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[Evaluation of exposure to benzene and naphthalene in coke plant workers].

Sixty two workers of a coke-chemical plant exposed to benzene, naphthalene, toluene, o-xylene, p-xylene, phenol and pyridine were examined. In urine samples collected before and after occupational exposure significant differences in concentration values of phenol (21.1-97.6 mg/l), 1--naphthol (0.1-9.38 mg/l), hippuric acid (95.5-873.9 mg/l) and m-methylhippuric acid (29.0-93.5 mg/l) were found. There was correlation between benzene and naphthalene in the breathing zone air and phenol and 1-naphthol in the urine of coke plant workers.

Air Pollutants, Occupational↗

Mortality in the coke oven plant of Carrara, Italy.

A mortality study was undertaken on a cohort of 538 male workers employed at a coke plant in Carrara in the period 1960-1985. The follow-up period ranged from January 1 1960 to December 31 1990, with 10,665 person-years accumulated. A significant excess in mortality for lung cancer was observed: 19 observed deaths vs 10.02 expected deaths using national rates, SMR 190 (C.I. 95% = 114-296), and vs 11.19 expected deaths using regional rates, SMR 170 (C.I. 95% = 102-265). The results suggest the possible influence of this occupation on mortality from lung cancer, as was observed in previous studies performed on larger cohorts of coke oven workers.

Adult↗

[Cytoenzymatic and ultramicroscopic investigations of blood in coke oven workers].

White blood cell count, cytoenzymology (acid and alkaline phosphatase, beta-glucuronidase and myeloperoxidase of granulocytes) and ultrastructure of granulocytes and NBT reduction test were performed in peripheral blood obtained from cokery plant workers. All the subjects were divided into groups according to degree of exposure to BaP. Occupational exposure to many factors during coke production, especially to high concentration of BaP cause perceptible changes of NBT reduction test in the group more exposed workers. A statistically significant of the totally activity of the acid phosphatase and beta-glucuronidase of granulocytes were found in this risk group. The changes in granulocyte function correlated with ultrastructural changes. The coking plant environment represent a strong stimulator of the neutrophil metabolism.

Adult↗

Metabolic activation of organic extracts from diesel, coke oven, roofing tar, and cigarette smoke emissions in the Ames assay.

Four environmental emissions samples were ranked by their genotoxic potency in several bioassays. Although the relative potency of a series of automotive emissions (diesel and gasoline) in the Ames assay correlated well with the relative potency in mammalian cell and mouse skin, this was not the case for the coke oven, roofing tar, and cigarette smoke condensate (CSC) emissions. This study examines the role of metabolic activation in determining the difference between a microbial and a mammalian bioassay in ranking the genotoxic potency of these environmental emissions. Uninduced and Aroclor 1254-induced S9 from both rat and hamster liver were compared as the metabolic activator in the Ames assay with Salmonella typhimurium TA98. The diesel emissions sample was direct-acting while the other samples required activation. The standard S9 concentration (only Aroclor-induced rat, approximately 1.25 mg protein/plate) also produced the maximum mutagenic activity. Induced S9s produced higher mutagenic activity than uninduced. The hamster S9 gave significantly higher mutagenic activities than rat S9 for the coke oven and CSC. The relative potency of these four samples was not significantly different between the microbial (Ames), mammalian cell (mouse lymphoma), and tumor initiation (mouse skin) assays. These results suggest that the differences observed between the relative mutagenic activity of these emissions in the mammalian cell and microbial assays was not due to a lack of optimization of the S9 system but may be inherent in the different response of the indicator cells to different chemical classes.

Animals↗

Fractal Dimensions of Coals and Cokes

Using adsorption data, we get formulas for the calculation of fractal dimensions: log[A CO2 (DP) /A N2 (BET) ] = -5.3984(2 - D 1 )/2 and log[A CO2 (BET) /A N2 (BET) ] = -4.9569(2 - D 2 )/2. The fractal dimensions (D ) of 27 coals and 2 cokes have been obtained. The D of coals decreased with the increase of fa and reached a maximum at H/C equal to 0.66 (or C daf about 86%). The fractal dimension is relative to ash and volatiles of coal: D = 2.2237 + 0.6249V daf + 0.8863A d . The relationship between D of coal coke and its conversions (X ) obeys the following equation: D = a exp(-bX ) + c .

