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PubMed2003

Urinary excretion of 8-hydroxy-2-deoxyguanosine and 1-hydroxypyrene in coke-oven workers.

Coke-oven workers (COWs) are occupationally exposed to high concentrations of polycyclic aromatic hydrocarbons (PAH). Urinary 8-hydroxy-2-deoxyguanosine (8-OH-dG) and 1-hydroxypyrene (1-OHP) are biological markers of oxidative DNA damage and PAH metabolism, respectively. We investigated the relationship between urinary 8-OH-dG and 1-OHP in 217 Taiwanese COWs, 55 topside-oven, and 162 sideoven workers. For topside-oven workers, mean 8-OH-dG and 1-OHP concentrations (ng/ml +/- SD) were 13.8 +/- 12.0 and 93.5 +/- 104.4, respectively. These levels were significantly higher than those for sideoven workers: 10.2 +/- 7.9 ng/ml (P = 0.04) and 19.8 +/- 28.6 ng/ml (P < 0.001), respectively. Individual urinary 8-OH-dG concentrations were directly correlated with urinary 1-OHP concentrations: the higher the 1-OHP level, the higher the 8-OH-dG level (Spearman correlation coefficients: r = 0.43, P < 0.0001, n = 217). Multiple regression analysis indicated that a 10-fold increase in 1-OHP was associated with a 1.91-fold increase in 8-OH-dG. Compared to no vitamin intake, intake of at least one multiple vitamin pill per week reduced 8-OH-dG excretion (P = 0.02). Our findings suggest that urinary 1-OHP and 8-OH-dG reflect occupational PAH exposure and oxidative DNA damage in COWs. In addition, multiple vitamins may reduce oxidative stress caused by PAH exposure.

8-Hydroxy-2'-Deoxyguanosine↗
PubMed2002

Ecotoxicological monitoring of remediation in a coke oven soil.

Assessment of contaminated sites is usually based on chemical analyses of hazardous compounds in soil. This is enough either to assess the environmental hazard of contaminated soil nor to evaluate the efficiency of applied remediation techniques. Information on the bioavailability of complex mixtures of xenobiotics and degradation products cannot be provided by chemical analytical data, but results from bioassays can integrate the effects of pollutants in mixtures. In the preservation of human health and environmental quality, it is important to evaluate ecotoxicological effects of contaminated industrial soils to complement the techniques of analytical chemistry. The monitoring of a coke oven soil and the evaluation of the landfarming treatment technique, conducted on-site in a pilot scale installation, was done by a battery of ecotoxicological tests: acute, chronic, and genotoxicity tests. Contaminated soil samples revealed toxic effects for different species mainly due to high concentrations of polycyclic aromatic hydrocarbons (PAHs). After landfarming treatment, soil samples presented significant reduction in toxicity, confirming the effectiveness of the landfarming process pointed out by a significant reduction in low molecular weight PAH concentrations. Comparative analysis of the different ecotoxicological tests allowed the establishment and validation of a more suitable procedure for the monitoring of PAH contaminated soils.

Animals↗
PubMed1993

Biomonitoring of polycyclic aromatic hydrocarbons in highly exposed coke plant workers by measurement of urinary phenanthrene and pyrene metabolites (phenols and dihydrodiols).

