenols. A gas chromatographic-mass spectrometric (GC-MS) procedure for the determination of chlorophenols in urine was developed. Chlorophenols were determined from hydrolysed urine as acetylated derivatives and determined by GC-MS using selected ion monitoring (SIM). Isolation of the chlorophenols with toluene gave the best extraction efficiencies (65-119%). Stability tests at -20 degrees C showed no degradation of the chlorophenols studied during 6 months. The limit of quantification was 3.6 ng mg-1 creatinine for 2,4,6-trichlorophenol, 5.5 ng mg-1 for 2,3,4,6-tetrachlorophenol and 3.6 ng mg-1 for pentachlorophenol. Traces of 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol and pentachlorophenol were found both in previously exposed workers and in non-exposed controls, the urinary concentrations ranging from 1.1 to 15.9 ng mg-1 creatinine. The concentrations of urinary chlorophenols in previously exposed workers were of the same magnitude as those found in non-exposed controls and in the general population. The results show that it is unlikely that sawmill workers would be currently occupationally exposed to chlorophenols or polychlorinated dibenzo-p-dioxins and dibenzofurans via a contaminated work environment.

The exposure of paving workers to polycyclic aromatic hydrocarbons (PAH) during stone mastic asphalt (SMA) paving and remixing was evaluated. The effects on the workers' PAH exposure were also evaluated during the use of an industrial by-product, coal fly ash (CFA), instead of limestone as the filler in the SMA. The PAH exposure was measured by personal air sampling and by analysing the levels of urinary naphthols, phenanthrols and 1-hydroxypyrene (1-OHP) in the workers' pre- and post-shift urine samples. The respiratory PAH exposure of the paving workers (geometric mean (GM) 5.7 microg m(-3)) was about ten-fold that of the traffic controllers (GM 0.43 microg m(-3)). The levels of PAH metabolites were significantly higher (p < 0.05) in the post-shift urine samples than in the pre-shift urine samples, and the levels of metabolites in the post-shift urine of paving workers were significantly higher than in that of the controls (p < 0.01). Urinary 1-naphthol correlated well with the airborne concentrations of the two- to three-ring PAHs (r = 0.544, p = 0.003) and naphthalene (r = 0.655, p < 0.001), when non-smoking paving workers were tested. A good correlation was observed between urinary 1-OHP and the airborne concentrations of the four- to six-ring PAHs (r = 0.524, p = 0.003) as well as total PAHs (r = 0.575, p = 0.001). The concentrations of 1-OHP and phenanthrols in the urine of the pavers were significantly higher (p < 0.01) during remixing than during SMA paving. The CFA in the asphalt had no effect on the airborne PAH exposure or on the concentrations of the PAH metabolites in the paving workers' urine.

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The use of chlorophenol-containing antistain agents (e.g., Ky5, a wood preservative) ceased in Finland at the end of the 1980s, after 5 decades of use. Exposure of workers to the impurities in these agents (i.e., polychlorinated dibenzo-p-dioxins [PCDDs] and dibenzofurans [PCDFs]) was assessed at three sawmills at which personnel used a sodium chlorophenate product as an antistain agent. Given that compounds accumulate in body fat and their half-lives in humans are long, we could determine 2,3,7,8-substituted PCDDs and PCDFs 5-9 y after the last exposure occurred. We used high-resolution gas chromatography/high-resolution mass spectrometry to determine PCDDs/PCDFs in plasma from 39 Ky5-exposed workers and 18 nonexposed workers. The average total plasma concentration of PCDD/PCDF of the Ky5-exposed workers at the three sawmills were 1018, 945, and 1165 pg/g fat, and corresponding concentrations in the nonexposed workers were 743, 1124, and 844 pg/g fat, respectively. We found no significant differences in total levels between Ky5-exposed workers and nonexposed workers. However, concentrations of the 1,2,3,4,6,7,8-HpCDF isomer were significantly higher (p < .01) among the Ky5-exposed workers at all three sawmills (averages of 224, 99, and 148 pg/g fat) than among their respective nonexposed workers (averages of 43, 48, and 44 pg/g fat). These results indicate that workers had handled Ky5. When we expressed concentration levels in international toxic equivalents (I-TEQs), the mean total I-TEQ PCDD/PCDF of Ky5-exposed workers was significantly lower at one of the sawmills (average = 42 pg I-TEQ/g) than at the other two sawmills (averages of 64 and 62 pg I-TEQ/g)(p < .05). Nevertheless, total concentrations at the sawmills studied were within the range of background levels in the general population.

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