Journal Article↗

Application of the Salmonella mutagenicity assay and determination of polycyclic aromatic hydrocarbons in workplaces exposed to petroleum pitch and petroleum coke.

Workplaces of an Italian carbon electrode factory, exposed to petroleum pitch and petroleum coke, were studied using a coupled chemical and biological approach to evaluate occupational mutagenic/carcinogenic hazards. Analytical procedures for the determination of polycyclic aromatic hydrocarbons (PAH) and Salmonella/microsome mutagenicity tests (with TA98 and TA100 strains) were performed on both industrial ingredients (pitch and coke) and airborne particulate matter of the working environment, after fractionating by sequential Soxhlet extractions with four organic solvents of increasing polarity (benzene, chloroform, methanol and acetone). The results showed: (a) the presence of extraordinarily high PAH (carcinogenic and non-carcinogenic) contents in the benzene extracts of petroleum pitch (3.6 wt% of total PAH) and of airborne particulate samples (up to 0.35 wt% of total PAH), in correlation with very high indirect (after metabolic activation) mutagenic responses of benzene extracts with strain TA98; (b) very high indirect mutagenic responses in the other extracts of the airborne particulate samples (especially with strain TA98); (c) the production during the processing at high temperatures of directly acting mutagens (without metabolic activation) which were absent in the starting materials and their release in the air of workplaces. The comparison of chemical analytical and mutagenicity data has proved to be an interesting approach for better defining the relative health hazards due to occupational exposure to potentially mutagenic/carcinogenic petroleum products.

Air Pollutants↗

The influence of cytochrome P450 1A1 and glutathione S-transferase M1 genotypes on biomarker levels in coke-oven workers.

The present study has the aim of evaluating gene-environment interaction on the levels of different biomarkers in coke-oven workers exposed to PAH. In order to assess whether the levels of some biomarkers (PAH-DNA adducts, nitro-PAH adducts to Hb and MN frequency) could be modulated by the genetic metabolic polymorphisms for CYP1A1 and GSTM1, we analysed in 76 coke-oven workers and 18 controls the CYP1A1 (MspI and Ile/Val sites) and the GSTM1 genotypes by a PCR assay. In individuals with shared setup of CYP1A1 or GSTM1 genotypes, we analysed how the specified biomarkers correlated with total PAH exposure (urinary levels of 1-hydroxypyrene) both by a stratified analysis and logistic regression modelling. Statistically significant (P = 0.03 and P = 0.01) higher percentages of the more susceptible GSTM1- subjects compared to the GSTM1+ subjects and of the more susceptible CYP1A1 Ile/Val individuals compared to the CYP1A1 Ile/Ile individuals were detected for high levels of PAH-DNA adducts in the high exposure group (namely high levels of 1-OHP). A statistically significant association was observed between increased PAH-DNA adduct levels and the more susceptible GSTM1- genotype (P.O.R. = 4.18, P = 0.03) in a logistic regression modelling and a significant interaction between PAH exposure and GSTM1-genotype was found for PAH-DNA adducts. No effect of these metabolic genotypes was observed for MN frequency and nitro-PAH adducts to Hb. In conclusion, a gene-environment interaction between PAH exposure and two metabolic genotypes involved in activation (CYP1A1) and detoxification (GSTM1) of PAHs, respectively, has been identified.

Adult↗

Liver, lung and kidney homogenates used as an activation system in mutagenicity studies of airborne particles and of expectorate and urine samples from exposed workers in a coke plant.