A filter combination consisting of an impregnated glass fibre and a control filter was used for the collection of air samples in which gaseous and particulate polycyclic aromatic hydrocarbons (PAHs) were determined. To estimate the loss of lower boiling PAHs, d10-phenanthrene was applied as internal standard. A simple, well-producible method for the determination of 1-, 2-, 3-, 4- and 9-hydroxyphenanthrene, 1,2-, 3,4- and 9,10-dihydroxydihydrophenanthrene, 1-hydroxypyrene and 1,2-dihydroxy-1,2-dihydropyrene is described. By means of personal air samplers the exposure to PAHs of four coke plant employees working at different locations was measured over 4 days. Simultaneously the 24-h urine was collected and stored frozen until analysed. The main excretion product of pyrene is a 1-hydroxypyrene conjugate, whereas phenanthrene is excreted predominantly as dihydrodiol conjugate. As expected, workers on the battery topside were exposed the most and accordingly excreted by far the highest amounts of PAHs. Up to 34.0 micrograms phenanthrol conjugates (total of all isomeric phenols) and 195.5 micrograms dihydrodiol conjugates (total of all isomeric dihydrodiols) were excreted in the 24-h urine (mean of 4 days). The metabolite profiles of five isomeric phenanthrene phenols and three isomeric dihydrodiols exhibited only small percentage variations within one individual whereas significant interindividual differences were observed. These findings may indicate a genetically determined enzyme pattern responsible for the metabolic conversion of PAHs.

Air Pollutants, Occupational↗
PubMed1993

Correlation between PAH airborne concentration and PAH-DNA adducts levels in coke-oven workers.

In order to evaluate the correlation between peripheral blood leukocyte DNA adducts as an indicator of exposure to polycyclic aromatic hydrocarbons (PAH) and the airborne contamination of PAH at the work places, a survey of a cohort of coke-oven workers has been carried out. In each workplace, total and specific PAH airborne concentrations were measured. Among the job title groups, the highest proportion of subjects with levels of adducts above the detection limit and the highest mean value were observed in the door-operators. The correlation between median values of environmental benzo(a)pyrene concentration and mean values of adducts concentration support the fact that the maintenance workers group has a higher relative risk (RR) to have detectable level of PAH-adducts, which is estimated to be 1.84 for an increase of 1 micrograms/m3 of benzo(a)pyrene.

Air Pollutants, Occupational↗
PubMed1994

Determinants of urinary thioethers, D-glucaric acid and mutagenicity after exposure to polycyclic aromatic hydrocarbons assessed by air monitoring and measurement of 1-hydroxypyrene in urine: a cross-sectional study in workers of coke and graphite-electrode-producing plants.

A cross-sectional epidemiological study was performed on 286 workers from two coke oven and one graphite electrode plants. The aim was to evaluate the usefulness of monitoring 1-hydroxypyrene (1-HOP) in urine for assessing exposure to polycyclic aromatic hydrocarbons (PAHs), and that of the urinary excretion of thioethers and D-glucaric acid, and the mutagenic activity of urine as indicators or biological effects of PAHs. The results confirm that 1-HOP determination in urine probably reflects exposure to PAHs by all routes and is not significantly influenced by the smoking habit. In comparison with the total PAHs in the air and 1-hydroxypyrene in urine, taken as reference exposure parameters, the results indicate that urinary D-glucaric acid excretion is not positively influenced by PAHs exposure; thioethers determination in urine is of poor value, since the smoking habit is a strong confounding factor. The determination of urinary mutagenicity might contribute to the detection of groups of workers exposed to potentially genotoxic PAHs.

Adult↗
PubMed2006

Cloning of environmental genomic fragments as physical markers for monitoring microbial populations in coking wastewater treatment system.

The association between community functional shift and dynamics of genomic DNA composition can be used to identify functionally relevant populations as indicator organisms for systems monitoring. In this work, fingerprinting-based community DNA hybridization was used to monitor community structural dynamics and identify genomic fragments whose abundance shifts were concomitant to changes in COD removal capacity in a reactor. A laboratory-scale anaerobic-anoxic-oxic fixed biofilm system treating coking wastewater was operated with (LR mode) or without effluent recirculation (LNR mode). The contribution to total chemical oxygen demand (COD) removal by the anoxic reactor increased from 4% in LNR mode to 26% in LR mode. Long primer RAPD (randomly amplified polymorphic DNA) community fingerprints of the anoxic reactor also changed most significantly from the one similar to the anaerobic reactor to one similar to the oxic reactor. DNA hybridization revealed one signature band of 2.1 kb shared by the anoxic and oxic reactors in LR, but not LNR mode. Clone library profiling of this band resulted in one predominant 2.1-kb genomic fragment (B3) with no homologous sequences in GenBank. Real-time polymerase chain reaction indicated that copy numbers of B3 in the anoxic reactor under LR mode were 69 times higher than that under LNR mode, concomitant to a significant increase in COD removal capacity in this reactor. The different patterns of distribution of B3 in the laboratory system and a comparable malfunctioning industrial system demonstrated the potential of this genomic fragment as physical markers in systems monitoring. In addition, this genomic fragment may allow sequence-guided isolation of the host microbe.

