Measured exposures by personal monitoring for respirable suspended particles and environmental tobacco smoke of housewives and office workers resident in Bremen, Germany

Objective : Exposures to respirable suspended particles (RSP) and environmental tobacco smoke (ETS) were assessed in Bremen, Germany, as part of a European air quality study. The range and level of personal exposures were assessed for housewives and office workers. Design : Nonsmokers were randomly selected from a representative sample of the population of Bremen. Housewives were recruited into one group primarily for assessment of exposures in the home and office workers, into a second group for assessment of the contribution of the workplace to overall exposure. Methods : A total of 190 subjects collected air samples from areas close to their breathing zone by wearing personal monitors for 24 h. Samples collected were analysed for RSP, ultraviolet-absorbing particulate matter (UVPM), fluorescing particulate matter (FPM), solanesol-related particulate matter (SolPM), nicotine and 3-ethenylpyridine (3-EP). Saliva cotinine levels for all subjects were also established. Results : Overall the levels found were quite low, with the majority of results being below the limit of quantification. Workers both living and working with smokers were exposed to the highest 24-h median quantities of RSP (789 μg) and ETS particles (128 μg) measured by FPM. The highest nicotine levels, based on median 24-h time-weighted average concentrations, were experienced by office workers working with smokers (0.69 μg m⁻³). These workers were also found to have␣the highest median cotinine levels (1.6 ng ml⁻¹). Conclusions: The most highly exposed workers, both living and working with smokers, would potentially inhale over 20 cigarette equivalents (CE) per annum as based on the upper decile levels. Housewives living with smokers could inhale up to 11 CE per annum as based on the upper decile levels. Locations outside the workplace, including the home, contribute most to overall RSP and ETS particle exposure. Consideration should be given to extending the personal monitoring period in cities where levels appear to be quite low. Received: 9 May 1997 / Accepted: 17 October 1997     

Assessment of environmental tobacco smoke and respirable suspended particle exposures for nonsmokers in Prague using personal monitoring

Objective: Exposures to respirable suspended particles (RSP) and environmental tobacco smoke (ETS) were assessed in Prague, Czech Republic, to determine the range and degree of personal exposure by means of personal monitoring over a 24-h period. Design: Self-reported nonsmokers were randomly selected from a representative sample of the population of Prague. Housewives were recruited into one group, primarily for assessment exposures in the home, and office workers were recruited into a second group for assessment of the contribution from the workplace. Methods: A total of 238 randomly selected nonsmoking subjects collected air samples near their breathing zone by wearing personal monitors for 24 h. Samples collected were analyzed for RSP, nicotine, 3-ethenylpyridine, and ETS particles (using ultraviolet absorbance, fluorescence, and solanesol measurements). Saliva cotinine analyses were also undertaken to confirm the nonsmoking status of the subjects. Results: The most highly exposed subjects in this study were office workers both living and working with smokers. Median time-weighted average exposure concentrations of 60 μg m⁻³ RSP, 16 μg m⁻³ ETS particles, and 1.6 μg m⁻³ nicotine were determined for these subjects, who also had the highest median saliva cotinine level of 2.4 ng ml⁻¹. Housewives living in nonsmoking households were the least exposed subjects in this study, showing levels of 32 μg m⁻³ RSP, 0.17 μg m⁻³ ETS particles, and 0.15 μg m⁻³ nicotine. As based upon median levels of ETS particles and nicotine, no group would potentially inhale or be exposed to more than 10 cigarette equivalents per year (CE/y) and the least exposed would inhale less than 1 CE/y. The most highly exposed (90th percentile levels) nonsmokers in this study, who both worked and lived with smokers, would potentially inhale up to 29 CE/y. Overall, the workplace was estimated to contribute between 45% and 49% of the annual exposure to nicotine and ETS particles, respectively. On the basis of determined saliva cotinine concentrations, a misclassification rate of between 1.7% and 2.5% was calculated. Conclusions: Highest exposures were apparent for office workers both working and living in smoking environments, and our findings suggest a significant contribution to overall ETS particle and nicotine levels from the workplace where smoking takes place. Overall, the rates at which subjects were determined to have misclassified their smoking status in this study were the lowest observed in any of the European cities investigated to date. Clearly, a more sensitive method of analysis for cotinine in body fluids is needed for more accurate determination of the levels expected for nonsmokers. Received: 19 November 1997 / Accepted: 26 February 1998     

Occupational exposure to polycyclic aromatic hydrocarbons in a fireproof stone producing plant: biological monitoring of 1-hydroxypyrene, 1-, 2-, 3- and 4-hydroxyphenanthrene, 3-hydroxybenz(a)anthracene and 3-hydroxybenzo(a)pyrene