A comparison was made between lung and kidney homogenates on the one hand and liver S9 from rats on the other hand in order to compare their ability to activate promutagens. The Salmonella reversion assay was used on extracts of airborne particles from the top of coke oven batteries, and of expectorate and urine samples from exposed workers in the same coke plant. The contents of benzo[a]anthracene and benzo[a]pyrene in the different test solutions were measured by high-resolution gas chromatography/mass spectrometry. Both mutagens were detected in the filter extract and in the expectorates from the exposed workers but not in the expectorates from the control groups or in the urine samples. The liver S9 gave significantly higher mutagenicity than lung and kidney activation with both filter samples and expectorate and urine samples.

Adult↗

Influence of GSTM1, GSTT1, GSTP1, and EPHX gene polymorphisms on DNA adduct level and HPRT mutant frequency in coke-oven workers.

To evaluate the influence of individual susceptibility factors on the level of polyaromatic (PAH) hydrocarbon DNA adducts and hypoxanthine guanine phosphoribosyl transferase (HPRT) mutants in peripheral lymphocytes, 70 coke-oven workers exposed to PAH were genotyped for four metabolic enzyme polymorphisms of potential importance in PAH metabolism. The examined genetic polymorphisms concerned glutathione S-transferases M1 (GSTM1; gene deletion; 96 workers), T1 (GSTT1; gene deletion), P1 (GSTP1; Ile-->Val substitution at codon 104 or Ile-->Val at codon 104 and Val-->Ala at codon 113), and microsomal epoxide hydrolase (EPHX; Tyr-->His substitution at codon 113 and His-->Arg at codon 139). The workers were classified in a high- and low-exposure group on the basis of urinary concentration of 1-pyrenol. The GSTM1 null genotype increased the number of DNA adducts in smoking coke-oven workers with high PAH exposure. DNA adducts were affected by PAH-exposure in non-smokers and in GSTM1 null smokers and by smoking in GSTM1 null individuals. In a multiple linear regression analysis, the interaction of the GSTM1 genotype was statistically significant (p = 0.04) with smoking (yes/no) and of borderline significance (p = 0.06) with PAH-exposure (high/low). As smoking also increased urinary 1-pyrenol, the genotype modification seemed to concern DNA adducts due to smoking rather than occupational exposure. GSTT1 positive individuals showed an elevated level of DNA adducts in comparison with GSTT1 null subjects (p = 0.04), and EPHX genotypes associated with slow hydroxylation reaction yielded a higher (p = 0.05) HPRT mutant frequency than fast EPHX genotypes; these findings were, however, based on small numbers of subjects and need to be clarified in further studies. In conclusion, our findings indicate that homozygous deletion of GSTM1 results in an increased sensitivity to genotoxic PAHs in tobacco smoke, which is seen as an increase in aromatic DNA adducts in blood mononuclear cells.

Adult↗

The optimisation of the fast neutron and gamma-ray transmission set-up for moisture measurement of coke.

In the present paper, modelling calculations with the Monte Carlo (MCNP4C) code were performed for the optimisation of the fast neutron and gamma-ray transmission, set-up, used for the humidity measurement of coke. The optimisation focused on maximising the sensitivity of the neutron flux to humidity changes and on lowering neutron-counting error, both leading to higher accuracy of coke moisture determination. Different materials used for the source shielding and neutron collimation, together with different dimensions of the neutron collimators were studied. The results obtained from the Monte Carlo modelling correlate with the real instrument performance.

Journal Article↗

Observations of anomalous mass-loss behavior in SRM coals and cokes on drying.

The determination of moisture content in coal and coke is required for the accurate reporting of physical and chemical constituents on a dry mass basis. Interlaboratory comparisons are reported on a dry mass basis and require reproducible assessments of moisture content to minimize differences among laboratories. Comparability between laboratories is necessary to ensure equity in trade and to avoid costly disputes between buyer and seller. Moisture loss was measured as mass (M) loss as a function of time (t) at constant temperature in a dynamic inert nitrogen atmosphere on 10 SRM coals (7 bituminous and 3 subbituminous) and 4 SRM cokes. Three different patterns of mass-loss were observed-ideal (dM/dt = 0), and two anomalous behaviors, negative deviation (dM/ dt < 0) and positive deviation (dM/dt > 0). Bituminous coals with lower moisture (1-4%) and volatile content (33-38%) tend to display either ideal or positive behavior while subbituminous coals with higher moisture (12-17%) and volatile content (41-47%) display negative behavior. The identification of these different mass-loss patterns demonstrates the potential for method bias depending on the drying end-point definition (ASTM and LECO) used.