Bacteria↗
PubMed2005

Sperm DNA damage correlates with polycyclic aromatic hydrocarbons biomarker in coke-oven workers.

OBJECTIVES: The aim was to determine whether occupational exposure to polycyclic aromatic hydrocarbons (PAHs) in men has adverse effect on semen quality. METHODS: Forty-eight coke-oven workers, including 16 topside-oven (TO) workers and 32 sideoven (SO) workers, were studied. Ambient PAHs exposure, urinary 1-hydroxypyrene (1-OHP) levels, and parameters of semen quality were determined. RESULTS: TO workers had significantly higher ambient PAHs exposure (3,436.1+/-3,411.0 vs. 1,123.1+/-1,829.3 ng/m3, P < 0.01), urinary 1-OHP levels (207.8+/-176.4 vs. 54.0+/-44.8 microg/g, P < 0.001), frequency of oligospermia (18.8 vs. 0%, P < 0.05), and morphological abnormality in sperm (32.3 vs. 14.6%, P < 0.01) than SO workers. Among cigarette smokers, TO workers had significantly higher rates of DNA denaturation in spermatozoa (alphaT) and percentage of sperm with increased DNA denaturation (COMP alphaT) levels than SO workers (246.2+/-49.5 vs. 198.1+/-30.3 for alphaT; 34.8+/-14.4 vs. 19.3+/-13.9% for COMP alphaT, P < 0.05). There was a positive correlation between urinary 1-OHP and alphaT, COMP alphaT, and abnormal sperm morphology and a tenfold increase in urinary 1-OHP associated with a 2.35-fold increase in alphaT, as well as a 1.07-fold increase in percentage of sperm with abnormal morphology. CONCLUSIONS: A potential risk of sperm dysfunction should be considered for workers occupationally exposed to high levels of PAHs. Cigarette smoking may aggravate this risk. Urinary 1-OHP can be used as a biomarker predicting sperm dysfunction.

Adult↗
PubMed1997

Urinary excretion of phenols as an indicator of occupational exposure in the coke-plant industry.

OBJECTIVE: In the present study the relationship between the level of exposure to o-cresol and of 2,4- +2,5-, 3,4-, and 3,5-xylenols and the urinary excretion of their metabolites was examined. The mixed exposure to phenolic derivatives of exposed workers during their work shift was monitored by personal air sampling of the breathing-zone air and by measurements of phenol, o-cresol, and xylenol isomer concentrations in shift-end urine. METHODS: The study subjects were 76 men working at a coke plant who were 22-58 years old and 34 nonexposed subjects. Concentrations of phenolic compounds were determined in the breathing-zone air during the work shift, whereas concentrations of phenol, cresol, and xylenol isomers were measured in urine collected after the work shift. Concentrations of phenols in air and urine were determined by gas chromatography with flame-ionization detection. Urine samples were extracted after acid hydrolysis of glucuronides and sulfates by solid-phase extraction. The gas chromatography-mass spectrometry method was applied to identify metabolites in urine samples. RESULTS: The time-weighted average concentrations of phenol, cresol, and xylenol isomers detected in breathing-zone air showed that the exposure level of the workers was relatively low. The geometric mean values were as follows: 0.26 mg/m3 for phenol, 0.09 mg/m3 for o-cresol, 0.13 mg/m3 for p- and m-cresol, and 0.02-0.04 mg/m3 for xylenols at the tar-distillation process. Corresponding urinary concentrations were 10.39, 0.53, and 0.25-0.88 mg/g creatinine for phenol, o-cresol, and xylenol isomers, respectively. The correlation coefficients between the o-cresol and 2,4-, 2,5-, 3,4-, and 3,5-xylenol concentrations measured in urine and in the breathing-zone air were statistically significant, varying in the range of 0.54-0.74 for xylenol isomers and being 0.69 for o-cresol. CONCLUSION: We have found that the presence of o-cresol and xylenol isomers in urine can be used as a biomarker for phenol exposure. Analysis performed on workers at the tar-distillation process showed that they were exposed to relatively low concentrations of phenolic compounds.