Objectives: Assessment of external and internal exposure to polycyclic aromatic hydrocarbons (PAH) in a fireproof stone producing plant. Methods: Five personal and four stationary air measurements were performed to determine the concentrations of benz(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene, chrysene, dibenz(a,h)anthracene, fluoranthene, phenanthrene and pyrene, in air. To estimate internal exposure, we determined the urinary excretion of 1-hydroxypyrene, 1-, 2-, 3-, and 4-hydroxyphenanthrene, 3-hydroxybenz(a)anthracene and 3-hydroxybenzo(a)- pyrene in 19 workers, using a sensitive and reliable high-performance liquid chromatographic method with fluorescence detection. Results: During the production of fireproof stones, the German technical exposure limit (TRK) for benzo(a)pyrene of 2 μg/m³ was exceeded in two cases. The mean values of the sum of eight PAHs were 12.6 μg/m³ (stationary air measurement) and 22.2 μg/m³ (personal air measurement). Urinary 1-hydroxypyrene excretion predominated, with a median of 11.1 μg/g creatinine (creat.), followed by 3-hydroxyphenanthrene (median 2.2 μg/g creat.), 1-hydroxyphenanthrene (median 1.9 μg/g creat.) and 2-hydroxyphenanthrene (median 1.6 μg/g creat.). 4-Hydroxyphenanthrene (median 0.3 μg/g creat.) and 3-hydroxybenz(a)anthracene (median 0.17 μg/g creat.) were found in far lower concentrations, while 3-hydroxybenzo(a)pyrene was found only in very low concentrations (median 0.014 μg/g creat.). No correlations could be detected for a relationship between external and internal exposure. A significant correlation between urinary metabolite concentrations could be calculated only for 3-hydroxybenz(a)anthracene and 1-hydroxypyrene. Conclusions: In comparison with other industries, the internal PAH exposure at workplaces in a fireproof stone producing plant is high. This is probably caused by dermal PAH-absorption. Therefore, biological monitoring must be performed in the health surveillance of fireproof stone producing workers. The urinary PAH metabolites should be determined: 3-hydroxybenz(a)anthracene could probably be used as a biomarker representing the group of carcinogenic PAH. Received: 3 November 1999 / Accepted: 26 January 200     

Biomonitoring of manganese in blood, urine and axillary hair following low-dose exposure during the manufacture of dry cell batteries

Objectives: A cross-sectional study was carried out on 100 workers from three different workplace areas in a dry cell battery manufacturing plant and on 17 currently nonexposed referents, to examine the relationship between the external exposure to manganese dioxide (MnO₂) and the body burden of manganese in blood, urine and hair. Methods: Inhalable dust was measured gravimetrically after stationary active sampling. Manganese was analyzed in dust samples, blood, urine and axillary hair by atomic absorption spectro- metry. Results: The average air concentrations of manganese in the three workplace areas were 4 μg/m³ (range: 1–12 μg/m³), 40 μg/m³ (12–64 μg/m³) and 400 μg/m³ (137–794 μg/m³). Manganese in blood and axillary hair correlated with airborne manganese in group-based calculations but not on an individual level. The manganese concentrations varied between 3.2 μg/l and 25.8 μg/l in the blood (mean: 12.2 ± 4.8 μg/l) and between 0.4 μg/g and 49.6 μg/g in hair (mean: 6.2 ± 6.2 μg/g in the proximal sequence), respectively. The results for the nonexposed referents were 7.5 ± 2.7 μg/l (mean) in the blood (range: 2.6–15.1 μg/l) and 2.2 ± 1.8 μg/g (mean) in axillary hair (range: 0.4–6.2 μg/g). In these matrices, manganese differed significantly between the highly exposed workers and both the reference and the low-exposure group. Manganese in blood revealed the lowest background variance. No differences for manganese in urine were observed between workers (mean: 0.36 ± 0.42 μg/l, range: 0.1–2.2 μg/l) and referents (mean: 0.46 ± 0.47 μg/l, range: 0.1–1.7 μg/l). Conclusions: Manganese in blood is a specific and suitable parameter for the biomonitoring of MnO₂ exposure, although its validity is limited to group-based calculations. Urinary manganese failed to allow a differentiation between exposed workers and referents. The suitability of manganese analysis in hair for biomonitoring purposes suffers from a relatively great background variation as well as from analytical problems. Received: 11 December 1998 / Accepted: 17 July 1999     

Normal liver function in women in the general Japanese population subjected to environmental exposure to cadmium at various levels

