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PubMed2001

A study on carbothermal reduction of sulfur dioxide to elemental sulfur using oilsands fluid coke.

Experiments and reaction equilibrium calculations were carried out for the SO2 gas and oilsands fluid coke system. The goal was to develop a coke-based sulfur-producing flue gas desulfurization (SP-FGD) process that removes SO2 from flue gases and converts it into elemental sulfur. The conversion of SO2 to elemental sulfur proceeded efficiently at temperatures higher than 600 degrees C, and the sulfur yield reached a maximum (> 95%) at about 700 degrees C. An increase of temperature beyond 700 degrees C enhanced the reduction of product elemental sulfur, resulting in the formation of reduced sulfur species (COS and CS2), which lowered the sulfur yield at 900 degrees C to 90%. Although equilibrium calculations suggest that a lower temperature favors the conversion of SO2 as well as the yield of elemental sulfur, experiments showed no formation of elemental sulfur at 600 degrees C and below, likely due to hindered kinetics. Faster reduction of SO2 was observed at a higher temperature in the range of 700-1000 degrees C. A complete conversion of SO2 was achieved in about 8 s at 700 degrees C. Prolonging the product gas--coke contact, the yield of elemental sulfur decreased due to the formation of COS and CS2 while the SO2 conversion remained complete. Equilibrium calculations suggest that the ultimate yield of elemental sulfur maximizes at the C/SO2 ratio of 1, which represents the stoichiometry of SO2 + C-->CO2 + S. For the C/SO2 ratio < 1, equilibrium calculations predict elemental sulfur and CO2 being major products, suggesting that SO2 + C-->CO2 + S is the predominant reaction if SO2 is in excess. Experiments revealed that elemental sulfur and CO2 were only major products if the conversion of SO2 was incomplete, which is in agreement with the result of the equilibrium modeling.

Air Pollution↗
PubMed1998

Estimation of unit risk for coke oven emissions.

In 1984, based on epidemiological data on cohorts of coke oven workers, USEPA estimated a unit risk for lung cancer associated with continuous exposure from birth to 1 microgram/m3 of coke oven emissions, of 6.2 x 10(-4). This risk assessment was based on information on the cohorts available through 1966. Follow-up of these cohorts has now been extended to 1982 and, moreover, individual job histories, which were not available in 1984, have been constructed. In this study, lung cancer mortality in these cohorts of coke oven workers with extended follow-up was analyzed using standard techniques of survival analysis and a new approach based on the two stage clonal expansion model of carcinogenesis. The latter approach allows the explicit consideration of detailed patterns of exposure of each individual in the cohort. The analyses used the extended follow-up data through 1982 and the detailed job histories now available. Based on these analyses, the best estimate of unit risk is 1.5 x 10(-4) with 95% confidence interval = 1.2 x 10(-4)-1.8 x 10(-4).

Aged↗
PubMed2006

Occupational exposure to carbon/coke fibers in plants that produce green or calcined petroleum coke and potential health effects: 1. Fiber characteristics.

Carbon/coke fibers are found in bulk samples of calcined petroleum coke. Carbon/coke and other fibers, including calcium silicate, cellulose, gypsum, and iron silicate, have been found in exposure monitoring of workers who make or handle green or calcined petroleum coke. Carbon/coke fibers are not classified or regulated as carcinogens by any agency, and the available literature (summarized in this article) has not reported significant adverse health effects associated with exposure to these fibers or dusts containing these fibers. However, available epidemiological and toxicological studies have limitations that prevent a definitive assessment of carbon/coke fiber toxicity. Therefore, it is prudent to monitor and control workplace concentrations. Analyses by transmission electron microscopy (TEM) indicate that the carbon/coke fibers are amorphous, irregularly shaped, and generally rather short (94% less than 20 microm long). Nearly all carbon/ coke fibers satisfying NIOSH 7400 B counting criteria are detectable by phase-contrast optical microscopy (PCOM), which permits the use of a highly efficient sequential sampling strategy for analysis. Data are presented on the distribution of carbon/coke structure and fiber lengths and diameters. Bootstrap resampling results are presented to determine confidence intervals for structure/fiber length and diameter. Data on time-weighted average concentrations are given in a companion article, but nearly all time-weighted average carbon/coke fiber concentrations were beneath 0.1 fibers per milliliter.

Calcium Compounds↗
PubMedDate not supplied

Assessment of the effectiveness of respirator usage in coke oven workers.