Adult↗
PubMed1995

Occupational PAH exposure: urinary 1-hydroxypyrene levels of coke oven workers, aluminium smelter pot-room workers, road pavers, and occupationally non-exposed persons in Sweden.

Polycyclic aromatic hydrocarbon (PAH) levels in air, and worker urinary 1-hydroxypyrene levels were studied in a coke oven, a Söderberg aluminium smelter pot-room, and during road-paving. Increased PAH exposure was shown to cause increased 1-hydroxypyrene excretion. Road-paving gave low PAH exposure, but resulted in a detectable elevated urinary 1-hydroxypyrene level. Background urinary 1-hydroxypyrene levels in office workers were determined, and a statistically significant difference between smokers and non-smokers was observed. It is suggested that urinary 1-hydroxypyrene can be used as biological exposure index for PAH exposure.

Air Pollutants, Occupational↗
PubMed1989

Mutagenicity of expectorate from workers in a coke plant.

Methanol extracts of hydrolyzed expectorate samples from workers in a coke plant were tested with the Salmonella reversion assay. The expectorates from exposed smokers (but also to a certain extent from exposed non-smokers) were mutagenic; however, the control samples from both smokers and non-smokers were not. The positive results produced by the expectorate samples from exposed smokers suggest a synergistic relationship between exposure to air pollution in the working atmosphere and smoking.

Air Pollutants, Occupational↗
PubMed1992

Cytogenetics study on coke oven workers with abnormal blood counts.

Thirty steelworkers with abnormal blood counts and 22 controls were studied cytogenetically. Fifty percent of the workers had a combination of leukopenia, neutropenia and lymphocytosis, and the remaining 50% showed different combinations or even a single type of alteration. The frequency of chromosome and chromatid gaps and chromosome deletions was significantly higher among workers than among controls, and the same was true for the number of individuals with some type of chromosome alteration. We also noted that the major factor related to the production of chromosome breaks is not the total time of work in the steel mill, but specifically the time of work at the coke oven.

Adult↗
PubMed1996

Cytogenetic studies in coke oven workers.

Chromosome aberrations, micronuclei, and sister chromatid exchanges (SCE) were evaluated in cultured lymphocytes of coke oven workers of an Italian steel industry plant, occupationally exposed to polycyclic aromatic hydrocarbons, and in a group of unexposed controls from a non-oven plant in the same area. No differences were found between exposed and controls for rates of total abnormal metaphases (including and excluding gaps), chromatid-type and chromosome-type aberrations, cells with 2 or more breaks, and for micronuclei. On the contrary, SCE were significantly increased in the exposed versus the controls, but, when smoking habits were considered, the increase was significant only for smokers.

Adult↗
PubMed2006

Study of the aerobic biodegradation of coke wastewater in a two and three-step activated sludge process.