Objectives: Whereas it is well established that environmental exposure to cadmium (Cd) may induce kidney dysfunction, less attention has been paid to the possible disturbance of liver function by Cd exposure. The possibility that liver function is adversely affected by current levels of environmental exposure to Cd as investigated in women in the general population in Japan, where the background level of exposure to Cd is known to be high. Methods: From 1991 to 1997, 24-h food duplicate, peripheral blood and morning spot urine samples were collected from 607 non-smoking and non-habitually drinking women (age range 19–78 years) at 30 survey sites (with no known environmental pollution from heavy metals) throughout Japan. Liver function parameters in serum were examined by conventional methods. After wet-ashing, the food duplicate, blood and urine samples were analyzed for Cd intake via food (Cd-F), Cd in blood (Cd-B), and Cd in urine (Cd-U) by inductively-coupled plasma mass spectrometry. Results: The geometric mean values for Cd-F, Cd-B, and Cd-U were 24.7 (27.1) μg/day, 1.76 (2.07) μg/l, and 3.94 (4.61) μg/g creatinine (values in parentheses for 41- to 60 year-old women), respectively. It as found that the three parameters of ALP, ALT, and AST activity were positively and significantly related to the age of the subjects (whereas no association as detected in cases of γ-GTP, LAP, and albumin). Accordingly, a further analysis as made with 367 women selected by age (41–60 years; about 60% of the total population). Essentially, no Cd dose-dependent changes in liver function parameters were observed in the selected population of this narrower age range. Conclusions: Overall, it seemed prudent to conclude that liver function as not disturbed by the current environmental exposure to Cd in Japan. Received: 16 March 1999 / Accepted: 17 July 1999     

Comparison between blood and urinary toluene as biomarkers of exposure to toluene

Objectives: To compare blood toluene (TOL-B) and urinary toluene (TOL-U) as biomarkers of occupational exposure to toluene, and to set a suitable procedure for collection and handling of specimens. Method: An assay based on headspace solid-phase microextraction (SPME) was used both for the determination of toluene urine/air partition coefficient (λ_urine/air) and for the biological monitoring of exposure to toluene in 31 workers (group A) and in 116 non-occupationally exposed subjects (group B). Environmental toluene (TOL-A) was sampled during the work shift (group A) or during the 24 h before specimen collection (group B). Blood and urine specimens were collected at the end of the shift (group A) or in the morning (group B) and toluene was measured. Results: Toluene λ_urine/air was 3.3 ± 0.9. Based on the specimen/air partition coefficient, it was calculated that the vial in which the sample is collected had to be filled up to 85% of its volume with urine and 50% with blood in order to limit the loss of toluene in the air above the specimen to less than 5%. Environmental and biological monitoring of workers showed that the median personal exposure to toluene (TOL-A) during the work-shift was 80 mg/m³, the corresponding TOL-B was 82 μg/l and TOL-U was 13 μg/l. Personal exposure to toluene in environmentally exposed subjects was 0.05 mg/m³, TOL-B was 0.36 μg/l and TOL-U was 0.20 μg/l. A significant correlation (P < 0.05) was observed between TOL-B or TOL-U and TOL-A (Pearson's r=0.782 and 0.754) in workers, but not in controls. A significant correlation was found between TOL-U and TOL-B both in workers and in controls (r=0.845 and 0.681). Conclusion: The comparative evaluation of TOL-B and TOL-U showed that they can be considered to be equivalent biomarkers as regards their capacity to distinguish workers and controls and to correlate with exposure. However, considering that TOL-U does not require an invasive specimen collection, it appears to be a more convenient tool for the biological monitoring of exposure to toluene. Received: 20 October 1999 / Accepted: 4 March 2000     

Urinary lead as a possible surrogate of blood lead among workers occupationally exposed to lead

Objectives: The aim of the present study is to investigate whether lead (Pb) in urine (Pb-U) can be a valid surrogate of lead in blood (Pb-B), the traditional biomarker of exposure to lead in occupational health. Methods: Blood and spot urine samples were collected from 258 workers of both sexes occupationally exposed to lead. The samples were analyzed for lead by graphite furnace atomic absorption spectrometry, and the correlation between Pb-B and Pb-U was examined by linear regression analysis before and after logarithmic conversion. Results: The correlation coefficient (0.824; P < 0.01) was largest when the relationship between Pb-B and Pb-U was examined with 214 cases of one sex (i.e., men) after Pb-U was corrected for a specific gravity (1.016) of urine (Pb-Usg) and both Pb-B and Pb-Usg were converted to logarithms. The geometric means (GMs) of Pb-B and Pb-Usg for the 214 men were 489 μg/l and 81 μg/l, respectively. When Pb-Usg was assumed to be 100 μg/l in this set of correlations, the 95% confidence range of Pb-B for the group mean was narrow, i.e., 543–575 μg/l (with GM of 559 μg/l), whereas that for individual Pb-B values was as wide as 355–881 μg/l. Conclusions: The correlation of Pb-U with Pb-B among workers occupationally exposed to Pb was close enough to suggest that Pb-U may be a good alternative to Pb-B on a group basis, but not close enough to allow Pb-U to predict Pb-B on an individual basis. Received: 6 April 1999 / Accepted: 17 July 1999     

Urinary N -acetyl-β-glucosaminidase as an indicator of renal dysfunction in electroplating workers