This program protection factor study was conducted to evaluate the effectiveness of filter cartridge respirators while coke oven workers performed their normal work. Benzene soluble fraction (BSF) of total particulate concentrations was measured inside and outside the respirators of nine coke oven workers who worked on the top of the battery of one older coke oven plant and who reported regular use of respirators. The measurements were taken for 3 consecutive days. Excluding two undetectable measurements inside the respirator, it was found that the outside respirator BSF concentrations (25 sets) ranged from 87 to 807 microg/m3, whereas the inside respirator BSF concentrations ranged from 16 to 509 microg/m3. A program protection factor (PPF) for each set of observations was calculated as the ratio of outside to inside air BSF concentrations. The mean PPF was 2.5 with a range of 1.1 to 9.6, and 12 of the 25 measurements (48%) were below 2.0. Although the workers claimed they regularly wore their respirators, the wide range and the low PPF findings suggest that worker behavior and respirator fit may influence the level of protection provided by the respirator.

Air Pollutants, Occupational↗
PubMed1995

Occupationally related cancer risk among coke oven workers: 30 years of follow-up.

This study concerns the update of cause-specific mortality among coke oven workers. Updated information provides 3 decades of work history and vital status follow-up on 15,818 workers. Mortality patterns are summarized by race, cumulative exposure, and period of follow-up. The findings are consistent with those from earlier assessments, indicating that occupational exposure to coke oven emissions is associated with significant excess mortality from cancer of the respiratory system and of the prostate. Depending on the segment of the population considered, the respiratory cancer risk for coke oven workers ranged as high as 4.45 times that for non-oven workers. Relative risk values for cancer of the prostate ranged as high as 1.93. Rates of respiratory cancer across period of follow-up are declining, suggesting that the implementation of emissions control and occupational exposure limits has been beneficial.

Air Pollutants, Occupational↗
PubMed2004

Respiratory symptoms and lung function of coke oven workers: a lung function surveillance system from 1990-2000.

This study investigated the association of exposure to coke oven emissions with respiratory symptoms and with lung function. Data for respiratory symptoms and lung function were repeatedly collected from 764 male coke oven workers between 1990 and 2000. The data were analyzed cross-sectionally and longitudinally. Working in "Operation" increased the risk for cough (odds ratio [OR] = 2.37), phlegm (OR = 2.55), and shortness of breath (OR = 1.52). Cross-sectionally, each year of working in Operation was associated with a reduction in FEV1 of approximately 10 mL (P = 0.006) and in FVC of around 21 mL (P = 0.0001). From longitudinal analysis, each year of working in Operation was associated with an extra annual decline in FEV1 of 1.5 mL (P = 0.0012) and in FVC of around 1.8 mL (P = 0.0017). Exposure to coke oven emissions increased the risk for respiratory symptoms and adversely affected lung function.

Adult↗
PubMed2004

Lung function changes in coke oven workers during 12 years of follow up.

AIMS: To investigate the effect of exposure to coke oven emissions on the lung function of coke oven workers. METHODS: The study population, followed from 1978 and 1990, was 580 male workers with at least two sets of lung function measurements (FVC, FEV1, FEV1/FVC, and FEF25-75%). An annual rate of change (time slope) for age and height adjusted lung function index was estimated for each subject. This "time slope" was then treated as the response variable in a weighted multiple regression analysis with selected predictors. RESULTS: For all 580 subjects, each year of working in the "operation" group (the most exposed) was found to increase the FVC decline by around 0.7 ml/year (95% CI 0.1 to 1.3 ml/year). After the exclusion of 111 subjects without detailed work history, the above finding was confirmed and each year of exposure in "operation" was also found to increase the FEV1 decline by around 0.8 ml/year (95% CI 0.1 to 1.4 ml/year). CONCLUSIONS: These findings are consistent with the results of previous cross-sectional studies. Work duration in the most exposed position in the coke ovens was associated with increased annual decline for FVC and FEV1. The estimated effect of one year of work exposure in "operation" is equivalent, in terms of the reduction in lung function, to an estimated 2.1 pack-years of smoking for FVC and 1.2 pack-years of smoking for FEV1.

Adult↗
PubMed1998

Health survey of former workers in a Norwegian coke plant: Part. 1. Estimation of historical exposures.