A laboratory-scale biological plant composed of two aerobic reactors operating at 35 degrees C was used to study the biodegradation of coke wastewater. The main pollutants to be removed are organic matter, especially phenols, thiocyanate and ammonium nitrogen. The concentrations of the main pollutants in the wastewater during the study ranged between 922 and 1,980 mg COD/L, 133 and 293 mg phenol/L, 176 and 362 mg SCN/L and 123 and 296 mg NH(4)(+)-N/L. The biodegradation of these pollutants was studied employing different hydraulic residence times (HRT) and final effluent recycling ratios in order to minimize inhibition phenomena attributable to the high concentrations of pollutants. During the optimisation of the operating conditions, the removal of COD, phenols and thiocyanate was carried out in the first reactor and the nitrification of ammonium took place in the second. The best results were obtained when operating at an HRT of 98 h in the first reactor and 86 h in the second reactor, employing a recycling ratio of 2. The maximum removal efficiencies obtained were 90.7, 98.9, 98.6 and 99.9% for COD, phenols, thiocyanate and NH(4)(+)-N, respectively. In order to remove nitrate, an additional reactor was also implemented to carry out the denitrification process, adding methanol as an external carbon source. Very high removal efficiencies (up to 99.2%) were achieved.

Bioreactors↗
PubMed2006

Simultaneous removal of phenol, ammonium and thiocyanate from coke wastewater by aerobic biodegradation.

A laboratory-scale activated sludge plant composed of a 20 L volume aerobic reactor followed by a 12 L volume settling tank and operating at 35 degrees C was used to study the biodegradation of coke wastewater. The concentrations of ammonium nitrogen (NH(4)(+) -N), phenols, chemical oxygen demand (COD) and thiocyanate (SCN(-)) in the wastewater ranged between 504 and 2,340, 110 and 350, 807 and 3,275 and 185 and 370 mg/L, respectively. The study was undertaken with and without the addition of bicarbonate. The addition of this inorganic carbon source was necessary to favour nitrification, as the alkalinity of the wastewater was very low. Maximum removal efficiencies of 75%, 98% and 90% were obtained for COD, phenols and thyocianates, respectively, without the addition of bicarbonate. The concentration of ammonia increased in the effluent due to both the formation of NH(4)(+) as a result of SCN(-) biodegradation and to organic nitrogen oxidation. A maximum nitrification efficiency of 71% was achieved when bicarbonate was added, the removals of COD and phenols being almost similar to those obtained in the absence of nitrification. Batch experiments were performed to study the influence of pH and alkalinity on the biodegradation of phenols and thiocyanate.

Aerobiosis↗
PubMed2006

Mechanism for sludge acidification in aerobic treatment of coking wastewater.

This work was undertaken to investigate the cause of sludge acidification that led to disruption of the activated sludge process treating coking wastewater from a steel-making plant in Taiwan. An activated sludge reactor (ASR) with a working volume of 80 L was used as a model system to simulate the behavior of the real wastewater treatment process. Parameters that may cause acidification or inactivation of the sludge (NH(3), SCN(-), S(2)O(3)(2-) and CN(-)) were studied individually to examine for their effects on the performance of the ASR. The results show that high loading of NH(3), SCN(-) and CN(-) did not lead to pH decrease, while the ASR attained 85% COD removal and nearly 100% SCN degradation. In contrast, when the wastewater was supplemented with ca. 1,000 mg/L of S(2)O(3)(2-), the pH dropped to nearly 4.0 in 2 days and the COD and SCN removal yields were significantly lower (at 50 and 0-20%, respectively). Thus, overloading of S(2)O(3)(2-) was apparently a key factor causing sludge acidification. The results suggest that to ensure a normal functioning of the activated sludge, the influent S(2)O(3)(2-) concentration should be closely monitored and that the pH control of the ASR is indispensable when the S(2)O(3)(2-) loading is in excess.

Acids↗
PubMed1997

Ambient and biological monitoring of exposure to polycyclic aromatic hydrocarbons at a coking plant.