Objectives: To investigate chromium-induced renal dysfunction in electroplating workers. Methods: A cross-sectional study was used to evaluate four biochemical markers of renal function. A total of 178 workers were divided into 3 comparable groups consisting of 34 hard-chrome plating workers, 98 nickel-chrome electroplating workers, and 46 aluminum anode-oxidation workers, who represented the reference group. Ambient and biological monitoring of urinary chromium were performed to measure exposure concentrations. Results: Overall, urinary chromium concentrations were highest among hard-chrome plating workers (geometric mean 2.44 μg/g creatinine), followed by nickel-chrome electroplating workers (0.31 μg/g creatinine) and aluminum workers (0.09 μg/g creatinine). Airborne chromium concentrations were also highest in the hard-chrome plating area (geometric mean 4.20 μg/m³), followed by the nickel-chrome electroplating area (0.58 μg/m³) and the aluminum area (0.43 μg/m³). A positive correlation was found between urinary chromium and airborne concentrations (r = 0.54, P < 0.01). Urinary concentrations of N-acetyl-β-d-glucosaminidase (NAG) were also highest among hard-chrome plating workers (geometric mean 4.9 IU/g creatinine), followed by nickel-chrome workers (3.4 IU/g creatinine) and aluminum workers (2.9 IU/g creatinine). The prevalence of “elevated” NAG (>7 IU/g creatinine) was significantly highest among hard-chrome plating workers (23.5%), then among nickel-chrome workers (7.1%) and aluminum workers (8.7%). Differences in β₂-microglobulin, total protein, and microalbumin were not significant. Conclusion: The author's evidence indicates that NAG is an early indicator of renal dysfunction in hard-chrome plating workers.     

Indoor exposure to polycyclic aromatic hydrocarbons and carbon monoxide in traditional houses in Burundi

Objectives: Wood combustion is used as a major energy source in African countries and could result in indoor, pollution-related health problems. This exploratory study was undertaken to estimate polycyclic aromatic hydrocarbon (PAH) and carbon monoxide exposure in individuals living in traditional rural houses in Burundi. Methods: Standard methods were used to determine indoor air concentrations of 12 PAHs, and carbon monoxide. The urinary excretion of 1-hydroxypyrene (1-OHP) was measured in occupants of traditional houses, and compared with that of individuals living in the town of Bujumbura, the capital of Burundi. Results: Mean airborne concentration of four volatile PAHs, naphthalene, fluorene, phenanthrene and acenaphthene, exceeded 1 μg/m³, and that of benzo(a)pyrene was 0.07 μg/m³. Naphthalene was by far the main PAH contaminant, with a mean concentration (±standard deviation) of 28.7 ± 23.4 μg/m³, representing on average 60–70% of total PAH concentration. Carbon monoxide mean concentration (±standard deviation) was 42 ± 31 mg/m³, and correlated with total PAH concentration. Geometric mean urinary 1-OHP excretion (range) in people living in traditional houses was 1.50 (0.26–15.62) μmol/mol creatinine, a value which is on average 30 times higher than that of people living in the capital (0.05 (0.009–0.17) μmol/mol creatinine). Conclusions: It appears that the substantially high concentrations of the studied contaminants constitute a potential health hazard to the rural population of Burundi. Received: 15 July 1999 / Accepted: 20 November 1999     

Determination of N-nitrosodiethanolamine in urine by gas chromatography thermal energy analysis: application in workers exposed to aqueous metalworking fluids

 Objective: The aim of this study was to describe a detailed and validated methodology designed for the analysis of carcinogenic N-nitrosodiethanolamine (NDELA) down to sub-μg/l levels in urine and its application to a number of workers exposed to NDELA-contaminated aqueous metalworking fluids (MWF). Methods: Following a work-up procedure based on solid-phase extraction of NDELA, the urinary extracts were analysed without derivatization by gas chromatography on a polar wide-bore column with chemiluminescent detection using a thermal energy analyser (TEA). N-Nitroso-(2-hydroxypropyl)amine was used as an internal standard. The method was applied to 12 workers using “nitrite-free” or “nitrite-formulated” MWF and to 15 unexposed subjects. The NDELA content of the MWF was also determined using a similar, but simpler method able to easily quantify NDELA down to at least 0.1 mg/l. Results: Contamination by NDELA traces of some chemicals used for the sample preparation, particularly ethyl formate, must be carefully checked since it can give rise to false-positive results of up to 1 or 2 μg/l. The response was linear in the range of 0–500 μg/l. Between 0.5 and 10 μg/l, the recovery rate was close to 95%, while repeatability ranged from 12.5 to 6.4% (n = 5). The detection limit was 0.3 μg/l (Signal/noise = 3). No detectable NDELA could be observed in the control workers. There was no significant increase in NDELA levels at the end of shift spot samples from an exposed worker over 1 week. Higher NDELA concentrations were found in two workers (4.3 and 10.7 μg/l) exposed to “nitrite-formulated” fluids (contaminated with 65 and 18 mg NDELA per l, respectively) than in nine workers (range, 0.4–1.3 μg/l exposed to “nitrite-free” fluids with lower levels of NDELA (range, 0.5–6.6 mg/l). Conclusion: The detailed methodology described in this work and applied to a limited industrial situation was found to be suitable for monitoring NDELA in the urine of workers exposed to aqueous MWF. A much larger screening has been undertaken with the aim of obtaining better information on the real exposure of workers sometimes exposed to “nitrite-formulated” fluids that are still used. Received: 8 December 1998 / Accepted: 3 April 1999     

Urinary beryllium – a suitable tool for assessing occupational and environmental beryllium exposure?