Journal Article↗

Simultaneous determination of urinary 1- and 2-naphthols, 3- and 9-phenanthrols, and 1-pyrenol in coke oven workers.

A method was developed for simultaneous quantification of urinary 1- and 2-naphthols, 3- and 9-phenanthrols and 1-pyrenol using gas chromatography with mass spectrometry (GC-MS). This method was applied to urine samples from coke oven workers (n=28) and controls (n=22) from Northern China. Geometric mean levels of urinary 1-naphthol (58.8 microg l(-1)), 2-naphthol (34.1 microg l(-1)), 3-phenanthrol (7.35 microg l(-1)), 9-phenanthrol (1.28 microg l(-1)) and 1-pyrenol (25.4 microg l(-1)) were significantly higher among coke oven workers than controls. All the substances tested were highest among top-of-oven workers, who had 15-fold higher 1-naphthol, eight-fold higher 2-naphthol and 20-fold higher 1-pyrenol levels compared with controls. Using multiple linear regression models, 72.5% of the variation in 1- and 2-naphthol and 82.8% of the variation in 1-pyrenol were explained by the concentration of naphthalene or pyrene in the urine, the work category and the smoking intensity. Cigarette consumption significantly contributed to levels of urinary 1-pyrenol and naphthols, particularly 2-naphthol. A negative relationship between work category and the ratio of naphthols/1-pyrenol was observed among smokers. Our results suggest that urinary naphthols and phenanthrols reflect polycyclic aromatic hydrocarbon (PAH) exposure as well as the widely used 1-pyrenol, and that interactions between cigarette smoking and PAH exposure result in different patterns of metabolism for individual PAHs.

Adult↗

[Effect of anaerobic acidification treatment on nitrogen removal and toxicity reduction of coke plant wastewater].

Coke plant wastewater was treated by anaerobic acidification-anoxic-aerobic (A1-A2-O) biofilm process and anoxic-aerobic (A/O) biofilm process respectively. Toxicity reduction effects of the two processes were compared. The toxicity of coke plant wastewater was equal to that of mercury chloride with concentration of 0.19 mg/L. Its toxicity reduction was related to the removal of organic nitrogen. Anaerobic acidification unit acted an important role on removal of both organic nitrogen and reduction of toxicity of the wastewater. After treatment by A1-A2-O process, its toxicity can be decreased greatly. When HRT was 37.9 hours, The relative luminosity of the treated effluent to photobacterium can attain 96.8%, that is equal to the toxicity of mercury chloride with concentration of 0.023 mg/L.

Anaerobiosis↗

[A study on the inherited susceptibility of chromosomal damage in peripheral blood lymphocytes among coke oven workers].

OBJECTIVE: To investigate the association between polymorphisms of metabolic enzyme genes and chromosomal damage risk in peripheral blood lymphocytes among coke oven workers. METHODS: One hundred and fourty-nine coke oven workers and 24 referents without occupational polycyclic aromatic hydrocarbons (PAH) exposure were recruited in this study. Urinary 1-hydroxypyrene levels were measured as the internal dose of PAH exposure. The 6 per 1 000 of micronucleus value was used as the cut-off value to determine whether the individual's chromosomal damage was positive. The genotypes of CYP1A1, GSTM1, GSTT1, GSTP1, CYP2E1, NQO1, NAT2 and mEH genes were determined by PCR-based methods. Multiple logistic regression was used to calculate the adjusted ORs and the 95% CI for the risk of chromosomal damage and to analyze the gene-gene interaction. RESULTS: In 173 subjects, after adjusting the occupational exposure, age, sex, smoking and drinking status, the subjects with GSTM1 null genotype have significantly higher risk for chromosomal damage than subjects with GSTM1 positive genotype (adjusted OR = 2.01, 95% CI = 1.03 -3.91). Compared with the wild homozygotes at P187S site of NQO1 gene, the variant homozygotes have significantly higher risk for chromosomal damage (adjusted OR = 3.18, 95% CI = 1.18 - 8.62). The subjects with variant allele at H113Y site of mEH gene have significantly lower risk for chromosomal damage (adjusted OR = 0.40, 95% CI = 0.19 - 0.88). No significant associations were found for other gene polymorphisms and chromosomal damage risk. In addition, the gene-gene interactions were also found among GSTM1, NQO1 gene P187S and mEH gene H113Y polymorphisms for the risk of chromosomal damage risk. CONCLUSION: Significant associations between genetic polymorphisms in GSTM1, NQO1 and mEH gene and risk for chromosomal damage were found among occupational PAH-exposed workers, which related to the mechanism of PAH carcinogenesis.