OBJECTIVE: To estimate historical exposure levels at a coke plant for all agents considered to be of importance for epidemiological studies of mortality and cancer incidence. METHODS: Time weighted average exposure (8 h TWA) was estimated based on personal measurements for polycyclic aromatic hydrocarbons (PAHs) and carbonaceous particulates. Exposure to quartz was estimated relative to the concentration of carbonaceous particulates. These estimates were adjusted for the use of airstream helmets. Exposure to other agents were estimated qualitatively (asbestos, benzene, and arsenic) or semi-quantitatively (carbon monoxide (CO) and heat) based on measurements and other indicators of exposure. RESULTS: Exposure to PAHs was highest for those who worked at the top of the ovens (300 micrograms/m3) in the period from 1970-6. The estimated PAH exposure was reduced to an average of 65 micrograms/m3 after the introduction of exposure control measures in 1976. The estimates for carbonaceous particulates ranged from 1 to 16 mg/m3, with the highest exposure for workers at the top of the ovens and at the coke screening station. CONCLUSIONS: The exposure of greatest concern in this study is to PAHs, but exposures to carbonaceous particulates and CO may also be of importance. The major limitations of this study are the lack of personal measurements before 1975 and the total lack of measurements for some of the exposed categories of workers. Despite these limitations, we think that this assessment reflects the actual exposures for most of the former employees. The assessment thus provides a reasonable tool for the subsequent epidemiological study and for future epidemiological follow up studies at the coke plant.

Arsenic↗
PubMed2001

Urinary 1-hydroxypyrene in coke oven workers relative to exposure, alcohol consumption, and metabolic enzymes.

OBJECTIVES: To investigate the influence of personal lifestyle--such as smoking and alcohol consumption-on urinary 1-hydroxypyrene (1-OHP) concentrations in coke oven workers exposed to polycyclic aromatic hydrocarbons (PAHs) and to evaluate the association of 1-OHP concentrations with the genetic polymorphism of several metabolic enzymes including cytochrome P-450 (CYP) 1A1 and glutathione S-tranferases (GSTs). METHODS: The study population contained 162 coke oven workers and 58 controls employed at the largest iron and steel factory in China. Personal data were collected at the interview. 1-OHP in urine was measured with high performance liquid chromatography with fluorescence detection. Genetic polymorphisms were identified by the polymerase chain reaction (PCR) method. RESULTS: A positive association between excretion of urinary 1-OHP and the levels of exposure to PAHs was confirmed. Those people who consumed >or=50 g/day ethanol had significantly higher 1-OHP excretion than did other coke oven workers (p<0.01). No significant difference in urinary 1-OHP was found between smokers and non-smokers, in both controls and exposed subjects. The variant homozygotes at exon 7 of the CYP1A1 gene had significantly higher urinary 1-OHP concentrations than other CYP1A1 genotypes among the exposed workers (p=0.03). There was less association between the concentrations of 1-OHP and the GSTM1, GSTP1, or GSTT1 polymorphism. CONCLUSIONS: The present study confirmed that urinary 1-OHP is a good biomarker for exposure to PAHs. Alcohol consumption affected urinary 1-OHP excretion. The variant genotypes of the CYP1A1 gene may result in the enhancement of PAH metabolites. It is helpful to understand the role of individual susceptibility on metabolism of carcinogens. These findings suggest that the modulating effect of individual lifestyle factors or genetic nature should be considered in future studies on occupational exposure to PAHs and in evaluating the health risk from harmful chemicals.

Adult↗
PubMed2006

Association of polymorphisms in AhR, CYP1A1, GSTM1, and GSTT1 genes with levels of DNA damage in peripheral blood lymphocytes among coke-oven workers.

Accumulating evidence has shown that both DNA damage caused by the metabolites of polycyclic aromatic hydrocarbons (PAH) and genetic polymorphisms in PAH-metabolic genes contribute to individual susceptibility to PAH-induced carcinogenesis. However, the functional relevance of genetic polymorphisms in PAH-metabolic genes in exposed individuals is still unclear. In this study of 240 coke-oven workers (the exposed group) and 123 non-coke-oven workers (the control group), we genotyped for polymorphisms in the AhR, CYP1A1, GSTM1, and GSTT1 genes by PCR methods, and determined the levels of DNA damage in peripheral blood lymphocytes using the alkaline comet assay. We found that the ln-transformed Olive tail moment (Olive TM) values in the exposed group were significantly higher than those in the control group (P < 0.001). Furthermore, in the exposed group, the Olive TM values in subjects with the AhR Lys(554) variant genotype were higher than those with the AhR Arg(554)/Arg(554) genotype (P = 0.021). Similarly, the Olive TM values in the non-coke-oven workers with the CYP1A1 MspI CC + CT genotype were lower than the values of those with the CYP1A1 MspI TT genotype (P = 0.005). However, these differences were not evident for GSTM1 and GSTT1. These results suggested that the polymorphism of AhR might modulate the effects of PAHs in the exposed group; however, the underlying molecular mechanisms by which this polymorphism may have affected the levels of PAH-induced DNA damage warrant further investigation.