Objectives: The reasons for the slow progress and lack of new knowledge in the biological monitoring of beryllium (Be) are to be found in the presumed small number of working activities involving exposure to the metal, and the lack of adequate analytical methods. The reference values for urinary Be reported earlier in the literature appear to be too high, due to the poor specificity and sensitivity of the adopted methods. The aim of this study was to correlate Be air concentrations and Be urinary levels to ascertain whether the biological indicator was suitable for assessing occupational exposure to the metal. Methods: To investigate the relationship between the Be concentrations in air and those excreted in urine, we examined 65 metallurgical workers exposed to very low levels of the metal, and 30 control subjects. The exposed workers were employed in two electric steel plants and two copper alloy foundries. The alloys were produced in electric furnaces, starting with scrap containing Be as an impurity. The Be concentrations in the air were monitored by area samplers and the levels of Be in the urine of the workers were determined in samples taken at the end of the shift. Both determinations were carried out by ICP-MS. Results: The median airborne Be concentrations in the copper alloy plants were 0.27 μg/m³ in the furnace area and 0.31 μg/m³ in the casting area. Median values of 0.03 to 0.12 μg/m³ were determined in the steel plants, the relatively wide range probably due to differing amounts of Be in the scrap. Regression analysis was performed on the median values from four work areas and the corresponding urinary samples. A significant correlation was found for the relationship between external and internal exposure. The urinary Be levels were in the range between 0.12 and 0.15 μg/l with observation of the recommended TLV-TWA for inhalable dust of 0.2 μg/m³ (0.2 μg/l at the upper 95th percentile). Conclusions: Sufficient data are not currently available to be able to propose a BEI for urinary Be. Our results show that new investigations are necessary to improve the evaluation of dose indicators and the relationship between external and internal exposure to Be. Received: 15 May 2000 / Accepted: 8 September 2000     

Thyroid function in lead smelter workers: absence of subacute or cumulative effects with moderate lead burdens

Objective: To evaluate the effect of low to moderate occupational lead exposure on thyroid function we conducted a cross-sectional study of 151 male lead smelter workers. Methods: Parameters of thyroid function were assessed in relation to both subacute and cumulative lead exposure over a 10-year employment period. Blood lead levels, obtained from plant surveillance records, were used to establish four ordinal levels of current and cumulative exposure (<15, 15–24, 25–39, and ≥40 μ g/dl). Results: Mean values for the lowest as compared with the highest current exposure group were similar for thyroxine (T₄: 6.8 versus 6.1 μ g/dl), estimated free thyroxine (EFT₄: 1.6 ng/dl in both groups), and thyroid-stimulating hormone (TSH: 1.8 versus 1.7 mIU/l); there was no evidence of a significant trend for diminished thyroid function associated with increasing current lead exposure. Similarly, no significant difference was observed for T₄, EFT₄, or TSH in relation to the 10-year cumulative exposure or for adjusted analyses controlling for potential confounders, including age and alcohol use. Conclusion: In contrast to studies observing thyroid dysfunction in the setting of high lead exposure and related clinical poisoning, our findings weigh against a significant physiologic effect on thyroid function at lower levels (<60 μ g/dl) of occupational lead exposure. Received: 3 August 1997 / Accepted: 8 July 1998     

Further reduction in lead exposure in women in general populations in Japan in the 1990s, and comparison with levels in east and south-east Asia

Objective: The objective of the study was to elucidate the current level of environmental lead (Pb) exposure of women in general population in Japan, where the use of organic Pb in automobile gasoline was phased out from 1973 to reach a zero level early in the 1980s. Methods: A survey was conducted in 27 sites throughout Japan from 1991 to 1997. Five hundred and eighty-eight non-smoking women from the sites offered 24-h food duplicate, peripheral blood, and spot urine samples. Pb in food duplicates (Pb-F), blood (Pb-B), and urine (Pb-U) were analyzed by inductively-coupled plasma mass spectrometry. The results of Pb-F and Pb-B were compared with observations from a study conducted from 1977 to 1981 on 339 women at the same sites. Log-normal distribution was assumed for the evaluation of the results. Results: Geometric means (GMs) of Pb-F, Pb-B, and Pb-U in the 1991–1997 study were 9.0 μg/day, 20.2 μg/l, and 2.18 μg/g creatinine, respectively. The values for Pb-F and Pb-B were substantially lower than the values (32.8 μg/day for Pb-F and 31.7 μg/l for Pb-B) obtained in the 1977–1981 study, which were already low when compared internationally. Cd-U values in the period from 1991 to 1997 also appeared to be among the lowest in the world. Analysis for time-dependent changes in Pb-U was, however, not possible at the time of this study because no values were available for the period from 1977 to 1981. Conclusions: Substantial reductions from 1977–1981 levels in environmental Pb exposure were observed among the study populations in Japan. Current exposure levels appear to be lower than those in other parts of Asia, the USA, and Europe. Received: 16 March 1999 / Accepted: 27 August 1999     