The exposure to polycyclic aromatic hydrocarbons (PAH) was measured in a Finnish coking plant over a 7-year period (1988-1994), since the beginning of production. Hygienic measurements including dust and vapour sampling were performed and the correlations between the concentrations of airborne pyrene with the levels of pyrene metabolite 1-pyrenol in urine were calculated. The profile of measured 12 or 15 PAHs was very similar between mean concentrations of personal samples, which suggests that it is possible to calculate the concentrations of total PAH by using e.g. pyrene as a marker compound. Measurements suggest that the progress of working conditions has been very favourable because the mean exposure level of shift workers to benzo[a]pyrene has decreased from 2.5 micrograms/m3 to 0.3 micrograms/m3. This points to successful measures of technical prevention. The mean concentration of 1-pyrenol in urine has been 0.2-0.6 mumol/mol creatinine. The concentration increases slightly towards the end of the working day, but the correlation urinary pyrenol and air pyrene was weak. Therefore the usefulness of pyrenol level for predicting the pyrene concentration at low exposure level in the ambient air is very limited.

Air Pollutants, Occupational↗
PubMed1999

Bioassay-directed chemical analysis and detection of mutagenicity in ambient air of the coke oven.

In the present study, we summarize the results of studies on the mutagenic potential of the main fractions and subfractions of extractable organic material (EOM) in the ambient air at the workplaces of the coke oven. The objective of our experiments was to apply the Bioassay-Directed Chemical Analysis (with the use of the Ames test) for the identification of the differences in the mutagenicity of these fractions, in relationship to the complex mixture of EOM in occupational air. From the evaluation of results, it is possible to deduce the following conclusions: (1) The comparison of the mutagenicity in the main fractions (basic, acidic, neutral) demonstrates the existence of differences in mutagenic potential. Of the total mutagenicity, 20.4% is in the basic fraction, 25.4% in the acidic fraction and 54.2% in the neutral fraction. (2) In general, 90.1% of the mutagenicity found in the basic, acidic and neutral fractions together was associated with the requirement of metabolic activation in vitro (+S9). In the case of the neutral fraction, it was 51.8%. (3) These results also suggest that frameshift mutations are the major component (53.8%) of the total mutagenicity of the main fractions. (4) With regards to the mutagenicity of organic compounds in the neutral fraction it appeared that genotoxicants of its subfractions (slightly and moderately polar and aromatic) play the main role. Carcinogenic aromatic hydrocarbons (PAH) and genotoxic nitrocompounds play an important role as determinants of the mutagenic potential of complex mixtures of harmful compounds in ambient air. This is confirmed first by the results of short-term bacterial tests.

Air Pollutants, Occupational↗
PubMed1985

Detection of benzo[a]pyrene diol epoxide-DNA adducts in peripheral blood lymphocytes and antibodies to the adducts in serum from coke oven workers.

Coke oven workers are exposed to high levels of carcinogenic polycyclic aromatic hydrocarbons, including benzo[a]pyrene (B[a]P), and are at increased risk of lung cancer. Since B[a]P is enzymatically activated to 7 beta,8 alpha-dihydroxy(9 alpha, 10 alpha)epoxy-7,8,9,10-tetrahydrobenzo[a]pyrene (B[a]PDE) that forms adducts with DNA, the presence of these adducts was measured in DNA from peripheral blood lymphocytes by synchronous fluorescence spectrophotometry and enzyme radioimmunoassay. Approximately two-thirds of the workers had detectable levels of B[a]PDE-DNA adducts. Antibodies to the DNA adducts were also found in the serum of 27% of the workers. B[a]PDE-DNA adducts were not detectable in lymphocytes and antibodies to the adducts were not detected in sera from a control group of nonsmoking laboratory workers. DNA adducts and/or antibodies to the adducts indicate exposure to B[a]P and its metabolic activation to the carcinogenic metabolite that covalently binds to and damages DNA. Detection of adducts and antibodies to them may also be useful as internal dosimeters of the pathobiological effective doses of chemical carcinogens.

7,8-Dihydro-7,8-dihydroxybenzo(a)pyrene 9,10-oxide↗