Adult↗

[Evaluation of respiratory function in coke plant workers. I. Analysis of absenteeism].

The analysis of sick-levels of all employees of Nowa Huta Steel-Mill, including coke plant workers was performed. Disablement for work on account of different diseases, expressed per hundred of employees, and dynamics of absence in period from 1986-1988 years was presented on a background of general national work-absenteeism due to diseases. Disablement for work in Nowa Huta Steel-Mill, particularly in the coke division was higher than in the general population. The diseases of airways had the highest contribution to the coefficient of morbidity.

Absenteeism↗

Polycyclic aromatic hydrocarbon-DNA adducts in coke-oven workers.

Different approaches for measuring occupational exposure to polycyclic aromatic hydrocarbons (PAHs) are presented, (i) determination of PAHs in the workplace by personal sampling, (ii) determination of urinary PAHs and PAH metabolites, and (iii) measurements of aromatic DNA adducts in white blood cells by ultra-sensitive enzyme radioimmunoassay (USERIA) and 32P-postlabelling. Large amounts of PAHs, including benzo[a]pyrene (BP), are released from the coke ovens. Mean PAH exposure levels were reduced by 60% when the workers used masks during work. However, low PAH concentrations were found in the urine of the exposed workers. Approximately 40% of the coke-oven workers had detectable levels of benzo[a]pyrene diol epoxide (BPDE)-DNA adducts in the white blood cells measured by USERIA and 90% had levels of aromatic adducts detectable by the 32P-postlabelling assay. In this study there was a correlation between DNA adduct levels and estimated exposure.

Air Pollutants, Occupational↗

The mortality of coke workers in Britain.

Two studies of coke workers in Britain, comprising 6,767 men, gave similar results. The proportion of lung cancer deaths was about 20% higher than in manual workers generally. The excess occurred primarily among younger men. The ratio of lung cancers to all other cancers was also higher than expected, with limited data showing no evidence of excessive tobacco consumption. Death rates from other causes were generally favorable. Overall the lung cancer death rates in oven workers were similar to those in non-oven men, but in both studies some indications of a job-specific excess were noted. These findings are compared with results from earlier studies in the United States and Canada where a much higher excess lung cancer mortality was found in oven men, particularly those with longer exposure times. We discuss possible reasons for the differences, and conclude that the results reported now contribute further evidence that exposure to coal carbonization fumes can cause lung cancer.

Adolescent↗

Morbidity in retired coke oven plant workers.

The effect of past occupational exposure on morbidity was studied in 354 coke oven workers in Lorraine Collieries (France) who retired between 1963 and 1982, and were still alive in 1988; 96% of them participated in this study. Occupational exposure to respiratory hazards during the working life was retraced for each subject. No significant association between the occupational exposure and the frequency of ischemic cardiopathies, arterial hypertension, gastro-duodenal ulcers, and respiratory symptoms was revealed. However, subjects who had worked on the Ovens, in the Workshops, and in the Byproducts showed a prevalence of arterial hypertension significantly higher than the non- or slightly exposed subjects. The healthy worker effect phenomenon, the exclusion of deceased subjects, and the small size of this retiree population may conceal possible differences between exposure groups.

Age Factors↗