Biological monitoring of workers exposed to 4,4′-methylene-bis-(2-orthochloroaniline) (MOCA)

Objective: The objective of the study was to validate a new and simple method to determine MOCA in the urine of exposed workers. Methods: The separation, identification and quantification of urinary MOCA were performed in spiked urines by a sensitive and practical high-performance liquid chromatography (HPLC) method and applied to urine samples of 11 workers occupationally exposed to MOCA; the postshift urinary levels of MOCA in their urine samples with and without hydrolysis, “total” and “free” MOCA respectively, were determined. In addition, we investigated the use of citric or sulfamic acid as preservatives of urine samples. Results: The “total” and “free” MOCA were extracted with isooctane from hydrolysed and nonhydrolysed 20-ml urine samples respectively. After evaporation, the residue was dissolved in 4 ml of 2 · 10⁻² M aqueous hydrochloric acid and analysed by an isocratic HPLC system using both ultraviolet (UV) detection at 244 nm and electrochemical detection working in oxidation mode (0.9 V) with an Ag/AgCl reference electrode. Mobile phase (50% acetonitrile in water containing 0.4% acetate buffer solution pH = 4.6) was used to complete the 20-min analysis. “Free” and “total” MOCA were chromatographed on a reversed-phase C8 column (5 μm; 250 mm × 4 mm). The standard curve of MOCA was linear over the range 5–500 μg/l in human urine. The detection limit was 1 μg/l for a 20-μl injection volume; the repeatability ranged from 5.6 to 1.3% (n = 6) for spiked urines at 5 and 500 μg/l, with a percentage recovery of 94 ± 3%. The reproducibility of the method was 7.3% (n = 4) for spiked urine at 10 μg/l. The use of sulfamic acid as a preservative of urine samples is important to improve the precision and accuracy of the analysis. Conclusion: The results indicate that these analytical procedures using conventional apparatus may be used routinely and reliably with large numbers of urine samples for biological monitoring of the exposure to MOCA. The occupational exposure to MOCA in some factories in France is studied in the second part of this work. Received: 10 November 1998 / Accepted: 25 March 1999     

Cadmium exposure of women in general populations in Japan during 1991–1997 compared with 1977–1981

Objectives: The Japanese people are known to have high environmental exposure to cadmium (Cd). The present survey was initiated to elucidate possible changes in the intensity of Cd exposure to the population by comparison of the present exposure level with the situation some 15 years ago. Methods: During 1991–1997, 24-h food-duplicate samples, peripheral blood specimens and morning spot urine samples were collected from 588 non smoking women from 27 survey sites in six regions, where food-duplicate and blood samples had also been obtained during 1977–1981 from 399 women. The samples were wet-ashed (after homogenization in the case of food-duplicates), and Cd in the wet-ashed samples was analyzed by inductively-coupled plasma mass spectrometry for Cd intake via foods (Cd-F), Cd concentration in blood (Cd-B) and Cd concentration in urine (Cd-U). The Cd-F and Cd-B were compared with the Cd-F and Cd-B obtained at the same sites in the 1977–1981 survey. Results: The exposure levels during 1991–1997 were such that Cd-F, Cd-B and Cd-Ucr (Cd–U after correction for creatinine concentration) were 25.5 μg/day, 1.90 μg/l and 4.39 μg/g creatinine. Comparison with the 1977–1981 survey results (i.e., 37.5 μg/day for Cd-F and 3.47 μg/l for Cd-B) showed that there were significant reductions (by 32 and 45%) in both parameters respectively during the last 15 years. The dietary route was an almost exclusive (i.e., 99% of the sum of dietary and respiratory uptake) route of Cd uptake, of which Cd in rice (11.7 μg/day) contributed about 40% of the total dietary intake. When compared among survey sites, inter-site variation in dietary Cd intake was primarily due to differences in the intake through boiled rice. Despite the recent reduction in Cd exposure, the current exposure level for Japanese people is still higher than the levels among other rice-dependent populations in Asia as well as in other parts of the world. Comparison was made between the present findings in general populations and observations among known Cd-pollution cases in Japan. Conclusions: Dietary uptake is an almost exclusive route of Cd exposure in the general Japanese population. Boiled rice is a strong determinant of variation in dietary Cd intake. Whereas there was a substantial reduction in Cd exposure among Japanese populations in the last 15 years, the current level is still high when compared internationally. Received: 1 March 1999 / Accepted: 17 July 1999     

A comparison of different lead biomarkers in their associations with lead-related symptoms