Adult↗
PubMed2004

Effects of occupational polycyclic aromatic hydrocarbon exposure on T-lymphocyte functions and natural killer cell activity in asphalt and coke oven workers.

Polycyclic aromatic hydrocarbons (PAHs) are environmental carcinogens exhibiting potent immunosuppressive properties. In order to determine PAH-induced immunotoxicity in humans, we investigated possible immunomodulating effects on T-lymphocyte proliferative responses and natural killer (NK) cell activities, at two different exposure levels, in asphalt and coke oven workers. We evaluated the efficiency of urinary 1-hy droxypyrene as a measure of exposure to PAHs. We found a statistically significant inhibition in T-lymphocyte proliferative responses of asphalt and coke oven workers compared to the controls. On the other hand, interestingly, we found significantly higher NK cell activities at three effector:target (E:T) ratios in the asphalt group compared to coke oven and control groups. We conclude that PAHs may cause suppression of T-lymphocyte proliferation at both exposure levels and augment NK cell activity only at low levels of exposure. Our results are in line with others reported in the literature indicating that chronic exposure to PAHs at different levels may alter some immune responses in different ways.

Adult↗
PubMed1983

Comparative carcinogenic potencies of particulates from diesel engine exhausts, coke oven emissions, roofing tar aerosols and cigarette smoke.

Mammalian cell mutagenesis, transformation and skin tumorigenesis assays show similar results in comparing the potencies of diesel, coke oven, roofing tar and cigarette smoke particulates. These assay results are reasonably consistent with the comparative carcinogenic potencies of coke oven and roofing tar emissions as determined by epidemiological studies. The bacterial mutagenesis assay tends to show disproportionately high potencies, particularly with diesel particulates. Results to date encourage the approach to the assessment for carcinogenic risks from diesel emissions based on the use of epidemiological data on cancer induced by coke oven emissions, roofing tar particulates and cigarette smoke with the comparative potencies of these materials determined by in vivo and in vitro bioassays.

Animals↗
PubMed1993

Biomarkers of carcinogen exposure and cancer risk in a coke plant.

To evaluate the association between an indicator of carcinogen exposure (peripheral blood leukocyte DNA adducts of polycyclic aromatic hydrocarbons) and an early indicator of neoplastic transformation (sputum epithelial cell membrane antigens binding by monoclonal antibodies against small cell lung cancer and against nonsmall cell lung cancer), a survey of 350 coke-oven workers and 100 unexposed workers was planned. This paper reports a pilot investigation on a subgroup of 23 coke-oven workers and 8 unexposed controls. A "gas regulator" worker with positive tumor antigen binding was identified. Results show that smokers, subjects with decreased pulmonary function (forced expiratory volume in 1 sec/forced vital capacity% < 80), and those with morphological dysplasia of sputum cells have higher levels of DNA adducts. The gas regulators showed the highest values for adducts; however, no significant difference of adduct levels was found between the coke-oven group and unexposed controls.

Adult↗
PubMed2002

Association of HSP70 and genotoxic damage in lymphocytes of workers exposed to coke-oven emission.

Heat shock proteins (Hsps) have been reported to protect cells, tissues, and organisms against damage from a wide variety of stressful stimuli. Whether they protect against deoxyribonucleic acid (DNA) damage in individuals exposed to environmental stresses and chemical carcinogens is unknown. In the study, we investigated the association between Hsp70 levels (the most abundant mammalian Hsp) and genotoxic damage in lymphocytes of workers exposed to coke-oven emission using Western dot blot and 2 DNA damage assays, the comet assay and the micronucleus test. The data show that there is a significant increase in Hsp70 levels, DNA damage score, and micronucleus rates in lymphocytes of workers exposed to coke-oven emission as compared with the control subjects. Furthermore, there was a significant negative correlation of Hsp70 levels with DNA damage scores in the comet assay (r = -0.663, P < 0.01) and with micronucleus rates (r = -0.461, P < 0.01) in the exposed group. In the control group, there was also a light negative correlation between Hsp70 with DNA damage and micronuclei rate (r = -0.236 and r = 0.242, respectively), but it did not reach a statistically significant level (P > 0.05). Our results show that individuals who had high Hsp70 levels generally showed lower genotoxic damage than others. These results suggest a role of Hsp70 in the protection of DNA from genotoxic damage induced by coke-oven emission.

Adult↗
PubMed2003

Polycyclic aromatic hydrocarbon-deoxyribonucleic acid (PAH-DNA) adduct levels and exposure to coke oven emissions among workers in Taiwan.