Objectives: To evaluate whether dimercaptosuccinic acid (DMSA) -chelatable lead, an estimate of current bioavailable lead stores, is a better predictor of lead-related symptoms than are other commonly used lead biomarkers. Methods: A total of 95 male lead workers from three lead industries (one secondary lead smelting facility, one polyvinyl chloride-stabilizer manufacturing plant, and one lead-acid storage battery factory), and 13 workers without occupational lead exposure recruited from an occupational health institute, were studied. Blood lead, blood zinc protoporphyrin (ZPP), 4 h DMSA-chelatable lead (after oral administration of 10 mg/kg DMSA), urine lead, and urinary δ-aminolevulinic acid levels were evaluated as predictors of 15 lead-related symptoms, assessed by self-administered questionnaire, with linear and logistic regression controlling for covariates. Total symptoms and symptoms in three categories (gastrointestinal, neuromuscular, and general) were evaluated. Results: The mean (SD) 4 h DMSA-chelatable lead level was 288.7 (167.7) μg, with a range from 32.4 to 789 μg in the 95 lead workers. The mean (SD) in the non-exposed subjects was 23.7 (11.5) μg with a range from 10.5 to 43.5 μg. Blood lead, blood ZPP, and spot urine lead levels ranged from 21.4 to 78.4 μg/dl, 40 to 331 μg/l, and 7.5 to 153.0 μg/l, respectively, in the lead workers, and from 4.0 to 7.2 μg/dl, 27 to 52 μg/l, and 2.9 to 15.5 μg/l in the non-exposed controls, respectively. The overall mean symptom score (SD), derived as the sum of 0 or 1 point for absence or presence of 15 symptoms, of the lead workers was 3.7 (2.0), compared to 1.2 (1.5) for the non-exposed workers. DMSA-chelatable lead was the best predictor of symptom scores in both crude and adjusted analyses, compared with the other biomarkers. Lead workers with DMSA-chelatable lead values greater than the median (260.5 μg) were 6.2 times more likely to have frequent tingling or numbness of the arms or legs and 3.3 times more likely to have muscle pain than subjects with lower chelatable lead values. Three symptoms (tingling or numbness of arm or leg, muscle pain, and feeling irritation at the slightest disturbance) evidenced a dose-dependent relationship with DMSA-chelatable lead levels. Conclusions: DMSA-chelatable lead was found to be the best predictor of lead-related symptoms, particularly of both total symptom scores and neuromuscular symptoms, than were the other other lead biomarkers. Received: 27 January 1999 / Accepted: 29 January 2000     

Manganese exposure in foundry furnacemen and scrap recycling workers

Objectives: Cast iron products are alloyed with small quantities of manganese, and foundry furnacemen are potentially exposed to manganese during tapping and handling of smelts. Manganese is a neurotoxic substance that accumulates in the central nervous system, where it may cause a neurological disorder that bears many similarities to Parkinson's disease. The aim of the study was to investigate the sources and levels of manganese exposure in foundry furnacemen by a combined measuring of blood-manganese (B-Mn) and manganese in ambient air (air-Mn). Methods: During a period of 16 months, Air-Mn and B-Mn (denoted `exposure values') were measured involving 24 furnacemen employed in three small size foundries and 21 scrap recycling workers from one plant. In the study period, 18 furnacemen had B-Mn measured 3–4 weeks after decreasing or stopping exposure (denoted `post-exposure values'). The reference group for the B-Mn measurements consisted of 90 Danish male subjects. Results: Furnacemen who work in insufficiently ventilated smelting departments inhale, absorb, and retain significant amounts of manganese in their blood (approx. 2.5–5 μg/l above reference values) despite a generally low measured airborne level of manganese fumes (0.002–0.064 mg/m³). The `exposure values' compared with `post-exposure values' revealed a significant decrease in the B-Mn (on average 3.7 μg/l) level of the most exposed furnacemen. Two persons in our study were suspected of suffering clinically subacute manganese intoxication as both had B-Mn levels beyond the normal limit (25 and 29 μg/l, respectively). The potential problem disappeared completely after cessation of exposure, and the B-Mn levels decreased to 9.4 and 14.1 μg/l, respectively. Conclusions: Risk assessment based on combined measurements of B-Mn and air-Mn seems to be valid in the interpretation of workers' hazard. Our study indicates that B-Mn may be a valuable parameter for estimating recent exposure (within 1–2 weeks). However, more knowledge is needed about the B-Mn level and its relation to neurological symptoms. Received: 20 January 1999 / Accepted: 14 June 1999     

Carcinogenicity assays of wood dust and wood additives in rats exposed by long-term inhalation