In this study, the authors evaluated the relationship between polycyclic aromatic hydrocarbon-deoxyribonucleic acid (PAH-DNA) adduct levels in workers' peripheral white blood cells (WBCs) and their occupational exposures to coke oven emissions (measured by air and urinary 1-hydroxypyrene [1-OHP]). Personal exposures to smoking, charbroiled food, changing clothes in the workplace, and respirator use were determined by questionnaire. Eighty-nine coke oven workers were divided into 3 exposure groups on the basis of job description: topside workers, cokeside workers, and plant office staff. Referent subjects comprised 63 individuals from the same company who worked at a site remote from the coking plant. The geometric mean (GM) PAH-DNA adduct levels determined from the WBCs of the exposed groups were 6.86, 1.56, and 0.90 adducts/10(8) nucleotides, respectively (referents = 0.38 adducts/10(8) nucleotides). GM personal benzene soluble fraction (BSF) exposures for the exposed groups were 483.2 microg/m3, 70.1 microg/m3, and 43.2 microg/m3, respectively (referents = 10.7 microg/m3). There was a significant correlation (p < 0.05) between individual BSF and PAH-DNA adduct levels for the exposed groups. The authors also found a significant correlation (p < 0.05) between urinary 1-OHP levels from the day 2 samples of the exposed groups and their PAH-DNA adduct levels. The logistic-regression model revealed that PAH-DNA adduct levels were significantly different between job categories. The results of this study indicate that BSF exposure is the primary contributor to PAH-DNA adduct levels determined from WBCs.

Adult↗
PubMed2000

Detection of benzo[a]pyrene-DNA adducts in leukocytes of coke oven workers.

Coke oven workers are often heavily exposed to polynuclear aromatic hydrocarbons (PAHs) and particularly to benzo[a]pyrene (B[a]P), which has been associated with a high incidence of cancer. B[a]P is metabolically activated to its diol-epoxide derivative, benzo[a]pyrene-trans-7,8-dihydrodiol-9,10-epoxide (BPDE-I), a potent carcinogen which binds covalently to DNA, thereby producing BPDE-I-DNA adducts. In this study, an investigation was made of the exposure of coke oven workers to PAH via the measurement of urinary 1-hydroxypyrene (1-OHP) levels, and of exposure to B[a]P by the analysis of BPDE-I-DNA adducts in leukocytes using an ELISA competitive immunoassay. 1-OHP levels measured in post-shift samples correlated with those of DNA adducts detected in leukocytes, with a mean value (140.11 fM/50 micrograms of DNA) which differed significantly from the control value (P < 0.001). It is concluded that measurement of BPDE-I-DNA adduct levels in coke plant workers is essential in determining cancer risk due to high exposure to PAHs, and in particular of B[a]P.

Air Pollutants, Occupational↗
PubMed1992

Assessment of PAH-exposure among coke oven workers.

Coke oven workers are exposed to high concentrations of polycyclic aromatic hydrocarbons. Only recently have methods been developed to try to assess the individual, biologically significant exposure. The only coke oven plant in Finland started to function in 1987, in Raahe, enabling the implementation of a cohort study among the workers to determine the usefulness of some currently available biomonitoring methods, e.g. methods of measuring PAH-DNA adducts. Urine and blood samples were taken several times from a sample of workers starting from before they worked at the plant. A questionnaire (smoking, diet, former and current occupations) was filled in by the workers at every sampling, and air samples (personal and stationary) were collected at the same time. The mean values of both benzo(a)pyrene diolepoxide (BPDE)-DNA adducts were measured by synchronous fluorescence spectrophotometry (SFS) and the antibodies to these adducts increased somewhat after the work at the plant started. However, all the adduct values were low, and no differences between the smokers and non-smokers at any time point were detected. Battery workers had slightly increased means of BPDE-DNA adducts compared to non-battery workers. Also, coke oven workers had slightly higher adduct values than age, sex and smoking matched controls.

7,8-Dihydro-7,8-dihydroxybenzo(a)pyrene 9,10-oxide↗
PubMedDate not supplied

[Granulocyte metabolism in workers at a coke-processing plant].

Acid phosphatase activity examinations and nitrotetrazolium blue reduction test after latex stimulation in peripheral blood neutrophils were performed in the group of 32 coking plant workers. Reference group consisted of 150 men not exposed to any toxic substances. Neutrophils of coking plant workers, comparing with the reference group, revealed decreased activity of acid phosphatase and impaired reduction of nitrotetrazolium blue after latex stimulation. The results suggest the possibility of toxic influence of coking plant environment on the lysosomal enzymes and oxygen-dependent metabolism of neutrophils what subsequently may diminish bactericidal powers.

Acid Phosphatase↗