Objective: This study evaluates whether wood dust and/or wood preservatives develop a carcinogenic potential against the tissues of the airways of rats. Methods: The formation of tumors of the respiratory tract after exposure to wood dust was studied in six groups of approximately 60 female Fischer 344 rats exposed by long-term inhalation to mean concentrations of (1) 18 mg/m³ of untreated oak wood dust, (2) wood preservatives containing ca. 1 μg/m³ lindane and 0.2 μg/m³ of pentachlorophenol (PCP) in the exposure air, or lindane and 18 μg/m3 of PCP (group lindane/PCP vapors, and group oak wood treated with lindane/PCP), (3) 21 or 39 μg/m³ of sodium dichromate (calculated as CrO₃, group chromate aerosol and group oak wood with chromate), and 72 μg/m³ of N-nitrosodimethylamine vapors as positive control. The negative control group consisted of 115 animals (sham-exposed). Results: Tumors of the nasal cavity developed in two rats exposed to chromate aerosol or in combination with wood dust (2/102, 2%). Malignant tumors of the lower respiratory tract were induced only in exposed groups of rats (three adenocarcinomas of the lung and four bronchiolar lung carcinomas, 7/254, 2.8%). More respiratory tract tumors were observed in rats exposed to chromate or wood with chromate (5/102, 5%), also in groups exposed to oak wood dust (oak untreated, oak + chromate, oak + lindane/PCP; together 5/155, 3.2%). Analysis of `unpreserved' oak wood dust revealed up to 5 μg/m³ of chromate. When this exposure was taken into account, eight of nine animals with respiratory tract tumors (including nasal cavity) had exposure to chromate, while only one tumor occurred in the group lindane/PCP. Otherwise the incidence of systemic tumors was increased in animals exposed to lindane/PCP, due in particular to a significantly increased incidence of liver tumors (OR=3.7; 1.24–11.3; P=0.019). Fatal (mucoepidermoid) tumors were induced by N-nitrosodimethylamine (NDMA) in the positive control (14/46, 30%). No such tumors of the respiratory tract were observed in the negative control. Conclusions: Tumors in the respiratory tract were found only in exposed animals, predominantly in the groups which inhaled oak wood dust and chromate stain. Chromate may play a decisive role for the etiology of tumors of the nasal cavity in wood workers. This assumption should be supported by further dose-response studies. Received: 23 May 2000 / Accepted: 13 September 2000     

Urinary nickel as bioindicator of workers' Ni exposure in a galvanizing plant in Brazil

Objectives: We measured urinary nickel (U-Ni) in ten workers (97 samples) from a galvanizing plant that uses nickel sulfate, and in ten control subjects (55 samples) to examine the association between occupational exposure to airborne Ni and Ni absorption. Methods: Samples from the exposed group were taken before and after the work shift on 5 successive workdays. At the same time airborne Ni (A-Ni) was measured using personal samplers. Ni levels in biological material and in the airborne were determined by a graphite furnace atomic absorption spectrometry validated method. In the control group the urine samples were collected twice a day, in the before and after the work shift, on 3 successive days. Results: Ni exposure low to moderate was detected in all the examined places in the plant, the airborne levels varying between 2.8 and 116.7 μg/m³ and the urine levels, from samples taken postshift, between 4.5 and 43.2 μg/g creatinine (mean 14.7 μg/g creatinine). Significant differences in U-Ni creatinine were seen between the exposed and control groups (Student's t test, P ≤ 0.01). A significant correlation between U-Ni and A-Ni (r = 0.96; P ≤ 0.001) was detected. No statistical difference was observed in U-Ni collected from exposed workers in the 5 successive days, but significant difference was observed between pre- and postshift samples. Conclusions: Urinary nickel may be used as a reliable internal dose bioindicator in biological monitoring of workers exposed to Ni sulfate in galvanizing plants regardless of the day of the workweek on which the samples are collected. Received: 28 January 1999 / Accepted: 10 July 1999     

Trends in the musk xylene concentrations in plasma samples from the general population from 1992/1993 to 1998 and the relevance of dermal uptake

Objectives: Musk xylene (MX), an environmentally important nitromusk compound, is used in different fragrances and soaps as substitute for natural musk. MX is known to occur in breast milk and plasma samples from the general population. Biological monitoring was carried out to study the change in MX concentrations in plasma from the general population over a period of about 6 years. Methods: Forty-one human plasma samples from the general population were collected and analyzed in 1998. The MX concentrations in plasma were compared with those in samples collected from the general population in 1992/1993. In order to␣study possible routes of exposure, we also analyzed perfumes (n=8), various body-care products (n=17), and detergents (n=5) in the households from the persons who were exposed in 1998. The body-care products or the detergents were used every day or at least 3–4 times per week. Results and Discussion: A remarkable decrease in MX levels was found on comparing the values from 1992/1993 and 1998. In 1998 12% (five out of 41) of the samples analyzed yielded positive results for MX (median: <0.1 μg/l, range: <0.1–0.29 μg/l), while in 1993 MX was found in 92% (66 out of 72) of the samples (median: 0.24 μg/l, range: <0.1–1.12 μg/l). The observed decrease is explained by the discontinued use of MX in detergents in Germany since 1993. As a consequence, no MX could be found in the investigated detergents in the present study. However, MX could be analyzed in at least one perfume and/or perfumed body-care product of the exposed individuals. The concentrations were in the range between 8.8 and 28.8 mg/kg in the investigated products. Because other confounding factors, e.g. diet and occupational exposure, could be excluded, the results point to the possibility that MX can be taken up through the skin. However, the small number of investigated persons limits this assumption. Received: 23 October 2000 / Accepted: 18 April 2001